CN113690419B - Ternary positive electrode composite material, preparation method thereof and lithium ion battery - Google Patents
Ternary positive electrode composite material, preparation method thereof and lithium ion battery Download PDFInfo
- Publication number
- CN113690419B CN113690419B CN202110980031.8A CN202110980031A CN113690419B CN 113690419 B CN113690419 B CN 113690419B CN 202110980031 A CN202110980031 A CN 202110980031A CN 113690419 B CN113690419 B CN 113690419B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- manganese
- equal
- nickel
- electrode composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 239000011258 core-shell material Substances 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 68
- 239000011572 manganese Substances 0.000 claims description 45
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 28
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 229910052748 manganese Inorganic materials 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 239000011162 core material Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000002019 doping agent Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 7
- 239000011824 nuclear material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 22
- 229910052596 spinel Inorganic materials 0.000 description 14
- 239000011029 spinel Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 11
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element 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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- 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
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of lithium ion battery anode materials, in particular to a ternary anode composite material, a preparation method thereof and a lithium ion battery. The ternary cathode composite material has a core-shell structure, and the core-shell structure has a chemical general formula of Li a Ni b Co c Mn d M e O 2 Is a core of a compound of the formula (II) with the chemical formula Li x Ni (0.5‑y) Mn (1.5+y) O 4 The compound of (a) is a shell; wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.8 and less than or equal to 1, c is more than 0 and less than 0.2, d is more than 0 and less than 0.2, b + c + d =1, e is more than 0 and less than or equal to 0.01, M is selected from at least one of Cs, ru, ce, sm, sr, ir, V, zr, W, nb and Mo elements; x is more than or equal to 1 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 0.2. The ternary cathode composite material has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
Description
Technical Field
The invention relates to the technical field of ternary cathode materials, in particular to a ternary cathode composite material, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, good cycle performance and the like, and is widely applied to various fields of electronic products, automobiles, spaceflight and the like. With the increasing requirements of people on environmental protection, endurance, service life and the like of lithium ion batteries, the design and optimization of the batteries are more and more important. As a core in lithium ion batteries, the quality of a positive electrode material directly determines the performance of the battery. The ternary cathode material has become an important cathode active material of the current power lithium ion battery, and has been commercialized in a large scale, such as NCM523, NCM622, and the like. Compared with the traditional LiNiO 2 ，LiCoO 2 And LiMnO 2 The material, the ternary positive electrode material, has a more stable structure, better cycle performance and higher capacity.
However, the NCM ternary positive electrode material also has defects such as micro-cracks, phase transition, mechanical stress, and side reactions between the electrode and the electrolyte during the similar cycle, which may cause problems of structural damage, irreversible capacity loss, and the like. In addition, the ternary cathode material in the prior art is of a pure-phase layered crystal structure, and the stability of the ternary cathode material is poorer as the content of nickel is increased, so that the safety cannot be guaranteed. Simultaneously, the increase of residual alkali is accompanied, so that the slurry is unstable and is in a jelly shape during subsequent homogenization.
In addition, the traditional synthesis process of the ternary cathode material is to synthesize a precursor through coprecipitation, and then mix lithium and calcine to obtain a target product, and the process has the following defects: more industrial wastewater is generated, more synthetic process steps are required, the cost is higher, the doping is surface doping, and the stabilizing effect is not obvious.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a ternary cathode composite material, which forms a core-shell structure by doping modification and coating a layer of nano spinel nickel-manganese material, and has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
The second purpose of the invention is to provide a preparation method of the ternary cathode composite material, the method comprises the steps of doping modification, inducing to form a mixed layer, coating a layer of nano spinel nickel lithium manganate to form a core-shell structure, and improving the stability and safety of the material while reducing the residual alkali of the material. Moreover, the preparation method also has the advantages of simple process, low cost and the like.
The third purpose of the invention is to provide the lithium ion battery, wherein the anode of the lithium ion battery is mainly prepared from the ternary anode composite material, and the lithium ion battery has the advantages of excellent cyclicity, stability and safety performance, low preparation cost and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the ternary cathode composite material has a core-shell structure, and the core-shell structure adopts a chemical general formula of Li a Ni b Co c Mn d M e O 2 With a compound of the formula Li as a nucleus x Ni (0.5-y) Mn (1.5+y) O 4 The compound of (a) is a shell;
wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.8 and less than or equal to 1, c is more than 0 and less than 0.2, d is more than 0 and less than 0.2, b + c + d =1, e is more than 0 and less than or equal to 0.01, M is selected from at least one of Cs, ru, ce, sm, sr, ir, V, zr, W, nb and Mo elements; x is more than or equal to 1 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 0.2.
