CN110364721A - Nickel cobalt manganese stuff and other stuff and preparation method thereof, nickle cobalt lithium manganate anode material for lithium-ion batteries and preparation method thereof and lithium ion battery - Google Patents
Nickel cobalt manganese stuff and other stuff and preparation method thereof, nickle cobalt lithium manganate anode material for lithium-ion batteries and preparation method thereof and lithium ion battery Download PDFInfo
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- CN110364721A CN110364721A CN201910694489.XA CN201910694489A CN110364721A CN 110364721 A CN110364721 A CN 110364721A CN 201910694489 A CN201910694489 A CN 201910694489A CN 110364721 A CN110364721 A CN 110364721A
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- nickel
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 50
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000010405 anode material Substances 0.000 title claims abstract description 30
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010941 cobalt Substances 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229910001868 water Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000010792 warming Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- QJFSQWZVVOVYEZ-UHFFFAOYSA-N [Li+].[Li+].[Co++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Li+].[Co++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O QJFSQWZVVOVYEZ-UHFFFAOYSA-N 0.000 claims description 7
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 5
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- BXRRQHBNBXJZBQ-UHFFFAOYSA-L dichloromanganese;hydrate Chemical compound O.Cl[Mn]Cl BXRRQHBNBXJZBQ-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 vacuum drying Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910006178 NixCoyMn(1-x-y)(OH)2 Inorganic materials 0.000 description 1
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
Abstract
The invention discloses a kind of nickel cobalt manganese stuff and other stuff and preparation method thereof, nickle cobalt lithium manganate anode material for lithium-ion batteries and preparation method thereof and lithium ion batteries, are related to technical field of lithium batteries.The preparation method of the nickel cobalt manganese stuff and other stuff include the soluble salt of the soluble salt of nickel, the soluble salt of cobalt and manganese is soluble in water, mixed solution is made to being completely dissolved in stirring；Then mixed solution is dried, obtains nickel cobalt manganese stuff and other stuff.The nickel cobalt manganese stuff and other stuff of acquisition can be mixed directly with lithium source, be then sintered.The application eliminates the preparation process of ternary precursor, and in ternary precursor preparation process waste water subsequent processing, furthermore, the preparation process for preparing ternary precursor is complicated, the high requirements on the equipment, leads to that entire the production cost increases, using preparation method provided by the present application, without preparing ternary precursor, cost is saved, has improved the market competitiveness of battery to a certain extent.
Description
Technical field
The present invention relates to technical field of lithium batteries, in particular to a kind of nickel cobalt manganese stuff and other stuff and preparation method thereof,
Nickle cobalt lithium manganate anode material for lithium-ion batteries and preparation method thereof and lithium ion battery.
Background technique
Positive electrode is the important component of lithium ion battery, and the height of cost directly affects the cost of battery,
Have many advantages, such as the ternary material of layer structure because cheap, capacity is high, good cycle, security performance are higher, is considered
It is one of the anode material for lithium-ion batteries of most prospect.Currently, the ternary material of mass production mainly uses hydro-thermal method, solid phase
Method, coprecipitation etc. prepare ternary precursor, then again by ternary precursor and lithium source mixed sintering；Wherein, ternary forerunner
Body material is nickel cobalt manganese hydroxide NixCoyMn(1-x-y)(OH)2, it is ternary composite cathode material presoma product, is with nickel
Salt, cobalt salt, manganese salt are raw material, and the ratio (x:y:z) of the inside nickel cobalt manganese can adjust according to actual needs.
In the preparation process of ternary material, preparing for ternary precursor is particularly important, and preparation process is complicated, to each side
Face requirement is relatively high, while can generate a large amount of waste water during the preparation process.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide the preparation method of nickel cobalt manganese stuff and other stuff, nickel cobalt manganese stuff and other stuff, nickel cobalt mangaic acids
Preparation method, nickle cobalt lithium manganate anode material for lithium-ion batteries and the lithium ion battery of lithium ion battery positive electrode.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of preparation method of nickel cobalt manganese stuff and other stuff comprising:
The soluble salt of the soluble salt of nickel, the soluble salt of cobalt and manganese is soluble in water, and it is molten that mixing is made to being completely dissolved in stirring
Liquid；
Then the mixed solution is dried, obtains the nickel cobalt manganese stuff and other stuff；
Preferably, the drying is spray drying.
