CN115490276B - Surface modified positive electrode material precursor and preparation method and application thereof - Google Patents
Surface modified positive electrode material precursor and preparation method and application thereof Download PDFInfo
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- CN115490276B CN115490276B CN202211162472.8A CN202211162472A CN115490276B CN 115490276 B CN115490276 B CN 115490276B CN 202211162472 A CN202211162472 A CN 202211162472A CN 115490276 B CN115490276 B CN 115490276B
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- 239000002243 precursor Substances 0.000 title claims abstract description 70
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 132
- 239000000243 solution Substances 0.000 claims description 117
- 239000000463 material Substances 0.000 claims description 64
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 59
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 59
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000012266 salt solution Substances 0.000 claims description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 239000011164 primary particle Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 17
- 239000008139 complexing agent Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000011163 secondary particle Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 4
- GVVNVWMBOHQMEV-UHFFFAOYSA-N n'-(1-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)C(CC)NCCN GVVNVWMBOHQMEV-UHFFFAOYSA-N 0.000 claims description 3
- LTOKKZDSYQQAHL-UHFFFAOYSA-N trimethoxy-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](OC)(OC)CCCCC1CO1 LTOKKZDSYQQAHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000002585 base Substances 0.000 description 48
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 26
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 26
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 26
- 239000002244 precipitate Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 description 13
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 13
- 235000019341 magnesium sulphate Nutrition 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 239000000347 magnesium hydroxide Substances 0.000 description 7
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 7
- 229910017069 Ni0.6Co0.2Mn0.2O Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 5
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910019440 Mg(OH) Inorganic materials 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910002801 Si–O–Mg Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- 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
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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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
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a surface modified positive electrode material precursor, a preparation method and application thereof, wherein the chemical formula of the surface modified positive electrode material precursor is as follows: ni (Ni) a Co b Mn c O·xMgO·ySiO 2 Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, a+b+c=1, and y is more than 0 and less than x and less than or equal to 0.1. The surface modified positive electrode material precursor can improve the cycle performance of the subsequent sintered positive electrode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a surface modified anode material precursor, and a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) are widely used in the fields of portable electronic products, electric vehicles, energy storage systems and the like due to the numerous advantages of high specific energy, small self-discharge, high open-circuit voltage, no memory effect, long cycle life, small environmental pollution and the like. Along with the increasing requirements of new energy automobiles on the endurance mileage, the requirements on the energy density and the cycle life of the power type lithium ion battery are also increased. The ternary material has the advantages of high specific capacity, stable cycle performance, relatively low cost, good safety performance and the like, so that the ternary material becomes a novel lithium ion battery anode material which is paid attention to at present.
At present, a ternary positive electrode material is mainly prepared by a coprecipitation method, namely a hydroxide precursor is prepared by taking nickel salt, cobalt salt and manganese salt as raw materials, and a spherical nickel cobalt manganese hydroxide precursor is obtained by controlling reaction conditions and reaction rates in an alkaline environment, wherein the proportion of nickel, cobalt and manganese can be adjusted according to actual needs. And then mixing the precursor with lithium salt and sintering to obtain the ternary material.
However, the application of the ternary material has more problems and challenges, especially the problems of structural phase change at the interface with the electrolyte, dissolution of transition metal, oxygen precipitation, continuous oxidative decomposition of the electrolyte and the like, which results in poor cycle performance of the ternary material.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the surface modified positive electrode material precursor, and the preparation method and application thereof, so that the precursor can be coated directionally after the positive electrode material precursor is doped, and the cycle performance of the subsequent sintered positive electrode material is improved.
The technical aim of the invention is realized by the following technical scheme:
a surface-modified positive electrode material precursor having the formula: ni (Ni) a Co b Mn c O·xMgO·ySiO 2 Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, a+b+c=1, and y is more than 0 and less than x and less than or equal to 0.1.