According to the invention, a core-shell structure is formed by doping modification and coating a layer of nano spinel nickel-manganese material, so that the ternary cathode composite material has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
The invention also provides a preparation method of the ternary cathode composite material, which comprises the following steps:
(a) Mixing a nickel source, a cobalt source, a manganese source, a lithium source and a doping agent with water, grinding, drying and calcining to obtain the nuclear material with the core-shell structure;
(b) Crushing and sieving the nuclear material obtained in the step (a), testing the total alkali of the nuclear material after sieving, and according to the test result and the chemical general formula Li of the spinel lithium nickel manganese oxide x Ni (0.5-y) Mn (1.5+y) O 4 And x is more than or equal to 1 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 0.2, the addition amounts of the nickel source and the manganese source are obtained through calculation, the nickel source and the manganese source are added, and the ternary cathode composite material is obtained through mixing and calcining.
According to the invention, the mixed-arrangement layer is formed by doping modification and induction, and the nano spinel nickel lithium manganate is coated to form a core-shell structure, so that the stability and safety of the material are improved while the residual alkali of the material is reduced. In addition, the preparation method also has the advantages of simple process, low cost and the like.
The preparation method directly carries out bulk phase doping in the raw material, so that the doping elements uniformly enter the interior of crystal lattices. Therefore, the stability of the cathode material is improved more than that of the conventional surface doping.
Wherein the method for testing the total alkali of the core material specifically comprises the following steps:
dispersing a certain amount of cathode material in deionized water, stirring and dispersing for a certain time (generally more than 30 minutes), and then filtering to obtain an upper layerAcid-base titration is carried out on clear liquid by using calibrated dilute hydrochloric acid, phenolphthalein and methyl orange are respectively used as indicators of titration end points to obtain two titration end points, and LiOH and Li are obtained by calculation 2 CO 3 The content of (a).
Meanwhile, the coating consumes the residual lithium on the surface of the calcined material, so that a nano spinel lithium nickel manganese oxide coating layer is formed while the residual alkali is reduced, and a core-shell structure is formed.
Preferably, in step (a), the nickel source comprises a salt of nickel and/or an oxide of nickel.
Preferably, the nickel source comprises at least one of nickel oxide, nickel sesquioxide, nickel sulfate, nickel nitrate, and nickel chloride; more preferably nickel oxide.
Preferably, the cobalt source comprises a salt of cobalt and/or an oxide of cobalt.
Preferably, the cobalt source comprises at least one of cobaltosic oxide, cobalt sulfate, cobalt nitrate, and cobalt chloride; more preferably, tricobalt tetroxide.
Preferably, the manganese source comprises a salt of manganese and/or an oxide of manganese.
Preferably, the manganese source comprises at least one of manganous manganic oxide, manganese carbonate, manganese oxide, manganese dioxide, manganese sulfate, manganese nitrate and manganese chloride; more preferably trimanganese tetroxide.
Preferably, the lithium source comprises a salt of manganese and/or a hydroxide of lithium.
Preferably, the lithium source includes at least one of lithium carbonate, lithium hydroxide, lithium nitrate, and lithium sulfate.
The dopant comprises Cs, rb, ru, ce, sm, sr, ir, V, zr, W, nb, mo element salt and/or oxide thereof.
Preferably, the dopant comprises ZrO 2 、WO 3 、Nb 2 O 5 、MoO 3 、Cs 2 O、Rb 2 O、Ru 2 O、Ce 2 O、Sm 2 O 3 、SrO、IrO 2 And V 2 O 5 At least one of (1).
Preferably, in step (a), the solids content of the mixed mixture is from 20% to 60%; including but not limited to, a point value of any one of 25%, 30%, 35%, 40%, 45%, 50%, 55%, 58%, or a range value between any two; more preferably 30% to 40%.
Preferably, in step (a), the water is deionized water.
Preferably, in step (a), the milled grinding media comprises zirconia beads having a particle size of 0.1 to 0.2mm, more preferably the zirconia beads are 95 zirconium yttrium stabilized zirconium beads.