In alternative embodiments, in the mixed solution, the molar ratio of nickel ion, cobalt ions and manganese ion is
5.5-6.5:1.5-2.5:1.5-2.5；
Preferably, in the mixed solution, the molarity of the soluble salt of the nickel is 0.68-0.82 mol/L,
The molarity of the soluble salt of the cobalt is 0.18-0.32mol/L, and the molarity of the soluble salt of the manganese is
0.18-0.32mol/L。
In alternative embodiments, the particle size distribution range of the nickel cobalt manganese stuff and other stuff is 1-20 μm.
Second aspect, the embodiment of the present invention provide a kind of nickel cobalt manganese stuff and other stuff, are appointed using such as aforementioned embodiments
The preparation method of nickel cobalt manganese stuff and other stuff described in one is prepared；
Preferably, the sphericity of the nickel cobalt manganese stuff and other stuff is 0.83-0.95；
Preferably, the particle size distribution range of the nickel cobalt manganese stuff and other stuff is 1-20 μm.
The third aspect, the embodiment of the present invention provide a kind of preparation method of nickle cobalt lithium manganate anode material for lithium-ion batteries,
Nickel cobalt manganese stuff and other stuff as described in the previous embodiments is mixed with lithium source, is then sintered.
In alternative embodiments, the nickel in the molal quantity of the lithium in the lithium source and the nickel cobalt manganese stuff and other stuff,
The ratio between cobalt, total mole number of manganese are (1.01-1.1): 1.
In alternative embodiments, the sintering includes: to handle at 850-980 DEG C under air or oxygen atmosphere
12-20h；
Preferably, before handling 12-20h at 850-980 DEG C, further include first being warming up to 150-250 DEG C, keep the temperature 2-3h,
Then it is warming up to 500-600 DEG C again, keeps the temperature 2-3h, is then warming up to 850-980 DEG C again；
Preferably, it is heated up with the heating rate of 8-12 DEG C/min.
In alternative embodiments, the nickel cobalt manganese stuff and other stuff is mixed with the lithium source by ball milling；
Preferably, ball milling mixing is carried out using planetary ball mill；
Preferably, incorporation time 20-30min.
Fourth aspect, the embodiment of the present invention provide a kind of nickle cobalt lithium manganate anode material for lithium-ion batteries, are using such as
The preparation method of the described in any item nickle cobalt lithium manganate anode material for lithium-ion batteries of aforementioned embodiments is prepared.
5th aspect, the embodiment of the present invention provide a kind of lithium ion battery comprising nickel as described in the previous embodiments
Cobalt manganic acid lithium anode material for lithium-ion batteries.
The invention has the following advantages:
Directly the fusion solution of the soluble salt of the soluble salt of nickel, the soluble salt of cobalt and manganese is dried in the application, is obtained
Obtain spherical nickel cobalt manganese stuff and other stuff.Nickel cobalt manganese stuff and other stuff obtained can be in nickle cobalt lithium manganate anode material for lithium-ion batteries
Process directly mixed with lithium source after roasted, eliminate the preparation process of ternary precursor, while also eliminating existing
There is the subsequent processing of waste water in ternary precursor preparation process in technology, in addition, the preparation process for preparing ternary precursor is complicated,
The high requirements on the equipment, cause it is entire the production cost increases, using preparation method provided by the present application, without preparing ternary forerunner
Body, has saved cost, improves the market competitiveness of battery to a certain extent.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the SEM picture of nickle cobalt lithium manganate anode material for lithium-ion batteries prepared by the embodiment of the present application 4；
Fig. 2 is that the cycle-index-gram of nickle cobalt lithium manganate anode material for lithium-ion batteries prepared by the embodiment of the present application 4 is held
Spirogram.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below just to nickel cobalt manganese stuff and other stuff provided in this embodiment and preparation method thereof, nickle cobalt lithium manganate lithium ion battery
Pole material and preparation method thereof and lithium ion battery.
On the one hand, this application provides a kind of nickel cobalt manganese stuff and other stuff and preparation method thereof.
Preparation method include the soluble salt of the soluble salt of nickel, the soluble salt of cobalt and manganese is soluble in water, stirring is to complete
Mixed solution is made in dissolution；Then mixed solution is dried, obtains nickel cobalt manganese stuff and other stuff.