Preferably, the surface-modified positive electrode material precursor is a secondary particle formed by agglomeration of primary particles, wherein the particle size of the primary particles is 0.01-1.0 μm, and the particle size of the agglomerated secondary particles is 1.0-15.0 μm.
Preferably, the silicon element in the surface-modified cathode material precursor is present only on the surface of the primary particles.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
(1) Mixing nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent, a soluble magnesium salt solution and alkaline base solution for reaction to obtain mixed solution;
(2) Carrying out solid-liquid separation on the mixed liquid obtained in the step (1), washing the separated solid, and drying to obtain a dried material;
(3) And (3) mixing the dried material obtained in the step (2) with an aqueous solution of a silane coupling agent, drying, and calcining under an oxygen atmosphere to obtain the surface modified positive electrode material precursor.
Preferably, in the step (1), the molar ratio of the nickel element, the cobalt element and the manganese element in the nickel-cobalt-manganese mixed salt solution is a:b:c.
Preferably, in the step (1), the total concentration of nickel cobalt manganese ions in the nickel cobalt manganese mixed salt solution is 0.5-3.0mol/L.
Further preferably, in the step (1), the total concentration of nickel cobalt manganese ions in the nickel cobalt manganese mixed salt solution is 1.0-2.5mol/L.
Preferably, in the step (1), the precipitant is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the precipitant is 3.0-10.0mol/L.
Further preferably, the concentration of the precipitant is 4.0 to 8.0mol/L.
Preferably, in the step (1), the complexing agent is ammonia water with the concentration of 5.0-15.0 mol/L.
Further preferably, in the step (1), the complexing agent is ammonia water with a concentration of 6.0-12.0 mol/L.
Preferably, in step (1), the soluble magnesium salt solution is at least one of a magnesium sulfate solution, a magnesium chloride solution and a magnesium nitrate solution.
Preferably, in step (1), the concentration of the soluble magnesium salt solution is 0.5-3.0mol/L.
Further preferably, in step (1), the concentration of the soluble magnesium salt solution is 1.0 to 2.5mol/L.
Preferably, in the step (1), the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH of the alkaline base solution is 9.0-11.0, and the concentration of the ammonia water in the alkaline base solution is 1.0-12.0g/L.
Further preferably, in the step (1), the pH of the alkaline base solution is 10.0-11.0, and the concentration of ammonia water in the alkaline base solution is 2.0-10.0g/L.
Preferably, in the step (1), the mixing mode is that the nickel cobalt manganese mixed salt solution, the precipitator, the complexing agent and the soluble magnesium salt solution are added into the alkaline base solution in parallel, the flow rate of the soluble magnesium salt is controlled to be 0.01-1 time of the flow rate of the nickel cobalt manganese mixed salt solution in the adding process, the ratio of the adding amount of final magnesium ions to nickel cobalt manganese ions is controlled to be Mg: ni: co: mn=x: a: b: c, the pH value of the mixed solution is controlled to be 9.0-11.0, and the concentration of ammonia water is controlled to be 1.0-12.0g/L.
Further preferably, the pH of the mixture is controlled to be 10.0-11.0, and the concentration of ammonia water is controlled to be 2.0-10.0g/L.
Preferably, in step (1), the temperature of the reaction is 40-70 ℃.
Further preferably, in step (1), the temperature of the reaction is 45-65 ℃.
Preferably, in step (1), the feeding is stopped when it is detected that the particle size of the material in the mixed liquor reaches 1.0-15.0 μm.
Preferably, in the step (2), the washing mode is that alkali liquor is used for washing, and then water is used for washing.
Preferably, the alkali liquor is at least one of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the alkali liquor is 0.5-2.5mol/L.
Further preferably, the concentration of the alkali liquor is 1-2.0mol/L.
Preferably, in the step (2), the drying temperature is 220-280 ℃ and the drying time is 1-2h.
Preferably, in the step (3), the mass concentration of the aqueous solution of the silane coupling agent is 0.5% -2.5%.