Preferably, the milling time is 1-5 hours, including but not limited to the point value of any one of 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or a range of values between any two.
Preferably, in step (a), the grinding is performed in a ceramic grinder.
The ceramic grinding machine achieves the grinding effect by mutual extrusion of the surfaces of the three horizontal rollers and friction at different speeds, and the granularity of the ground material is adjusted by adjusting the size of a gap between the rollers through adjusting the flat-row hand wheel screw, so that the ceramic grinding machine is simple and accurate and is convenient to operate.
Preferably, the D50 of the slurry after polishing is 0.4 μm or less.
Preferably, the drying is spray drying.
More preferably, the particle size of the powder obtained after the spray drying is 5 μm or less.
Preferably, in step (a), the temperature of the calcination is 700-1100 ℃, including but not limited to the point value of any one of 750 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃, 870 ℃, 900 ℃, 930 ℃, 950 ℃, 970 ℃, 1000 ℃, 1050 ℃, 1080 ℃ or the range value between any two; more preferably 800-950 deg.c.
Preferably, the calcination time is 6 to 20 hours, including but not limited to, the point value of any one of 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours or a range value between any two, more preferably 8 to 15 hours.
Preferably, in step (a) and/or step (b), the calcination is carried out in an oxygen-containing atmosphere; more preferably, the oxygen-containing atmosphere comprises air and oxygen.
Preferably, in step (b), the manganese source and/or the nickel source has a particle size of 10 to 200nm.
Preferably, in step (b), the temperature of the calcination is 700 to 950 ℃, including but not limited to the values of any one of 725 ℃, 750 ℃, 770 ℃, 800 ℃, 820 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃ or the range values between any two, more preferably 800 to 900 ℃.
Preferably, the calcination time is 4-10h; including but not limited to, any one or a range of values between 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, more preferably 5-7h.
The invention also provides a lithium ion battery which comprises the ternary cathode composite material or the ternary cathode composite material prepared by the preparation method of the ternary cathode composite material.
The lithium ion battery has the advantages of good stability, high safety, simple synthesis process, low cost and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) The ternary cathode composite material provided by the invention forms a core-shell structure by doping modification and coating a layer of nano spinel nickel-manganese material, so that the ternary cathode composite material has the advantages of low total alkali content, excellent cyclicity, stability and safety performance and the like.
(2) According to the preparation method of the ternary cathode composite material, the mixed-arrangement layer is formed through doping modification and induction, and the nano spinel lithium nickel manganese oxide is coated to form a core-shell structure, so that the residual alkali of the material is reduced, and the stability and the safety of the material are improved. Moreover, the preparation method also has the advantages of simple process, low cost and the like.
(3) The lithium ion battery provided by the invention has the advantages of excellent cyclicity, stability and safety performance, low preparation cost and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows a ternary positive electrode composite material Li provided in example 2 of the present invention 1.06 Ni 0.9 Co 0.07 Mn 0.03 Rb 0.005 O 2 @Li 1.06 Ni 0.35 Mn 1.65 O 4 SEM image of (d).
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are a part of the embodiments of the present invention, rather than all of the embodiments, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The preparation method of the ternary cathode composite material comprises the following steps:
(a) And a lithium source Li 2 CO 3 NiO as nickel source and Co as cobalt source 3 O 4 Mn as a source of manganese 3 O 4 Dopant Cs 2 Mixing O with deionized water uniformly (the molar ratio of lithium element, nickel element, cobalt element, manganese element, and zirconium element is 1.06The suspension was fed into a ceramic mill, 1.6Kg of 95 zirconium yttrium stabilized zirconium beads having a diameter of 0.2mm were added, milling was carried out at a rotation speed of 2000r/min for 2 hours to give a slurry having a D50 of 0.31. Mu.m, and the slurry was spray-dried at 180 ℃ to give a powder having a D50 of 4.2. Mu.m. And calcining the powder in an oxygen atmosphere at the calcining temperature of 920 ℃ for 12 hours to obtain the core material with the core-shell structure.