The application, it is not necessary that precipitating reagent is added, without preparing ternary precursor, is omitted when preparing nickel cobalt manganese stuff and other stuff
The preparation process of ternary precursor in the prior art, reduces preparation section, the nickel cobalt manganese mangcorn obtained by spray drying
Son can directly be mixed with lithium source to be roasted.
Specifically, in mixed solution, the molar ratio of nickel ion, cobalt ions and manganese ion is 5.5-6.5:1.5-
2.5:1.5-2.5；In other embodiments of the invention, in mixed solution, mole of nickel ion, cobalt ions and manganese ion
Than for for example can be any one of 5.5:2.5:2,6:2:2,6.5:1.5:2,6.5:2:1.5 or it is any between the two
Value range.When the molar ratio of nickel ion, cobalt ions and manganese ion is 6:2:2, belong to typical 622 ternary material.
By the molar ratio of metal ion in three kinds of raw materials of control in the application, it is more fully mixed to enable to three's, and mix
The sphericity formed afterwards is preferable.
Preferably, the amount ratio of the weight of the soluble salt of the soluble salt of nickel, the soluble salt of cobalt and manganese and water is 1g:2.5-
4ml, to guarantee in mixed solution, the molarity of the soluble salt of nickel is 0.68-0.82mol/L, the soluble salt of cobalt
Molarity is 0.18-0.32mol/L, and the molarity of the soluble salt of manganese is 0.18-0.32mol/L.The application
By controlling soluble salt, the soluble salt of cobalt and the soluble salt molarity of manganese of nickel, this three's component can be guaranteed in water
In sufficiently dissolution mixing, for dry mixed, mix it is more preferably uniform, dispersion degree is more preferably.In the present embodiment, water can be
Deionized water, ultrapure water, purified water and distilled water etc..
Drying in the application is spray drying, is carried out especially by spray drying device, is obtained after spray-dried
Nickel cobalt manganese stuff and other stuff is spherical in shape, sphericity 0.83-0.95, and particle size distribution range, at 1-20 μm, particle diameter distribution is wide, vibration
Real density increases, and the positive electrode that can be packed into the battery of unit volume increases, this is conducive to the energy density for increasing battery
(specific capacity).Further, spherical nickel cobalt manganese stuff and other stuff also has excellent mobility, dispersibility and processability,
The coating for being conducive to make positive electrode slurry and electrode slice, improves electrode tablet quality.
The nickel cobalt manganese stuff and other stuff good sphericity obtained through above-mentioned preparation method, particle diameter distribution is wide, can be directly mixed with lithium source
It closes to be roasted, eliminates the preparation process of ternary precursor in the prior art, considerably reduce the cost of battery.
On the other hand, present invention also provides a kind of nickle cobalt lithium manganate anode material for lithium-ion batteries and preparation method thereof.
The preparation method of the nickle cobalt lithium manganate anode material for lithium-ion batteries is by by the above-mentioned nickel cobalt manganese prepared
After stuff and other stuff is directly mixed with lithium source, it is sintered acquisition.
Specifically, in the present embodiment, the molal quantity of the lithium in lithium source in nickel cobalt manganese stuff and other stuff nickel, cobalt, manganese it is total
The molar ratio of number is (1.01-1.1): 1, it can guarantee the mixture homogeneity of nickel cobalt manganese stuff and other stuff and lithium source.Typical but non-limit
Property processed, molar ratio can for 1.01:1,1.02:1,1.03:1,1.04:1,1.05:1,1.06:1,1.07:1,1.08:1,
Any one of 1.09:1 and 1.1:1 or any value range between the two.
In the present embodiment, lithium source includes but is not limited to one of lithium carbonate and lithium hydroxide or a variety of.In the present embodiment,
Being mixed into for nickel cobalt manganese stuff and other stuff and lithium source is dry-mixed, and the mode for directlying adopt ball milling is mixed, and only physical layer is mixed
It closes, lithium source is not added using the technique of wet-mixing, therefore, the lithium ion in the application is not easy to form lithium branch in negative terminal surface
Crystalline substance ensure that prepared ternary material gram volume with higher.Specific in the present embodiment preferably use planetary type ball-milling
Machine carries out ball milling mixing, incorporation time 20-30min.