Further preferably, in the step (3), the mass concentration of the aqueous solution of the silane coupling agent is 0.5% -2%.
Preferably, in the step (3), the silane coupling agent in the aqueous solution of the silane coupling agent is at least one of N- (β -aminoethyl) - α -aminopropyl trimethoxysilane, 3-glycidyl propyl trimethoxysilane, vinyl tris (β -methoxyethoxy) silane, vinyl triethoxysilane and vinyl trimethoxysilane.
Preferably, in the step (3), the solid-to-liquid ratio g/mL of the dry material to the aqueous solution of the silane coupling agent is 1: (1-5).
Further preferably, in the step (3), the solid-to-liquid ratio g/mL of the dry material to the aqueous solution of the silane coupling agent is 1: (1-3).
Preferably, in the step (3), the drying temperature is 100-120 ℃ and the drying time is 2-3h.
Preferably, in the step (3), the calcination temperature is 500-800 ℃ and the calcination time is 0.5-1h.
Preferably, a method for preparing a surface-modified positive electrode material precursor includes the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 1.0-2.5mol/L according to the element mole ratio of Ni to Co to Mn=a to b to c, wherein the soluble salts of nickel, cobalt and manganese are selected as raw materials;
step 2, preparing sodium hydroxide solution with the concentration of 4.0-8.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 6.0-12.0mol/L as a complexing agent;
step 4, preparing a magnesium sulfate/magnesium chloride/magnesium nitrate solution with the concentration of 1.0-2.5 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.0-11.0, and the concentration of the ammonia water is 2.0-10.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium sulfate/magnesium chloride/magnesium nitrate solution prepared in the step 4 are added into a reaction kettle in parallel to react, the reaction temperature in the kettle is controlled to be 45-65 ℃, the pH value is controlled to be 10.0-11.0, and the concentration of the ammonia water is controlled to be 2.0-10.0g/L; the flow rate of the magnesium sulfate/magnesium chloride/magnesium nitrate solution is 0.01-1 times of the flow rate of the mixed salt solution, and the ratio of the adding amount of the final magnesium ions to the nickel cobalt manganese ions is controlled to be Mg, ni, co, mn=x, a, b and c along with the progress of the reaction;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 1.0-15.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1-2.0mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 220-280 ℃ for 1-2 hours to obtain a dried material;
step 10, preparing an aqueous solution of a silane coupling agent with the mass concentration of 0.5% -2%, wherein the silane coupling agent is not limited to one or more of N- (beta-aminoethyl) -alpha-aminopropyl trimethoxy silane, 3-glycidyl propyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl triethoxy silane and vinyl trimethoxy silane;
step 11, mixing the dried material with an aqueous solution of a silane coupling agent according to a solid-to-liquid ratio of 1g to 1-3mL, and drying at 100-120 ℃ for 2-3h to obtain a pretreated dried material;
and step 12, calcining the pretreated dry material for 0.5-1h in the air or oxygen atmosphere at the temperature of 500-800 ℃ to obtain the surface modified positive electrode material precursor.
The application of the surface modified positive electrode material precursor in preparing lithium ion battery.
The beneficial effects of the invention are as follows:
(1) The surface modified positive electrode material precursor prepared by the preparation method has excellent cycle performance after being prepared into the positive electrode material, and the cycle retention rate can reach more than 90.94% after 300 times of cycles.