(b) Cooling, crushing and sieving the nuclear material obtained in the step (a), and then testing the total alkali, wherein the result shows that the content of LiOH is 0.42 percent, and Li 2 CO 3 The content is 1.23 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn 3 O 4 According to the mass ratio of 100:1.3:5.3 burdening, mixing in a high-speed mixer, calcining the mixture in an oxygen atmosphere at 850 ℃ for 5h to obtain the ternary cathode composite material Li with the core-shell structure 1.06 Ni 0.8 Co 0.1 Mn 0.1 Cs 0.006 O 2 @Li 1.05 Ni 0.4 Mn 1.6 O 4 。
The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.11 percent, and Li 2 CO 3 The content is 0.08%.
Example 2
(a) And a lithium source Li 2 CO 3 NiO as nickel source and Co as cobalt source 3 O 4 Mn as a source of manganese 3 O 4 And a dopant Rb 2 Mixing O and deionized water uniformly (the molar ratio of lithium element, nickel element, cobalt element, manganese element and rubidium element is 1.08. And calcining the powder in an oxygen atmosphere at 880 ℃ for 10 hours to obtain the core material with the core-shell structure.
(b) Obtained in step (a)The core material was cooled, crushed, sieved, and then tested for total alkali, the results showed 0.53% LiOH content, li 2 CO 3 The content is 1.43 percent, and the mass of the coating agent required to be added is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn 3 O 4 According to the mass ratio of 100:1.5:6.3, preparing materials, mixing the materials in a high-speed mixer, calcining the mixed materials in an oxygen atmosphere at 900 ℃ for 7 hours to obtain the ternary cathode composite material Li with the core-shell structure 1.06 Ni 0.9 Co 0.07 Mn 0.03 Rb 0.005 O 2 @Li 1.06 Ni 0.35 Mn 1.65 O 4 。
The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.15 percent, and Li 2 CO 3 The content is 0.06%.
The ternary cathode composite material prepared in this example was subjected to SEM test, and the results are shown in fig. 1.
As can be seen from figure 1, the ternary cathode material synthesized by the preparation method provided by the invention is a single crystal material, has round particles, good dispersion effect and less fine powder, and has better cycle performance and safety performance when being prepared into a lithium ion battery.
Example 3
(a) The lithium source LiOH and the nickel source Ni are mixed 2 O 3 Cobalt source Co 3 O 4 Manganese source MnCO 3 And a dopant Sm 2 O 3 Mixing the powder with deionized water uniformly (the molar ratio of lithium element, nickel element, cobalt element, manganese element and samarium element is 1.1. And calcining the powder in an oxygen atmosphere at 800 ℃ for 8h to obtain the core material with the core-shell structure.
(b) The steps of(a) The obtained core material was cooled, pulverized, sieved, and then subjected to a total alkali test, and the result showed that the content of LiOH was 0.59%, li 2 CO 3 The content is 1.64 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn 3 O 4 According to the mass ratio of 100:2.2:6.7 mixing materials, mixing the materials in a high-speed mixer, calcining the mixed materials in an oxygen atmosphere at 900 ℃ for 7 hours to obtain the ternary cathode composite material Li with the core-shell structure 1.1 Ni 0.95 Co 0.03 Mn 0.02 Rb 0.008 O 2 @Li 1.08 Ni 0.5 Mn 1.5 O 4 。
The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.04 percent, and Li 2 CO 3 The content is 0.12%.
Example 4
(a) And a lithium source Li 2 CO 3 NiO as nickel source and Co as cobalt source 3 O 4 MnO of manganese source 2 The dopant IrO 2 The mixture was uniformly mixed with deionized water (molar ratio of lithium element, nickel element, cobalt element, manganese element, and iridium element was 1.15. And calcining the powder in an air atmosphere at the temperature of 950 ℃ for 15h to obtain the core material with the core-shell structure.
(b) Cooling, crushing and sieving the nuclear material obtained in the step (a), and then testing the total alkali, wherein the result shows that the content of LiOH is 0.64 percent, and Li is 2 CO 3 The content is 1.58 percent, and the mass of the required coating agent is calculated according to the chemical general formula of the spinel lithium nickel manganese oxide. The obtained core material, nano NiO and nano Mn 3 O 4 According to the mass ratio of 100:1.2:7.1 compounding, mixing in a high-speed mixer, emptying the mixtureCalcining in a gas atmosphere at 950 ℃ for 10h to obtain the ternary cathode composite material Li with the core-shell structure 1.15 Ni 0.85 Co 0.1 Mn 0.05 Rb 0.01 O 2 @Li 1.15 Ni 0.3 Mn 1.7 O 4 . The total alkali of the ternary cathode composite material is tested, and the result shows that the content of LiOH is 0.08 percent, and Li 2 CO 3 The content is 0.09%.