The mixture of sintering nickel cobalt manganese stuff and other stuff and lithium source is sintered, lithium source is enabled to enter nickel cobalt manganese mixing
Particle is conducive to promote compacted density, improves cycle performance.Specifically, in the present embodiment, using three-stage sintering by the way of into
Row sintering, is first warming up to 150-250 DEG C with the heating rate of 8-12 DEG C/min, 2-3h is kept the temperature, then again with 8-12 DEG C/min's
Heating rate is warming up to 500-600 DEG C, keeps the temperature 2-3h, is then warming up to 850-980 again with the heating rate of 8-12 DEG C/min
DEG C, handle 12-20h.
In the present embodiment, first under lower temperature (150-250 DEG C) to the mixture of nickel cobalt manganese stuff and other stuff and lithium source into
Row processing, at this point, 150-250 DEG C of temperature is not up to sintering temperature, by drying at such a temperature to mixture, gradually
The moisture in mixture is reduced, is avoided at a high temperature of mixture is directly placed in sintering, aqueous vapor is acutely discharged, and leads to sintered part
Surface the phenomenon that being bubbled.It is also able to achieve mixture is preheated for 150-250 DEG C simultaneously, mixture internal-external temperature difference is made to contract
It is small, it avoids the problem that generating local burning.Then 500-600 DEG C at a temperature of mixture is handled, 500-600 at this time
DEG C temperature reach the temperature that mixture can be reacted, but temperature that not up to can be fully sintered, mixture is in the temperature
Under can existing carry out pre-burning, reaction time 2-3h in burn-in process, enables to mixture first to react a period of time, with
When reaching 850-980 DEG C of sintering temperature again afterwards, mixture can be sintered completely, and the processing time at this time is longer, reach 12-20h,
It can guarantee fully sintered, the mixing of nickel cobalt manganese stuff and other stuff and lithium source and sintering are more complete, more sufficiently.
Pass through the good sphericity for the nickle cobalt lithium manganate anode material for lithium-ion batteries that the above method prepares, particle diameter distribution
Extensively, gram volume is high, good cycle, has carried out after 30 circulations capacity retention ratio 93.9% or more, for the first time charge and discharge efficiency
Up to 93%.
In addition, present invention also provides a kind of lithium ion batteries comprising above-mentioned nickle cobalt lithium manganate lithium ion cell positive
Material.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of nickel cobalt manganese stuff and other stuff is present embodiments provided, preparation method includes: to weigh Nickelous nitrate hexahydrate
436.5g, cabaltous nitrate hexahydrate 145.5g, four water manganese nitrate 125.5g (Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate, four water at this time
The molar ratio of manganese nitrate is 6:2:2), it is dissolved in 2000mL deionized water, stirring, then will be molten by peristaltic pump to complete molten state
Liquid is squeezed into spray drying device and is dried, and nickel cobalt manganese stuff and other stuff, the particle size range of gained nickel cobalt manganese stuff and other stuff are obtained
At 1~20 μm.
Embodiment 2
A kind of nickel cobalt manganese stuff and other stuff is present embodiments provided, preparation method includes: to weigh Nickel dichloride hexahydrate
332.8g, cobalt chloride hexahydrate 142.8g, four chloride hydrate manganese 99.0g are dissolved in 2000mL deionized water (six hydration at this time
Nickel chloride, cobalt chloride hexahydrate, four chloride hydrate manganese molar ratio be 5.6:2.4:2), then stirring passes through to complete molten state
Solution is squeezed into spray drying device and is dried by peristaltic pump, obtains nickel cobalt manganese stuff and other stuff, gained nickel cobalt manganese stuff and other stuff
Particle size range at 1~20 μm.
Embodiment 3
Present embodiments provide a kind of nickel cobalt manganese stuff and other stuff, preparation method include: weigh nickel sulfate hexahydrate 420.6,
Cobalt monosulfate heptahydrate 140.6g, manganese sulfate monohydrate 67.6g are dissolved in 2000mL deionized water (six hydration nickel sulfate, seven water at this time
Close cobaltous sulfate, the molar ratio of manganese sulfate monohydrate is 6.4:2:1.6), then stirring to complete molten state passes through peristaltic pump for solution
It squeezes into spray drying device and is dried, obtain nickel cobalt manganese stuff and other stuff, the particle size range of gained nickel cobalt manganese stuff and other stuff is 1
~20 μm.
Embodiment 4
A kind of nickle cobalt lithium manganate anode material for lithium-ion batteries is present embodiments provided, preparation method includes:
By in nickel cobalt manganese stuff and other stuff made from the molal quantity of the lithium in lithium carbonate and embodiment 1 nickel, cobalt, manganese sum
Molar ratio matched by 1.05:1, in planetary ball mill ball milling 25min, obtain product to be burnt.