(2) The preparation method of the surface modified cathode material precursor comprises the steps of firstly adopting nickel cobalt manganese mixed salt solution, a precipitator, soluble magnesium salt and alkaline base solution to carry out coprecipitation reaction under the complexing of a complexing agent to generate magnesium doped nickel cobalt manganese hydroxide, drying at low temperature (220-280 ℃) to enable the nickel cobalt manganese hydroxide in the nickel cobalt manganese hydroxide to be dehydrated and decomposed into oxides, and enabling the magnesium hydroxide to still exist in the form of hydroxide at the temperature to form magnesium hydroxide doped nickel cobalt manganese oxide, reacting the magnesium hydroxide doped nickel cobalt manganese oxide with hydroxide on the surface of a drying material through directional modification of a silane coupling agent, selectively modifying the magnesium hydroxide to generate Mg-O-Si-R, keeping the nickel cobalt manganese oxide unchanged, and finally further calcining to remove organic chains remained by the silane coupling agent to form the magnesium silicate type surface coating. The reaction principle is as follows:
coprecipitation reaction:
aNi 2+ +bCo 2+ +cMn 2+ +2OH - →Ni a Co b Mn c (OH) 2
Mg 2+ +2OH - →Mg(OH) 2
drying and dehydrating:
Ni a Co b Mn c (OH) 2 →Ni a Co b Mn c O
surface modification of a silane coupling agent:
R 1 -Si(OR 2 ) 3 +3H 2 O→R 1 -Si(OH) 3 +3R 2 -OH
R 1 -Si(OH) 3 +Mg(OH) 2 →R 1 -Si-O-Mg+H 2 O。
(3) According to the preparation method of the surface modified cathode material precursor, the silane coupling agent is selectively used for modifying the magnesium hydroxide on the surface of the dried material, and the magnesium hydroxide is calcined to remove the organic chain to form the coating layer in the form of magnesium silicate, so that the interface stability of the material can be further improved, the silane coupling agent does not react with nickel cobalt manganese oxide, and the problem that the nickel cobalt lithium manganate is difficult to form in subsequent sintering due to the formation of nickel cobalt manganese silicate is avoided.
(4) According to the preparation method of the surface modified cathode material precursor, the characteristic that other hydroxides are difficult to decompose is utilized, nickel cobalt manganese hydroxide is selectively dehydrated to generate nickel cobalt manganese oxide, magnesium hydroxide is singly reacted with a silane coupling agent to form a silicon magnesium coating layer, magnesium is doped on the surface layer of particles, after the magnesium is combined with silicon, the formed coating layer is extremely stable and is difficult to fall off, and the cycle performance of the material can be further improved when the cathode material is sintered later.
Drawings
FIG. 1 is an SEM image at 10000 times of a surface-modified positive electrode material precursor prepared in example 1 of the present invention;
fig. 2 is an SEM image of a surface-modified cathode material precursor 50000 x prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1:
a surface modified positive electrode material precursor has a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO·0.01SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 6.0 mu m; elemental silicon is present only on the primary particle surface and SEM images of the surface modified positive electrode material precursor are shown in fig. 1 and 2.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 2.0mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.6:0.2:0.2;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 4, preparing a magnesium sulfate solution with the concentration of 2.0 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.8, and the concentration of the ammonia water is 8.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium sulfate solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 58 ℃, the pH is controlled to be 10.8, and the concentration of the ammonia water is 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 6.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1.5mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 280 ℃ for 1h to obtain a dried material;
step 10, preparing an aqueous solution of vinyl trimethoxy silane with the mass concentration of 1%;
step 11, mixing the dried material with an aqueous solution of vinyltrimethoxysilane according to a solid-to-liquid ratio of 1g to 2mL, and drying at 110 ℃ for 2.5h to obtain a pretreated dried material;
and step 12, calcining the pretreated dry material for 1h in an oxygen atmosphere at the temperature of 650 ℃ to obtain the surface modified positive electrode material precursor.
Example 2:
a surface modified positive electrode material precursor has a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO·0.025SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 10.0 mu m; elemental silicon is present only on the primary particle surface.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 2.5mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.6:0.2:0.2;
step 2, preparing sodium hydroxide solution with the concentration of 8.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 4, preparing a magnesium chloride solution with the concentration of 2.5 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.2, and the concentration of the ammonia water is 4.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium chloride solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 55 ℃, the pH is controlled to be 10.2, and the concentration of the ammonia water is 4.0g/L; the flow rate of the magnesium chloride solution is 0.1 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 10.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 2.0mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 220 ℃ for 2 hours to obtain a dried material;
step 10, preparing an aqueous solution of vinyl triethoxysilane with the mass concentration of 2%;
step 11, mixing the dried material with an aqueous solution of vinyltriethoxysilane according to a solid-to-liquid ratio of 1g to 3mL, and drying for 2 hours at 120 ℃ to obtain a pretreated dried material;
and step 12, calcining the pretreated dry material for 0.5h in an oxygen atmosphere at 800 ℃ to obtain the surface modified positive electrode material precursor.