Comparative example 1
This comparative example was prepared essentially identically to example 2, except that: in the step (b), nano NiO and nano Mn are added 3 O 4 Substitution with Al 2 O 3 According to the nuclear material and Al 2 O 3 The mass ratio of (A) to (B) is 100:0.05, batching; meanwhile, the calcination temperature is modified to 650 ℃, and the calcination time is modified to 5 hours, so that the Al-coated cathode material is obtained. The Al-coated positive electrode material is tested to be full alkali, and the result shows that the content of LiOH is 1.12 percent, and Li 2 CO 3 The content is 0.42%.
As can be seen from the results of the total alkali tests in the comparative examples 1 to 4 and 1, the core-shell structure ternary cathode material prepared in the examples 1 to 4 consumes residual alkali in the core material after the first sintering by coating a layer of nano spinel lithium nickel manganese oxide, so that the total alkali of the material is obviously reduced. Meanwhile, it can be seen by comparing example 2 with comparative example 1 that the total alkali cannot be significantly reduced by the conventional Al coating.
Test example 1
The ternary positive electrode composite materials prepared in examples 1 to 4 and comparative example 1 and the Al-coated positive electrode material prepared in the comparative example were mixed with carbon black (SP) and polyvinylidene fluoride (PVDF) at a ratio of 92:4:4 into N-methylpyrrolidone (NMP), uniformly mixing, coating on an aluminum foil, drying at 100 ℃ for 4h, cutting into positive plates with the diameter of 12mm, assembling into a button half-cell, standing for 12h, and carrying out electrochemical test, wherein the test results are shown in the following table 1.
TABLE 1 results of electrochemical testing of each group
| Group of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| 50 weeks circulation (%) | 97.6 | 98.5 | 97.9 | 98.2 | 93.1 |
| DSC(℃) | 231.2 | 235.4 | 229.1 | 230.2 | 215.2 |
As can be seen from table 1, the cycle and safety performance of the batteries manufactured by using the ternary cathode composite materials having the core-shell structure in examples 1 to 4 of the present invention are significantly higher than those of the battery manufactured by using the Al-coated cathode material in comparative example 1. Therefore, the mixed-arrangement layer is formed through doping modification in an inducing mode, the nano spinel nickel lithium manganate is coated to form a core-shell structure, and the stability and safety of the material are obviously improved while the residual alkali of the material is reduced.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not cause the essence of the corresponding technical solutions to depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (18)
1. The ternary cathode composite material is characterized by having a core-shell structure, wherein the core-shell structure has a chemical general formula of Li a Ni b Co c Mn d M e O 2 Is a core of a compound of the formula (II) with the chemical formula Li x Ni (0.5-y) Mn (1.5+y) O 4 The compound of (a) is a shell;
wherein a is more than or equal to 1 and less than or equal to 1.2, b is more than or equal to 0.8 and less than or equal to 1, c is more than 0 and less than 0.2, d is more than 0 and less than 0.2, b + c + d =1, e is more than 0 and less than or equal to 0.01, and M is selected from at least one of Ru, ir and V elements; x is more than or equal to 1.15 and less than or equal to 1.2, and y is more than or equal to 0 and less than or equal to 0.2;
the preparation method of the ternary cathode composite material comprises the following steps:
(a) Mixing a nickel source, a cobalt source, a manganese source, a lithium source and a doping agent with water, grinding, drying and calcining to obtain the nuclear material with the core-shell structure;
(b) Crushing and sieving the core material obtained in the step (a), testing the total alkali of the core material after sieving, and according to the test result and the chemical general formula Li x Ni (0.5-y) Mn (1.5+y) O 4 X is more than or equal to 1.15 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 0.2, the addition amounts of the nickel source and the manganese source are obtained through calculation, the nickel source and the manganese source are added, and the ternary positive electrode composite material is obtained through calcination after mixing;
wherein, the above-mentionedThe base includes LiOH content and Li 2 CO 3 And (4) content.