Product to be burnt is placed in atmosphere Muffle furnace, under air atmosphere, is first warming up to the heating rate of 10 DEG C/min
200 DEG C, 2h is kept the temperature, is then warming up to 550 DEG C again with the heating rate of 10 DEG C/min, 2h is kept the temperature, then again with 10 DEG C/min's
Heating rate is warming up to 950 DEG C, handles 15h, obtains nickle cobalt lithium manganate anode material for lithium-ion batteries.
The nickle cobalt lithium manganate anode material for lithium-ion batteries is subjected to electron-microscope scanning, referring to Fig. 1, can from figure
Out, prepared ternary material sphericity is 0.87, and particle diameter distribution is 2-18 μm, it can be seen that its good sphericity, partial size point
Cloth range is wider.
Embodiment 5
A kind of nickle cobalt lithium manganate anode material for lithium-ion batteries is present embodiments provided, preparation method includes:
By in nickel cobalt manganese stuff and other stuff made from the molal quantity of the lithium in lithium carbonate and embodiment 1 nickel, cobalt, manganese sum
Matched in molar ratio by 1.02:1, in planetary ball mill ball milling 22min, obtain product to be burnt.
Product to be burnt is placed in atmosphere Muffle furnace, under air atmosphere, is first warming up to the heating rate of 9 DEG C/min
160 DEG C, 3h is kept the temperature, is then warming up to 520 DEG C again with the heating rate of 9 DEG C/min, 3h is kept the temperature, then again with the liter of 9 DEG C/min
Warm speed is warming up to 860 DEG C, handles 18h.
Embodiment 6
A kind of nickle cobalt lithium manganate anode material for lithium-ion batteries is present embodiments provided, preparation method includes:
By in nickel cobalt manganese stuff and other stuff made from the molal quantity of the lithium in lithium carbonate and embodiment 1 nickel, cobalt, manganese sum
Molar ratio matched by 1.1:1, in planetary ball mill ball milling 29min, obtain product to be burnt.
Product to be burnt is placed in atmosphere Muffle furnace, under air atmosphere, is first warming up to the heating rate of 11 DEG C/min
240 DEG C, 2h is kept the temperature, is then warming up to 590 DEG C again with the heating rate of 11 DEG C/min, 2h is kept the temperature, then again with 11 DEG C/min's
Heating rate is warming up to 980 DEG C, handles 13h.
Embodiment 7
A kind of nickle cobalt lithium manganate anode material for lithium-ion batteries is present embodiments provided, preparation method includes:
By in nickel cobalt manganese stuff and other stuff made from the molal quantity of the lithium in lithium carbonate and embodiment 1 nickel, cobalt, manganese sum
Matched in molar ratio by 1.05:1, in planetary ball mill ball milling 25min, obtain product to be burnt.
Product to be burnt is placed in atmosphere Muffle furnace, under air atmosphere, is first warming up to the heating rate of 10 DEG C/min
550 DEG C, keep the temperature 2h, be then warming up to 950 DEG C again with the heating rate of 10 DEG C/min, handle 15h, obtain nickle cobalt lithium manganate lithium from
Sub- cell positive material.
It for the present embodiment is compared to embodiment 4, is omitted and " is first warming up to 200 DEG C with the heating rate of 10 DEG C/min, protects
The step of warm 2h ", is directly warming up to 550 DEG C, through inventor the study found that moisture when being directly warming up to 550 DEG C in sinter
It cannot be smoothly discharged, the gram volume in turn resulting in embodiment 7 can decrease to a certain extent.
Embodiment 8
Present embodiments provide a kind of nickle cobalt lithium manganate anode material for lithium-ion batteries, preparation method and 4 base of embodiment
This is identical, and difference is: in the present embodiment, by nickel cobalt manganese mangcorn made from the molal quantity of the lithium in lithium carbonate and embodiment 1
The sum of nickel, cobalt, manganese in son is matched by 0.9:1 in molar ratio.
Reduced in the present embodiment the molal quantity of the lithium in lithium carbonate in nickel cobalt manganese stuff and other stuff nickel, cobalt, manganese it is total
Number in molar ratio, through inventor the study found that since the deficiency of lithium will lead to fault in material, when then causing battery charging and discharging
The lithium of migration tails off and cycle performance is caused to reduce.