Example 3:
a surface modified positive electrode material precursor has a chemical general formula of Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO·0.0136SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 3.5 mu m; elemental silicon is present only on the primary particle surface.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 1.0mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.8:0.1:0.1;
step 2, preparing sodium hydroxide solution with the concentration of 4.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 4, preparing a magnesium nitrate solution with the concentration of 1.0 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 11.0, and the concentration of the ammonia water is 10.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium nitrate solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 48 ℃, the pH value is controlled to be 11.0, and the concentration of the ammonia water is controlled to be 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 3.5 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 250 ℃ for 1.5 hours to obtain a dried material;
step 10, preparing an aqueous solution of vinyl tri (beta-methoxyethoxy) silane with the mass concentration of 0.5%;
step 11, mixing the dried material with an aqueous solution of vinyl tri (beta-methoxyethoxy) silane according to a solid-to-liquid ratio of 1g to 1mL, and drying at 100 ℃ for 3 hours to obtain a pretreated dried material;
and step 12, calcining the pretreated dry material for 1h in an air atmosphere at the temperature of 500 ℃ to obtain the surface modified positive electrode material precursor.
Comparative example 1: (in comparison with example 1, the precipitate was not dried and was directly treated with an aqueous solution of a silane coupling agent)
A surface modified positive electrode material precursor has a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO·0.0128SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 6.0 mu m; elemental silicon is present only on the primary particle surface.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 2.0mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.6:0.2:0.2;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 4, preparing a magnesium sulfate solution with the concentration of 2.0 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.8, and the concentration of the ammonia water is 8.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium sulfate solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 58 ℃, the pH is controlled to be 10.8, and the concentration of the ammonia water is 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 6.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1.5mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, preparing an aqueous solution of vinyl trimethoxy silane with the mass concentration of 1%;
step 10, mixing the precipitate with an aqueous solution of vinyltrimethoxysilane according to a solid-to-liquid ratio of 1g to 2mL, and drying at 110 ℃ for 2.5h to obtain a pretreated dry material;
and 11, calcining the pretreated dry material for 1h in an oxygen atmosphere at the temperature of 650 ℃ to obtain the surface modified positive electrode material precursor.
Comparative example 2: (in comparison with example 2, the precipitate was not dried and was directly treated with an aqueous solution of a silane coupling agent)
A surface modified positive electrode material precursor has a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO·0.0308SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 10.0 mu m; elemental silicon is present only on the primary particle surface.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 2.5mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.6:0.2:0.2;
step 2, preparing sodium hydroxide solution with the concentration of 8.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 4, preparing a magnesium chloride solution with the concentration of 2.5 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.2, and the concentration of the ammonia water is 4.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium chloride solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 55 ℃, the pH is controlled to be 10.2, and the concentration of the ammonia water is 4.0g/L; the flow rate of the magnesium chloride solution is 0.1 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 10.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 2.0mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, preparing an aqueous solution of vinyl triethoxysilane with the mass concentration of 2%;
step 10, mixing the precipitate with an aqueous solution of vinyltriethoxysilane according to a solid-to-liquid ratio of 1g to 3mL, and drying for 2 hours at 120 ℃ to obtain a pretreated dry material;
and 11, calcining the pretreated dry material for 0.5h in an oxygen atmosphere at 800 ℃ to obtain the surface modified positive electrode material precursor.
Comparative example 3: (in comparison with example 3, the precipitate was not dried and was directly treated with an aqueous solution of a silane coupling agent)
A surface modified positive electrode material precursor has a chemical general formula of Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO·0.00163SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 3.5 mu m; elemental silicon is present only on the primary particle surface.
The preparation method of the surface modified positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 1.0mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.8:0.1:0.1;
step 2, preparing sodium hydroxide solution with the concentration of 4.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 4, preparing a magnesium nitrate solution with the concentration of 1.0 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 11.0, and the concentration of the ammonia water is 10.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium nitrate solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 48 ℃, the pH value is controlled to be 11.0, and the concentration of the ammonia water is controlled to be 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 3.5 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, preparing an aqueous solution of vinyl tri (beta-methoxyethoxy) silane with the mass concentration of 0.5%;
step 10, mixing the precipitate with an aqueous solution of vinyltris (beta-methoxyethoxy) silane according to a solid-to-liquid ratio of 1g to 1mL, and drying at 100 ℃ for 3 hours to obtain a pretreated dry material;
and 11, calcining the pretreated dry material for 1h in an air atmosphere at the temperature of 500 ℃ to obtain the surface modified positive electrode material precursor.
Comparative example 4: (in comparison with example 1, the treatment was not carried out with an aqueous solution of a silane coupling agent)
A precursor of positive electrode material has a chemical formula of Ni 0.6 Co 0.2 Mn 0.2 O.0.05 MgO; the particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 6.0 mu m.
The preparation method of the positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 2.0mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.6:0.2:0.2;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 8.0mol/L as a complexing agent;
step 4, preparing a magnesium sulfate solution with the concentration of 2.0 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.8, and the concentration of the ammonia water is 8.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium sulfate solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 58 ℃, the pH is controlled to be 10.8, and the concentration of the ammonia water is 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 6.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1.5mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 280 ℃ for 1h to obtain a dried material;
and 10, calcining the dried material for 1h in an oxygen atmosphere at the temperature of 650 ℃ to obtain a positive electrode material precursor.
Comparative example 5: (in comparison with example 2, the treatment was not carried out with an aqueous solution of a silane coupling agent)
A precursor of positive electrode material has a chemical formula of Ni 0.6 Co 0.2 Mn 0.2 O.0.1 MgO; the particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 10.0 mu m.
The preparation method of the positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 2.5mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.6:0.2:0.2;
step 2, preparing sodium hydroxide solution with the concentration of 8.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 12.0mol/L as a complexing agent;
step 4, preparing a magnesium chloride solution with the concentration of 2.5 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 10.2, and the concentration of the ammonia water is 4.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium chloride solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 55 ℃, the pH is controlled to be 10.2, and the concentration of the ammonia water is 4.0g/L; the flow rate of the magnesium chloride solution is 0.1 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 10.0 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 2.0mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 220 ℃ for 2 hours to obtain a dried material;
and 10, calcining the dried material for 0.5h in an oxygen atmosphere at 800 ℃ to obtain a positive electrode material precursor.
Comparative example 6: (no treatment with an aqueous solution of silane coupling agent compared with example 3)
A precursor of positive electrode material has a chemical formula of Ni 0.8 Co 0.1 Mn 0.1 O.0.02 MgO; the particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 3.5 mu m.