2. The ternary positive electrode composite according to claim 1, wherein in step (a), the nickel source comprises a salt of nickel and/or an oxide of nickel;
and/or;
the cobalt source comprises a salt of cobalt and/or an oxide of cobalt;
and/or;
the manganese source comprises a salt of manganese and/or an oxide of manganese;
and/or;
the lithium source comprises a salt of manganese and/or a hydroxide of lithium;
and/or;
the dopant includes a salt of Ru, ir, V element and/or an oxide thereof.
3. The ternary positive electrode composite of claim 2, wherein the nickel source comprises at least one of nickel oxide, nickel sesquioxide, nickel sulfate, nickel nitrate, and nickel chloride;
and/or;
the cobalt source comprises at least one of cobaltosic oxide, cobalt sulfate, cobalt nitrate and cobalt chloride;
and/or;
the manganese source comprises at least one of manganous manganic oxide, manganese carbonate, manganese oxide, manganese dioxide, manganese sulfate, manganese nitrate and manganese chloride;
and/or;
the lithium source comprises at least one of lithium carbonate, lithium hydroxide, lithium nitrate and lithium sulfate;
and/or;
the dopant comprises Ru 2 O、IrO 2 And V 2 O 5 At least one of (1).
4. The ternary positive electrode composite according to claim 3, wherein the nickel source is nickel oxide;
and/or;
the cobalt source is cobaltosic oxide;
and/or;
the manganese source is mangano-manganic oxide.
5. The ternary positive electrode composite according to claim 1, wherein in step (a), the solid content of the mixed mixture is 20% to 60%.
6. The ternary positive electrode composite according to claim 5, wherein in step (a), the solid content of the mixed mixture is 30% to 40%.
7. The ternary positive electrode composite according to claim 1, wherein in step (a), the milled grinding media comprise zirconia beads having a particle size of 0.1-0.2 mm.
8. The ternary positive electrode composite according to claim 7, characterized in that the grinding time is comprised between 1 and 5h.
9. The ternary positive electrode composite according to claim 7, wherein the D50 of the milled slurry is 0.4 μm or less.
10. The ternary positive electrode composite according to claim 1, wherein the drying is spray drying; the particle size of the powder obtained after spray drying is below 5 mu m.
11. The ternary positive electrode composite according to claim 1, wherein in step (a), the calcination temperature is 700-1100 ℃;
the calcination time is 6-20h.
12. The ternary positive electrode composite according to claim 11, wherein the temperature of the calcination is 800-950 ℃;
the calcining time is 8-15h.
13. The ternary positive electrode composite according to claim 1, wherein in step (a) and/or step (b), the calcination is carried out in an oxygen-containing atmosphere.
14. The ternary positive electrode composite according to claim 13, wherein the oxygen-containing atmosphere comprises air and oxygen.
15. The ternary positive electrode composite according to claim 1, wherein in step (b), the manganese source and/or the nickel source has a particle size of 10 to 200nm.
16. The ternary positive electrode composite according to claim 1, wherein in step (b), the calcination temperature is 700 to 950 ℃;
the calcining time is 4-10h.
17. The ternary positive electrode composite according to claim 16, wherein the temperature of the calcination is 800-900 ℃;
the calcining time is 5-7h.