Embodiment 9
Present embodiments provide a kind of nickle cobalt lithium manganate anode material for lithium-ion batteries, preparation method and 4 base of embodiment
This is identical, and difference is: in the present embodiment, by nickel cobalt manganese mangcorn made from the molal quantity of the lithium in lithium carbonate and embodiment 1
The sum of nickel, cobalt, manganese in son is matched by 1.2:1 in molar ratio.
Increased in the present embodiment the molal quantity of the lithium in lithium carbonate in nickel cobalt manganese stuff and other stuff nickel, cobalt, manganese it is total
Number in molar ratio, through inventor the study found that lithium to will cause surface residual alkali amount excessively high with excessively high, to influence its electrification
Performance is learned, irreversible capacity loss is such as increased, deteriorates cycle performance.
Test experience
Nickle cobalt lithium manganate anode material for lithium-ion batteries, conductive agent and binder prepared by above-described embodiment 4 is according to 80:
The ratio of 10:10 mixes, then prepared with vacuum ball grinder 600rmp ball milling 2h be uniformly mixed and the slurry of modest viscosity into
Electrode slice is prepared in row coating, vacuum drying, and conductive agent uses super " P ", and diaphragm is celgard 2300, and electrolyte is selected
LiPF6 conductive salt and DMC:DEC:EC (wt%)=1:1:1 solvent of 1mol/L, is added suitable VC in electrolyte solution
Do additive.Charge and discharge blanking voltage is 2.3~4.75V, and the first effect and cycle performance of battery are tested under 0.1C state.
Referring to Fig. 2, can be seen that nickle cobalt lithium manganate lithium ion battery prepared by embodiment 4 from the electric discharge gram volume of Fig. 2
Positive electrode gram volume is high, good cycle, has carried out after 30 circulations capacity retention ratio 93.9% or more, charge and discharge for the first time
Efficiency is up to 93%.
Comparative experiments
Comparative example 1: nickle cobalt lithium manganate lithium ion battery is prepared using the existing precipitation method (patent document CN108545786A)
Positive electrode.
By nickel chloride, cobalt chloride, manganese chloride, the ratio of 0.4:0.2:0.4 is dissolved in ammonium chloride solution and configures in molar ratio
Nickel cobalt manganese mixing salt solution；The solution is added dropwise in the sodium hydrate aqueous solution that temperature is 100 DEG C, pH value is maintained at
13；Sufficiently at change after addition, and mixing speed control particle size is controlled, it is compound that last washing of precipitate obtains nickel-cobalt-manganese multi
Presoma；The lithium nitrate aqueous solution that molarity is 2mol/L is added, is sufficiently mixed by mixing plant, then use
Atomizer drying-granulating machine, 105 DEG C of outlet temperature, obtains spherical precursor by 230 DEG C of inlet temperature；Presoma is put into
Continous way atmosphere protection stove is sintered under oxygen-enriched atmosphere, then 400 DEG C of Isothermal sinter 2h are warming up to 900 DEG C of Isothermal sinters again
7h is then cooled to room temperature to obtain the final product.It is 190.4mAh/g that the effect recorded from it, which can be seen that initial charge gram volume, for the first time
Electric discharge gram volume is 168.4mAh/g, first charge-discharge efficiency 88.5%.
Embodiment 4 and comparative example 1 are compared as can be seen that eliminating the preparation of ternary precursor in the application
Journey reduces preparation section, directly does the aqueous solution of Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and four nitric hydrate manganese by spraying
It is dry, obtain spherical nickel cobalt manganese stuff and other stuff.Due to eliminating the preparation process of ternary precursor in the application, also necessarily save
In the prior art in ternary precursor preparation process waste water subsequent processing, in addition, prepare the preparation process of ternary precursor
Complexity, the high requirements on the equipment, cause it is entire the production cost increases, using preparation method provided by the present application, without preparing ternary
Presoma, has saved cost, improves the market competitiveness of battery to a certain extent.And it puts for the first time as can be seen from Figure 2
Capacitance is apparently higher than 168.4mAh/g, and charging capacity is higher than 190.4mAh/g certainly accordingly.
Comparative example 2
Comparative example 2 is substantially same as Example 4, and difference is: lithium carbonate is obtained with after spray drying in embodiment 4
The mixing of nickel cobalt manganese stuff and other stuff, and in comparative example 2, it is in Nickelous nitrate hexahydrate, cabaltous nitrate hexahydrate and four nitric hydrate manganese
Lithium carbonate (realizing wet-mixing) is added before mixture spray drying, subsequent co-spray is dry.
Using wet-mixing Nickelous nitrate hexahydrate, the mixture and lithium carbonate of cabaltous nitrate hexahydrate and four nitric hydrate manganese,
Lithium ion is easy to form Li dendrite in negative terminal surface, to reduce gram volume.And using directly by six nitric hydrates in the application
The mixture of nickel, cabaltous nitrate hexahydrate and four nitric hydrate manganese is spray-dried, and obtains spherical nickel cobalt manganese stuff and other stuff, then right
Nickel cobalt manganese stuff and other stuff and lithium carbonate carry out ball milling mixing (dry method), can effectively reduce lithium ion in this way and be formed in negative terminal surface
Li dendrite, to ensure that prepared ternary material gram volume with higher.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nickel cobalt manganese stuff and other stuff, characterized in that it comprises:
The soluble salt of the soluble salt of nickel, the soluble salt of cobalt and manganese is soluble in water, and mixed solution is made to being completely dissolved in stirring；
Then the mixed solution is dried, obtains the nickel cobalt manganese stuff and other stuff；
Preferably, the drying is spray drying.
2. the preparation method of nickel cobalt manganese stuff and other stuff according to claim 1, which is characterized in that the soluble salt of the nickel,
The soluble salt of the soluble salt of the cobalt and the manganese is selected from one of nitrate, chlorate, sulfate or a variety of；
Preferably, in the mixed solution, the molar ratio of nickel ion, cobalt ions and manganese ion is 5.5-6.5:1.5-2.5:
1.5-2.5；
Preferably, in the mixed solution, the molarity of the soluble salt of the nickel is 0.68-0.82mol/L, the cobalt
The molarity of soluble salt be 0.18-0.32mol/L, the molarity of the soluble salt of the manganese is 0.18-
0.32mol/L。
3. the preparation method of nickel cobalt manganese stuff and other stuff according to claim 1, which is characterized in that the nickel cobalt manganese mangcorn
The particle size distribution range of son is 1-20 μm.
4. a kind of nickel cobalt manganese stuff and other stuff, which is characterized in that it is mixed using nickel cobalt manganese as described in any one of claims 1-3
The preparation method for closing particle is prepared；
Preferably, the sphericity of the nickel cobalt manganese stuff and other stuff is 0.83-0.95；
Preferably, the particle size distribution range of the nickel cobalt manganese stuff and other stuff is 1-20 μm.
5. a kind of preparation method of nickle cobalt lithium manganate anode material for lithium-ion batteries, which is characterized in that will be as claimed in claim 4
Nickel cobalt manganese stuff and other stuff mixed with lithium source, be then sintered.
6. the preparation method of nickle cobalt lithium manganate anode material for lithium-ion batteries according to claim 5, which is characterized in that institute
State the lithium in lithium source molal quantity and the nickel cobalt manganese stuff and other stuff in nickel, cobalt, manganese sum molar ratio be (1.01-
1.1):1。
7. the preparation method of nickle cobalt lithium manganate anode material for lithium-ion batteries according to claim 5, which is characterized in that institute
Stating sintering includes: to handle 12-20h at 850-980 DEG C under air or oxygen atmosphere；
Preferably, before handling 12-20h at 850-980 DEG C, further include first being warming up to 150-250 DEG C, keep the temperature 2-3h, then
It is warming up to 500-600 DEG C again, keeps the temperature 2-3h, is then warming up to 850-980 DEG C again；
Preferably, it is heated up with the heating rate of 8-12 DEG C/min.
8. the preparation method of nickle cobalt lithium manganate anode material for lithium-ion batteries according to claim 5, which is characterized in that institute
The nickel cobalt manganese stuff and other stuff stated is mixed with the lithium source by ball milling；
Preferably, ball milling mixing is carried out using planetary ball mill；
Preferably, incorporation time 20-30min.
9. a kind of nickle cobalt lithium manganate anode material for lithium-ion batteries, which is characterized in that it is using such as any one of claim 5-8
The preparation method of the nickle cobalt lithium manganate anode material for lithium-ion batteries is prepared.
10. a kind of lithium ion battery, which is characterized in that it includes nickle cobalt lithium manganate lithium ion battery as claimed in claim 9
Positive electrode.
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