The preparation method of the positive electrode material precursor comprises the following steps:
step 1, preparing a nickel cobalt manganese mixed salt solution with the total concentration of nickel cobalt manganese metal ions of 1.0mol/L by taking soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio Ni: co: mn=0.8:0.1:0.1;
step 2, preparing sodium hydroxide solution with the concentration of 4.0mol/L as a precipitant;
step 3, preparing ammonia water with the concentration of 6.0mol/L as a complexing agent;
step 4, preparing a magnesium nitrate solution with the concentration of 1.0 mol/L;
step 5, adding alkaline base solution into the reaction kettle until the alkaline base solution overflows a bottom stirring paddle, starting stirring, wherein the alkaline base solution is mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 11.0, and the concentration of the ammonia water is 10.0g/L;
step 6, the nickel-cobalt-manganese mixed salt solution prepared in the step 1, the sodium hydroxide solution prepared in the step 2, the ammonia water prepared in the step 3 and the magnesium nitrate solution prepared in the step 4 are added into a reaction kettle in parallel flow for reaction, the reaction temperature in the kettle is controlled to be 48 ℃, the pH value is controlled to be 11.0, and the concentration of the ammonia water is controlled to be 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times of the flow rate of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle reaches 3.5 mu m;
step 8, carrying out solid-liquid separation on materials in the kettle, washing with 1mol/L sodium hydroxide solution, and washing precipitate with pure water;
step 9, drying the precipitate at 250 ℃ for 1.5 hours to obtain a dried material;
and 10, calcining the dried material for 1h in an air atmosphere at the temperature of 500 ℃ to obtain a positive electrode material precursor.
Test example:
the positive electrode material precursors prepared in example 1, example 2, comparative example 1, comparative example 2, comparative example 4 and comparative example 5 were mixed with lithium carbonate according to a total molar ratio of lithium element to nickel cobalt manganese of 1.08:1, uniformly mixing, and calcining for 12 hours at 850 ℃ in an oxygen atmosphere to obtain corresponding anode materials respectively.
The positive electrode material precursors prepared in example 3, comparative example 3 and comparative example 6 were mixed with lithium hydroxide according to a total molar ratio of lithium element to nickel cobalt manganese of 1.08:1, uniformly mixing, and calcining for 12 hours at 800 ℃ in an oxygen atmosphere to obtain corresponding anode materials respectively.
The positive electrode material obtained above is prepared into a button cell for testing the electrochemical performance of a lithium ion battery, and the specific steps are as follows: mixing N-methylpyrrolidone as solvent, acetylene black and PVDF uniformly according to the mass ratio of 8:1:1, coating on aluminum foil, air drying at 80deg.C for 8 hr, and vacuum drying at 120deg.C for 12 hr. The battery is assembled in a glove box protected by argon, the negative electrode is a metal lithium sheet, the diaphragm is a polypropylene film, and the electrolyte is 1M LiPF6-EC/DMC (1:1, v/v). The current density is 1 C=160 mA/g, and the charge-discharge cut-off voltage is 2.7-4.3V. The cycle performance at 1C current density was tested and the results are shown in table 1 below.
Table 1: battery performance test results
As shown in Table 1, the surface modified positive electrode material precursor prepared by the preparation method has excellent electrochemical performance after being prepared into a positive electrode material, the 0.1C discharge capacity of the positive electrode material precursor can reach more than 182.9mAh/g, the discharge specific capacity of the positive electrode material precursor after 300 times of circulation can reach more than 172.0mAh/g, and the circulation retention rate of the positive electrode material precursor after 300 times of circulation can reach more than 90.94%.
Meanwhile, as is clear from comparative examples 1 and 1, examples 2 and 2, and examples 3 and 3, respectively, when the precipitate is directly treated with an aqueous solution of a silane coupling agent without drying the precipitate during the preparation of the positive electrode material precursor, the discharge capacity and cycle retention rate of the battery are reduced after the prepared surface-modified positive electrode material precursor is prepared into a positive electrode material.