18. A lithium ion battery comprising the ternary positive electrode composite of any of claims 1-17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110980031.8A CN113690419B (en) | 2021-08-25 | 2021-08-25 | Ternary positive electrode composite material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110980031.8A CN113690419B (en) | 2021-08-25 | 2021-08-25 | Ternary positive electrode composite material, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113690419A CN113690419A (en) | 2021-11-23 |
| CN113690419B true CN113690419B (en) | 2023-04-14 |
Family
ID=78582311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110980031.8A Active CN113690419B (en) | 2021-08-25 | 2021-08-25 | Ternary positive electrode composite material, preparation method thereof and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113690419B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975965B (en) * | 2022-06-28 | 2023-10-24 | 北京当升材料科技股份有限公司 | Core-shell type positive electrode material, and preparation method and application thereof |
| CN116525815B (en) * | 2023-06-30 | 2023-11-17 | 宜宾锂宝新材料有限公司 | Spherical lithium nickel manganese oxide positive electrode material, preparation method thereof and composite positive electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007213866A (en) * | 2006-02-07 | 2007-08-23 | Nissan Motor Co Ltd | Battery active material and secondary battery |
| CN103178257A (en) * | 2012-12-10 | 2013-06-26 | 深圳市天骄科技开发有限公司 | Method for preparing precursor of positive material of nickel manganese cobalt multi-element lithium ion battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101630736B (en) * | 2009-08-17 | 2011-11-02 | 深圳市天骄科技开发有限公司 | Improvement method of cycle performance of lithium battery tertiary cathode material |
| CN102394295B (en) * | 2011-11-23 | 2015-09-30 | 东莞新能源科技有限公司 | A kind of lithium ion battery and positive electrode thereof |
| CN103794783B (en) * | 2014-03-07 | 2015-12-09 | 哈尔滨工业大学 | A kind of preparation method of anode material for high-voltage lithium ion of nucleocapsid structure |
| CN105098177B (en) * | 2014-04-24 | 2018-05-29 | 宁德时代新能源科技股份有限公司 | Secondary lithium battery and preparation method of positive electrode material thereof |
| CN110571427B (en) * | 2019-09-09 | 2021-01-05 | 中伟新材料股份有限公司 | Ternary cathode material, preparation method thereof and lithium battery |
| CN113060776B (en) * | 2021-03-31 | 2023-07-25 | 蜂巢能源科技有限公司 | Layered cobalt-free positive electrode material, preparation method thereof and lithium ion battery |
-
2021
- 2021-08-25 CN CN202110980031.8A patent/CN113690419B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007213866A (en) * | 2006-02-07 | 2007-08-23 | Nissan Motor Co Ltd | Battery active material and secondary battery |
| CN103178257A (en) * | 2012-12-10 | 2013-06-26 | 深圳市天骄科技开发有限公司 | Method for preparing precursor of positive material of nickel manganese cobalt multi-element lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113690419A (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113060776B (en) | Layered cobalt-free positive electrode material, preparation method thereof and lithium ion battery | |
| CN110474026B (en) | Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof | |
| KR102669854B1 (en) | Single-crystal multi-element cathode material and its manufacturing method and application | |
| CN111509214B (en) | High-nickel layered composite material and lithium ion battery anode material prepared from same | |
| CN113707875B (en) | Spinel type lithium nickel manganese oxide, preparation method thereof and lithium ion battery | |
| JP6251843B2 (en) | Method for producing lithium metal composite oxide having layer structure | |
| CN113690419B (en) | Ternary positive electrode composite material, preparation method thereof and lithium ion battery | |
| JP7172301B2 (en) | Transition metal composite hydroxide, method for producing transition metal composite hydroxide, lithium transition metal composite oxide active material, and lithium ion secondary battery | |
| KR20160075404A (en) | Manufacuring method of cathode active material for lithium rechargeable battery, and cathode active material made by the same | |
| CN113078316B (en) | Lithium molybdate-coated lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| KR20130108630A (en) | Positive active material, process for producing same, and lithium secondary battery including same | |
| CN115924978A (en) | Manganese-based layered sodium-ion battery positive electrode material and preparation method and application thereof | |
| KR101338371B1 (en) | Manufacturing method of lithium nickel cobalt aluminium composite oxide, lithium nickel cobalt aluminium composite oxide made by the same, lithium secondary battery comprising the same | |
| CN114284470A (en) | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery | |
| CN113764638A (en) | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery | |
| CN113690431B (en) | Lithium manganate positive electrode material, preparation method, improvement method and application thereof | |
| CN114583150A (en) | Positive electrode active material and use thereof | |
| CN113666430A (en) | Lithium-rich cathode material, preparation method thereof and lithium ion battery | |
| WO2016011963A1 (en) | Method for preparing lithium nickel manganese oxide positive battery electrode material, and lithium nickel manganese oxide positive battery electrode material | |
| CN113120964A (en) | Preparation method of spherical lithium manganate material | |
| CN110808371A (en) | Multi-element lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| KR101547632B1 (en) | 5 5 manufacuring method of 5 spinel complex-oxide 5 spinel complex-oxide made by the same and lithium rechargeable batteries comprising the same | |
| TWI578601B (en) | Method of preparing lithium nickel manganese oxide cathode material | |
| CN115050937B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN116072858B (en) | Niobium-doped nickel-cobalt-manganese lithium aluminate quaternary material, preparation method thereof and lithium ion battery containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |