CN115490276A - 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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- CN115490276A CN115490276A CN202211162472.8A CN202211162472A CN115490276A CN 115490276 A CN115490276 A CN 115490276A CN 202211162472 A CN202211162472 A CN 202211162472A CN 115490276 A CN115490276 A CN 115490276A
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- 239000002243 precursor Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 title claims description 34
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000010405 anode material Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 132
- 239000000243 solution Substances 0.000 claims description 124
- 238000006243 chemical reaction Methods 0.000 claims description 61
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 59
- 239000012266 salt solution Substances 0.000 claims description 46
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000011572 manganese Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 33
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- 239000011164 primary particle Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 239000010406 cathode material Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000011163 secondary particle Substances 0.000 claims description 17
- 239000008139 complexing agent Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000012716 precipitator Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 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
- 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
- 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
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 4
- 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 24
- 239000002245 particle Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052748 manganese Inorganic materials 0.000 description 18
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 6
- 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229910017069 Ni0.6Co0.2Mn0.2O Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 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 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
- 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
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 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
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 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
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 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
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001351 cycling 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
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 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 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
- 150000002815 nickel Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation 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
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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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- 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
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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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Abstract
The invention discloses a surface modified anode material precursor, a preparation method and application thereof, wherein the chemical formula of the surface modified anode material precursor is as follows: 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 or equal to x and less than or equal to 0.1. The surface-modified positive electrode materialThe material precursor can improve the cycle performance of the subsequent sintering anode 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 their 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. With the requirement of new energy automobiles on the endurance mileage being higher and higher, higher requirements are also provided for the energy density and the cycle life of the power type lithium ion battery. 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 concerned at present.
At present, the ternary cathode material is mainly prepared by firstly preparing a hydroxide precursor through a coprecipitation method, for example, nickel salt, cobalt salt and manganese salt are used as raw materials, and a spherical nickel-cobalt-manganese hydroxide precursor is obtained by controlling reaction conditions and reaction rate 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, transition metal dissolution, oxygen precipitation, continuous oxidation and decomposition of the electrolyte and the like, so that the cycle performance of the ternary material is poor.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a surface-modified anode material precursor, and a preparation method and application thereof, so that the anode material precursor can be directionally coated after being doped, and the cycle performance of a subsequently sintered anode material is improved.
The technical purpose of the invention is realized by the following technical scheme:
a surface-modified cathode material precursor, the chemical formula of the surface-modified cathode material precursor is as follows: 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 or equal to x and less than or equal to 0.1.
Preferably, the surface-modified cathode material precursor is a secondary particle formed by agglomerating primary particles, wherein the primary particles have a particle size of 0.01-1.0 μm, and the agglomerated secondary particles have a particle size of 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.
A preparation method of the surface modified positive electrode material precursor comprises the following steps:
(1) Mixing a nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent, a soluble magnesium salt solution and an alkaline base solution for reaction to obtain a 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 a silane coupling agent aqueous solution, drying, and calcining in an aerobic atmosphere to obtain the surface-modified anode 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 and manganese ions in the nickel, cobalt and manganese mixed salt solution is 0.5-3.0mol/L.
Further preferably, in the step (1), the total concentration of nickel, cobalt and manganese ions in the nickel, cobalt and 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 the 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 the step (1), the concentration of the soluble magnesium salt solution is 0.5-3.0mol/L.
Further preferably, in the 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 to 11.0, and the concentration of the ammonia water in the alkaline base solution is 1.0 to 12.0g/L.
Further preferably, in the step (1), the pH of the alkaline base solution is 10.0 to 11.0, and the concentration of ammonia water in the alkaline base solution is 2.0 to 10.0g/L.
Preferably, in the step (1), the mixing manner is that the nickel-cobalt-manganese mixed salt solution, the precipitant, the complexing agent and the soluble magnesium salt solution are added into the alkaline base solution in a concurrent flow manner, the flow rate of the soluble magnesium salt is controlled to be 0.01-1 times of the flow rate of the nickel-cobalt-manganese mixed salt solution in the adding process, the ratio of the final magnesium ion addition amount to the nickel-cobalt-manganese ion is controlled to be Mg: ni: co: mn = x: a: b: c, the pH of the mixed solution is controlled to be 9.0-11.0, and the ammonia water concentration is 1.0-12.0g/L.
Further preferably, the pH of the mixed solution is controlled to 10.0 to 11.0, and the concentration of ammonia water is controlled to 2.0 to 10.0g/L.
Preferably, in step (1), the temperature of the reaction is 40-70 ℃.