As is clear from comparative examples 1 and 4, examples 2 and 5, and examples 3 and 6, respectively, when the surface modification treatment is not performed by using the aqueous solution of the silane coupling agent in the preparation process of the positive electrode material precursor, the discharge capacity and the cycle retention rate of the battery are greatly reduced after the prepared positive electrode material precursor is prepared into the positive electrode material.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a surface modified positive electrode material precursor is characterized by comprising the following steps: the chemical formula of the surface modified positive electrode material precursor is as follows: ni (Ni) a Co b Mn c O·xMgO·ySiO 2 Wherein a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, a+b+c=1, y is more than 0 and less than x and less than or equal to 0.1, and the preparation method comprises the following steps:
(1) Mixing nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent, a soluble magnesium salt solution and alkaline base solution for reaction to obtain mixed solution;
(2) Carrying out solid-liquid separation on the mixed liquid obtained in the step (1), washing the separated solid, and drying to obtain a dried material;
(3) Mixing the dried material obtained in the step (2) with an aqueous solution of a silane coupling agent, drying, and calcining under an oxygen atmosphere to obtain the surface-modified positive electrode material precursor;
in the step (2), the drying temperature is 220-280 ℃ and the drying time is 1-2h.
2. The method of manufacturing according to claim 1, characterized in that: the surface modified positive electrode material precursor is secondary particles formed by agglomeration of primary particles, wherein the particle size of the primary particles is 0.01-1.0 mu m, and the particle size of the agglomerated secondary particles is 1.0-15.0 mu m.
3. The method of manufacturing according to claim 1, characterized in that: the silicon element in the surface-modified positive electrode material precursor exists only on the surface of the primary particles.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), the molar ratio of nickel element, cobalt element and manganese element in the nickel-cobalt-manganese mixed salt solution is a:b:c.
5. The method of manufacturing according to claim 1, characterized in that: in the step (1), the concentration of the soluble magnesium salt solution is 0.5-3.0mol/L.
6. The method of manufacturing according to claim 1, characterized in that: in the step (1), the alkaline base solution is a mixed solution of sodium hydroxide and ammonia water, the pH value of the alkaline base solution is 9.0-11.0, and the concentration of the ammonia water in the alkaline base solution is 1.0-12.0g/L.
7. The method of manufacturing according to claim 1, characterized in that: in the step (3), the silane coupling agent in the aqueous solution of the silane coupling agent is at least one of N- (beta-aminoethyl) -alpha-aminopropyl trimethoxy silane, 3-glycidyl propyl trimethoxy silane, vinyl tri (beta-methoxyethoxy) silane, vinyl triethoxy silane and vinyl trimethoxy silane.
8. Use of the surface-modified cathode material precursor prepared by the preparation method of any one of claims 1 to 3 in the preparation of lithium ion batteries.
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| JP2018060759A (en) * | 2016-10-07 | 2018-04-12 | 住友金属鉱山株式会社 | Method for manufacturing nickel cobalt manganese-containing composite hydroxide, positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing the same, and nonaqueous electrolyte secondary battery arranged by use of positive electrode active material hereof |
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| CN114242970A (en) * | 2021-11-19 | 2022-03-25 | 广东邦普循环科技有限公司 | Composite coated ternary precursor and preparation method and application thereof |
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| CN106532029A (en) * | 2016-12-28 | 2017-03-22 | 四川富骅新能源科技有限公司 | High-voltage ternary positive electrode material for lithium-ion battery and preparation method of high-voltage ternary positive electrode material |
| CN112447962A (en) * | 2019-08-27 | 2021-03-05 | 荆门市格林美新材料有限公司 | Precursor for doped lithium ion battery, positive electrode material and preparation methods of precursor and positive electrode material |
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| JP2018060759A (en) * | 2016-10-07 | 2018-04-12 | 住友金属鉱山株式会社 | Method for manufacturing nickel cobalt manganese-containing composite hydroxide, positive electrode active material for nonaqueous electrolyte secondary battery, method for manufacturing the same, and nonaqueous electrolyte secondary battery arranged by use of positive electrode active material hereof |
| CN108899545A (en) * | 2018-06-26 | 2018-11-27 | 格林美（无锡）能源材料有限公司 | A kind of mesoporous core-shell structure surface cladding lithium electricity tertiary cathode material and preparation method thereof |
| CN114242970A (en) * | 2021-11-19 | 2022-03-25 | 广东邦普循环科技有限公司 | Composite coated ternary precursor and preparation method and application thereof |
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