Further preferably, in the step (1), the temperature of the reaction is 45 to 65 ℃.
Preferably, in the step (1), when the particle size of the material in the mixed solution is detected to reach 1.0-15.0 μm, the feeding is stopped.
Preferably, in the step (2), the washing mode is washing with alkali liquor firstly and then washing with water.
Preferably, the alkali liquor is at least one of a sodium hydroxide solution and a 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 silane coupling agent aqueous solution 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% to 2%.
Preferably, in the step (3), the silane coupling agent in the aqueous solution of silane coupling agent is at least one of N- (β -aminoethyl) - α -aminopropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane.
Preferably, in the step (3), the solid-to-liquid ratio g/mL of the drying material to the silane coupling agent aqueous solution is 1: (1-5).
Further preferably, in the step (3), the solid-to-liquid ratio g/mL of the drying material to the silane coupling agent aqueous solution 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 calcining temperature is 500-800 ℃, and the calcining time is 0.5-1h.
Preferably, the preparation method of the surface modified cathode 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 1.0-2.5mol/L by using nickel, cobalt and manganese soluble salts as raw materials according to the element molar ratio of Ni to Co to Mn = a to b to c;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0-8.0mol/L as a precipitator;
step 3, preparing ammonia water with the concentration of 6.0-12.0mol/L as a complexing agent;
step 4, preparing 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 a 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, adding 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 45-65 ℃, the pH value is 10.0-11.0, and the concentration of the ammonia water is 2.0-10.0g/L; the flow rate of the magnesium sulfate/magnesium chloride/magnesium nitrate solution is 0.01-1 times of that of the mixed salt solution, and the flow rate is adjusted optionally along with the reaction, and the ratio of the final addition amount of magnesium ions to nickel-cobalt-manganese ions needs to be controlled to be Mg, ni, co, mn = x, a, b and c;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 1.0-15.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials by using 1-2.0mol/L sodium hydroxide solution, and washing precipitates by using pure water;
step 9, drying the precipitate at 220-280 ℃ for 1-2h to obtain a dried material;
step 11, mixing the drying material with a silane coupling agent aqueous solution according to the solid-to-liquid ratio of 1g to 3mL, and drying at 100-120 ℃ for 2-3h to obtain a pretreated drying material;
and step 12, calcining the pretreated dried material for 0.5 to 1 hour in the air or oxygen atmosphere at the temperature of between 500 and 800 ℃ to obtain the surface-modified anode material precursor.
The surface modified anode material precursor is applied to the preparation of lithium ion batteries.
The beneficial effects of the invention are:
(1) The surface-modified cathode material precursor prepared by the preparation method has excellent cycle performance after being prepared into a cathode material, and after 300 cycles, the cycle retention rate can reach more than 90.94%.
(2) The preparation method of the surface modified anode material precursor comprises the steps of firstly carrying out coprecipitation reaction on a nickel-cobalt-manganese mixed salt solution, a precipitator, a soluble magnesium salt and an alkaline base solution under the complexation of a complexing agent to generate a magnesium-doped nickel-cobalt-manganese hydroxide, drying at low temperature (220-280 ℃), dehydrating the nickel-cobalt-manganese hydroxide and decomposing the nickel-cobalt-manganese hydroxide into an oxide, wherein the magnesium hydroxide still exists in the form of hydroxide at the temperature to form a magnesium hydroxide-doped nickel-cobalt-manganese oxide, selectively modifying the magnesium hydroxide to generate Mg-O-Si-R through directional modification of a silane coupling agent and reaction with hydroxyl on the surface of a dried material, keeping the nickel-cobalt-manganese oxide unchanged, and finally further calcining to remove an organic chain remained by the silane coupling agent to form a 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, the organic chain is removed through calcination, and a magnesium silicate-like coating layer is formed, so that the interface stability of the material can be further improved, the silane coupling agent cannot react with nickel-cobalt-manganese oxide, and the problem that the nickel-cobalt-manganese silicate is difficult to form nickel-cobalt lithium manganate through subsequent sintering due to formation of nickel-cobalt-manganese silicate is solved.
(4) According to the preparation method of the surface modified anode material precursor, the characteristic that other hydroxides are difficult to decompose in the decomposition of magnesium hydroxide is utilized, the nickel-cobalt-manganese hydroxide is selectively dehydrated to generate nickel-cobalt-manganese oxide, the magnesium hydroxide is independently reacted with a silane coupling agent to form a silicon-magnesium coating layer, magnesium is doped on the surface layer of particles, the formed coating layer is extremely stable and difficult to fall off after being combined with silicon, and the cycle performance of the material can be further improved during subsequent sintering of the anode material.
Drawings
Fig. 1 is an SEM image of a surface-modified positive electrode material precursor prepared in example 1 of the present invention at 10000 times;
fig. 2 is a SEM image at 50000 times of the surface-modified positive electrode material precursor prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a surface modified positive electrode material precursor with a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO·0.01SiO 2 (ii) a 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 silicon element exists only on the surface of the primary particles, and the SEM image of the precursor of the surface-modified cathode material is shown in the figure1 and 2.
The preparation method of the surface modified cathode 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.6;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0mol/L as a precipitator;
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 an 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 a 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, adding 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 58 ℃, the pH value is controlled to be 10.8, and the concentration of the ammonia water is controlled to be 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 6.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 1.5mol/L sodium hydroxide solution, and washing precipitates with pure water;
step 9, drying the precipitate at 280 ℃ for 1h to obtain a dried material;
step 11, mixing the drying material with an aqueous solution of vinyl trimethoxy silane according to the solid-to-liquid ratio of 1g;
and step 12, calcining the pretreated dried material for 1h in an oxygen atmosphere at the temperature of 650 ℃ to obtain the surface-modified anode material precursor.
Example 2:
a surface modified positive electrode material precursor with a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO·0.025SiO 2 (ii) a 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 surface of the primary particles.
The preparation method of the surface modified cathode 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.6;
step 2, preparing a sodium hydroxide solution with the concentration of 8.0mol/L as a precipitator;
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 an 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 a 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, adding 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 into a reaction kettle in a parallel flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 55 ℃, the pH value 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 time of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 10.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 2.0mol/L sodium hydroxide solution, and washing precipitates with pure water;
step 9, drying the precipitate at 220 ℃ for 2h to obtain a dried material;
step 11, mixing the drying material with an aqueous solution of vinyltriethoxysilane according to the solid-to-liquid ratio of 1g to 3mL, and drying at 120 ℃ for 2 hours to obtain a pretreated drying material;
and step 12, calcining the pretreated dried material for 0.5h in an oxygen atmosphere at the temperature of 800 ℃ to obtain a surface-modified positive electrode material precursor.
Example 3:
a surface modified positive electrode material precursor with a chemical general formula of Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO·0.0136SiO 2 (ii) a 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 surface of the primary particles.
The preparation method of the surface modified cathode 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.8;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0mol/L as a precipitator;
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 a 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, adding the mixed salt solution of nickel, cobalt and manganese 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 48 ℃, the pH value is 11.0, and the concentration of the ammonia water is 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 3.5 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials by using 1mol/L sodium hydroxide solution, and washing precipitates by using pure water;
step 9, drying the precipitate at 250 ℃ for 1.5h to obtain a dried material;
step 11, mixing the drying material with an aqueous solution of vinyl tris (beta-methoxyethoxy) silane according to the solid-to-liquid ratio of 1g to 1mL, and drying at 100 ℃ for 3h to obtain a pretreated drying material;
and step 12, calcining the pretreated dried material for 1 hour in an air atmosphere at the temperature of 500 ℃ to obtain the surface-modified anode material precursor.
Comparative example 1: (the precipitate was not dried as compared with example 1, but was treated with an aqueous silane coupling agent solution as it is)
A surface modified positive electrode material precursor with a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.05MgO·0.0128SiO 2 (ii) a 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 surface of the primary particles.
The preparation method of the surface modified cathode 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.6;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0mol/L as a precipitator;
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 an 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 a 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, adding 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 58 ℃, the pH value is controlled to be 10.8, and the concentration of the ammonia water is controlled to be 8.0g/L; the flow rate of the magnesium sulfate solution is 0.05 times of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 6.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 1.5mol/L sodium hydroxide solution, and washing the precipitate with pure water;
step 9, preparing an aqueous solution of 1% by mass of vinyltrimethoxysilane;
and 11, calcining the pretreated dried material for 1 hour at the temperature of 650 ℃ in an oxygen atmosphere to obtain a surface-modified positive electrode material precursor.
Comparative example 2: (in contrast to example 2, the precipitate was not dried and was treated with the aqueous silane coupling agent solution as it was)
A surface modified positive electrode material precursor with a chemical general formula of Ni 0.6 Co 0.2 Mn 0.2 O·0.1MgO·0.0308SiO 2 (ii) a 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 silicon element is present only on the surface of the primary particles.
The preparation method of the surface modified cathode 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.6;
step 2, preparing a sodium hydroxide solution with the concentration of 8.0mol/L as a precipitator;
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 an 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 a 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, adding 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 55 ℃, the pH value 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 time of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 10.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 2.0mol/L sodium hydroxide solution, and washing precipitates with pure water;
step 9, preparing an aqueous solution of 2 mass percent of vinyltriethoxysilane;
and 11, calcining the pretreated dried material for 0.5h in an oxygen atmosphere at the temperature of 800 ℃ to obtain the surface-modified anode material precursor.
Comparative example 3: (in contrast to example 3, the precipitate was not dried and was treated with the aqueous silane coupling agent solution as it was)
A surface modified positive electrode material precursor with a chemical general formula of Ni 0.8 Co 0.1 Mn 0.1 O·0.02MgO·0.00163SiO 2 (ii) a It is a secondary particle formed by agglomeration of primary particles, the primary particles have a particle size of 0.01-1.0 mum, the particle size of the agglomerated secondary particles is 3.5 μm; elemental silicon is present only on the surface of the primary particles.
The preparation method of the surface modified cathode 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.8;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0mol/L as a precipitator;
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 an 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 a 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, adding the mixed salt solution of nickel, cobalt and manganese 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 48 ℃, the pH value is 11.0, and the concentration of the ammonia water is 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 3.5 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 1mol/L sodium hydroxide solution, and washing precipitates with pure water;
step 9, preparing an aqueous solution of vinyl tri (beta-methoxyethoxy) silane with the mass concentration of 0.5%;
and 11, calcining the pretreated dried material for 1h in an air atmosphere at the temperature of 500 ℃ to obtain the surface-modified anode material precursor.
Comparative example 4: (treatment with no aqueous silane coupling agent solution as compared with example 1)
A precursor of a positive electrode material, the chemical general formula of which is Ni 0.6 Co 0.2 Mn 0.2 0.05MgO of O; it is a secondary particle formed by agglomerating 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 6.0 mu m.
The preparation method of the precursor of the cathode material 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.6;
step 2, preparing a sodium hydroxide solution with the concentration of 6.0mol/L as a precipitator;
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 an 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 a 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, adding 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 58 ℃, the pH value 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 that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 6.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 1.5mol/L sodium hydroxide solution, and washing precipitates with pure water;
step 9, drying the precipitate at 280 ℃ for 1h to obtain a dried material;
and step 10, calcining the dried material for 1h at the temperature of 650 ℃ in an oxygen atmosphere to obtain the precursor of the anode material.
Comparative example 5: (treatment with an aqueous silane coupling agent solution was omitted compared with example 2.)
A precursor of a positive electrode material, the chemical general formula of which is Ni 0.6 Co 0.2 Mn 0.2 0.1MgO of O.multidot.O; it is a secondary particle formed by agglomerating 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 10.0 mu m.
The preparation method of the precursor of the cathode material 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.6;
step 2, preparing a sodium hydroxide solution with the concentration of 8.0mol/L as a precipitator;
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 an 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 a 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, adding 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 55 ℃, the pH value 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 time of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 10.0 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials with 2.0mol/L sodium hydroxide solution, and washing the precipitate with pure water;
step 9, drying the precipitate at 220 ℃ for 2h to obtain a dried material;
and step 10, calcining the dried material for 0.5h in an oxygen atmosphere at the temperature of 800 ℃ to obtain a precursor of the anode material.
Comparative example 6: (treatment with an aqueous silane coupling agent solution was omitted compared with example 3.)
A precursor of a positive electrode material, the chemical general formula of which is Ni 0.8 Co 0.1 Mn 0.1 0.02MgO; it is a secondary particle formed by agglomerating 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 3.5 mu m.
The preparation method of the precursor of the cathode material 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 using soluble salts of nickel, cobalt and manganese as raw materials according to the element molar ratio of Ni to Co to Mn = 0.8;
step 2, preparing a sodium hydroxide solution with the concentration of 4.0mol/L as a precipitator;
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 an 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 a 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, adding the mixed salt solution of nickel, cobalt and manganese 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 into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 48 ℃, the pH value is 11.0, and the concentration of the ammonia water is 10.0g/L; the flow rate of the magnesium nitrate solution is 0.02 times of that of the mixed salt solution;
step 7, stopping feeding when the granularity of the materials in the reaction kettle is detected to reach 3.5 mu m;
step 8, performing solid-liquid separation on the materials in the kettle, washing the materials by using 1mol/L sodium hydroxide solution, and washing precipitates by using pure water;
step 9, drying the precipitate at 250 ℃ for 1.5h to obtain a dried material;
and step 10, calcining the dried material for 1h in an air atmosphere at the temperature of 500 ℃ to obtain the precursor of the positive electrode material.
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 in such a manner that the molar ratio of lithium element to the total of nickel, cobalt, and manganese was 1.08:1, uniformly mixing, and calcining at 850 ℃ for 12h in an oxygen atmosphere to respectively obtain corresponding positive electrode materials.
The positive electrode material precursors prepared in example 3, comparative example 3 and comparative example 6 were mixed with lithium hydroxide in a molar ratio of lithium element to nickel, cobalt and manganese of 1.08:1, uniformly mixing, and calcining for 12 hours at 800 ℃ in an oxygen atmosphere to respectively obtain corresponding anode materials.
The obtained anode material is prepared into a button cell for testing the electrochemical performance of the lithium ion battery, and the method comprises the following specific steps: the method comprises the steps of taking N-methyl pyrrolidone as a solvent, uniformly mixing a positive electrode active substance, acetylene black and PVDF according to the mass ratio of 8:1, coating on an aluminum foil, carrying out forced air drying at 80 ℃ for 8h, and carrying out vacuum drying at 120 ℃ for 12h. The battery is assembled in an argon-protected glove box, 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 1C =160mA/g, and the charge-discharge cut-off voltage is 2.7-4.3V. The cycling performance at 1C current density was tested and the results are shown in table 1 below.
Table 1: results of battery performance test
As can be seen from Table 1, the surface-modified cathode material precursor prepared by the preparation method disclosed by the invention has excellent electrochemical performance after being prepared into a cathode material, the 0.1C discharge capacity of the precursor can reach more than 182.9mAh/g, the discharge specific capacity after 300 cycles can reach more than 172.0mAh/g, and the cycle retention rate can reach more than 90.94% after 300 cycles.
Meanwhile, by comparing example 1 with comparative example 1, example 2 with comparative example 2, and example 3 with comparative example 3, it can be seen that, in the preparation process of the precursor of the positive electrode material, the precipitate is directly treated with the aqueous solution of the silane coupling agent without being dried, and the discharge capacity and the cycle retention rate of the battery are reduced after the prepared precursor of the surface-modified positive electrode material is prepared into the positive electrode material.
Comparing example 1 with comparative example 4, example 2 with comparative example 5, and example 3 with comparative example 6, respectively, it can be seen that, when the surface modification treatment is not performed using the silane coupling agent aqueous solution 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 surface modified positive electrode material precursor is prepared into the positive electrode material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A surface-modified positive electrode material precursor is characterized in that: the chemical formula of the surface modified anode material precursor is as follows: 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 or equal to x and less than or equal to 0.1.
2. A surface-modified positive electrode material precursor according to claim 1, characterized in that: the surface modified anode material precursor is secondary particles formed by agglomerating primary particles, wherein the granularity of the primary particles is 0.01-1.0 mu m, and the granularity of the agglomerated secondary particles is 1.0-15.0 mu m.
3. The surface-modified positive electrode material precursor according to claim 1, wherein: the silicon element in the surface modified anode material precursor exists on the surface of the primary particles only.
4. A method for producing the surface-modified positive electrode material precursor according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
(1) Mixing a nickel-cobalt-manganese mixed salt solution, a precipitator, a complexing agent, a soluble magnesium salt solution and an alkaline base solution for reaction to obtain a 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 a silane coupling agent aqueous solution, drying, and calcining in an aerobic atmosphere to obtain the surface-modified positive electrode material precursor.
5. The method for preparing a surface-modified positive electrode material precursor as claimed in claim 4, wherein: 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.
6. The method for preparing a surface-modified cathode material precursor according to claim 4, wherein: in the step (1), the concentration of the soluble magnesium salt solution is 0.5-3.0mol/L.
7. The method for preparing a surface-modified cathode material precursor according to claim 4, wherein: 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.
8. The method for preparing a surface-modified positive electrode material precursor as claimed in claim 4, wherein: in the step (2), the drying temperature is 220-280 ℃, and the drying time is 1-2h.
9. The method for preparing a surface-modified cathode material precursor according to claim 4, wherein: in the step (3), the silane coupling agent in the silane coupling agent aqueous solution is at least one of N- (beta-aminoethyl) -alpha-aminopropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltriethoxysilane and vinyltrimethoxysilane.
10. Use of the surface-modified positive electrode material precursor of any one of claims 1 to 3 for the preparation of a lithium ion battery.
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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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