CN106395920B - A kind of codoping modified ternary anode material for lithium-ion batteries of element and preparation method - Google Patents
A kind of codoping modified ternary anode material for lithium-ion batteries of element and preparation method Download PDFInfo
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- CN106395920B CN106395920B CN201610737994.4A CN201610737994A CN106395920B CN 106395920 B CN106395920 B CN 106395920B CN 201610737994 A CN201610737994 A CN 201610737994A CN 106395920 B CN106395920 B CN 106395920B
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 54
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 9
- 238000013459 approach Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000005253 cladding Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- -1 Zn2+ Chemical compound 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000004703 alkoxides Chemical class 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910052752 metalloid Inorganic materials 0.000 abstract description 2
- 150000002738 metalloids Chemical class 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical class O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical class [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical class O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical class O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical class [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical class [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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 present invention discloses a kind of codoping modified ternary anode material for lithium-ion batteries of element and preparation technology, first according to the difference of lithium ion in ternary material and transition metal ions ionic radius, selects two metalloid Me respectively1、Me2Compound and nickel cobalt manganese presoma carry out high temperature sintering, wherein metal Me1The radius of ion and lithium ion approaches, selected from Zn2+、Zr4+At least one；Metal Me2Ion and transition metal ions (Co3+Or Mn4+) radius approach, selected from Al3+、V5+、Ge4+One or more, the substandard products of high temperature sintering one are secondly subjected to secondary cladding process and handle to obtain a kind of ternary lithium ion anode material of modification.The ternary material prepared using this technique can give full play to the synergy of two kinds of metallic elements, effectively lift the cycle performance of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, is related to a kind of codoping modified ternary lithium ion cell positive of element
Material and preparation method.
Background technology
Lithium nickel cobalt manganese ternary material has higher energy density, less expensive cost and relatively reliable security because of it
As a kind of common electrokinetic cell positive electrode.Different from LiFePO4 olivine structural, lithium nickel cobalt manganese ternary material tool
Stratiform α-NaFeO2Structure, belong to RM space groups, oxonium ion cubic closest packing form octahedra basic framework, lithium ion and mistake
The gap that metal ion occupies oxygen octahedra is crossed, and lithium layer and transition metal layer are arranged alternately into along (111) crystal face.
Furthermore, Li in ternary material+Radius is 0.076 nm, t in Co ions2gThree tracks are full up, egTwo
Most stable, the Ni ions e of the full sky of individual trackgTwo tracks are occupied by two electronics respectively, manganese ion egTwo tracks are entirely empty, so
Overall electronic structure is most stable, so Co, Ni, Mn ion are respectively with Co3+、Ni2+、Mn4+Form exist, such transition metal from
Ni in son2+Radius is 0.069 nm, Co3+Radius is 0.0545 nm, Mn4+Radius is 0.053 nm.Can from ionic radius data
To find that metal ion radius is divided to two classes (to put aside Ni in ternary material2+), the bigger lithium ion of radius and radius ratio compared with
Small transition metal ions (Co3+Or Mn4+).Application No. CN201510072192 patent is by tertiary cathode material and La2O3
Mixing secondary high-temperature sinters to obtain doping La3+Ternary material；Application No. CN201510672398 patent discloses step burning
Knot prepares doping Ca2+The method of ternary material, burnt by the way that nickeliferous, cobalt, manganese, the compound of calcium and lithium source are ground into further high temperature
Knot is made, and above patent is by high temperature sintering it is difficult to ensure that the La with larger ionic radius3+Or Ca2+(radius is difference
For 0.1032 nm, 0.1 nm) smoothly, be evenly distributed in bulk structure.Application No. CN201510234496 patent side
Overweight and doping and the close Al of transition metal ions radius are prepared using coprecipitation3+Improve the bulk density and cyclicity of material
Energy.Because lithium layer is arranged alternately with transition metal layer along (111) crystal face, single introducing and lithium ion radius are close
Me1Ion or the Me close with transition metal ions radius2Ion, it can all cause the disproportionate change of cell parameter, cause lattice
Structural aberration, influence the performance of material.
The content of the invention
The characteristics of it is an object of the invention to for lithium nickel cobalt manganese ternary material lattice structure, targetedly selection are distinguished
The close Me with lithium ion radius1Ion and the close Me of transition metal ions radius2Ion co-doped, and pass through secondary working
Skill forms protective layer on surface, so as to prepare the ternary material with excellent multiplying power and cycle performance.
To achieve these goals, the present invention adopts the following technical scheme that：
A kind of codoping modified ternary anode material for lithium-ion batteries of element, formula Liα(NixCoyMnz)1-a-b Me1 a
Me2 bNcO2, the metal Me in chemical formula1The radius of ion and lithium ion approaches, selected from Zn2+、Zr4+At least one；Metal Me2
The radius of ion and transition metal ions approaches, selected from Al3+、V5+、Ge4+One or more, N is the cladding for being distributed in top layer
Element, the one or more selected from Al, Zr, Ti.Wherein 0.90≤α≤1.15,0.25≤x≤0.65,0.15≤y≤0.40,
0.15≤z≤0.40, x+y+z=1,0.0004≤a≤0.01,0.0004≤b≤0.01,0.0004≤c≤0.005.
The preparation technology of above-mentioned positive electrode, include two-step process step：
1) be first according in chemical formula each element mol ratio by the presoma of nickel and cobalt containing manganese, lithium source, containing Me1The chemical combination of ion
Thing and containing Me2The compound of ion is sufficiently mixed, and a high-temperature calcination in sintering furnace is placed in after the completion of batch mixing, sinters the material of completion
Block obtains adulterating Me by crushing process1And Me2A substandard products；
2) the doping Me for secondly obtaining previous step1And Me2A substandard products mixed with the compound containing N by formula mol ratio
Close uniformly, subsequent mixed material enters stove double sintering, obtains modified ternary lithium ion anode material.
Described nickel cobalt manganese presoma, can be the oxide, hydroxide, carbonate for including nickel, cobalt and manganese element
One or more；Described lithium source, can be lithium hydroxide, the lithium carbonate for including elemental lithium；Described Me1Ion combination
Thing, can include Zn2+、Zr4+Oxide, acetate, sulfate, nitrate, the one or more of ester salt；Described
Me2The compound of ion, can include Al3+、V5+、Ge4+Oxide, hydroxide, sulfate, nitrate, ammonium salt,
Alkoxide, ester salt, the one or more of mineral；Described compound containing N, can be include Al, Zr, Ti element oxide,
Hydroxide, alkoxide, the one or more of ester salt.
Processing step 1）Described in it is once sintered, sintering temperature be 800 ~ 1100 °C, sintering time be 5 ~ 15
h；Processing step 2）Described in double sintering, sintering temperature be 400 ~ 900 °C, sintering time is 4 ~ 8 h.
The tertiary cathode material and preparation technology of the present invention compares tool advantages below：
The codoping modified ternary anode material for lithium-ion batteries being prepared by the method for the present invention, there is excellent electrochemistry
Cycle performance.Reason is in lithium ion or transition metal ions radius in currently preferred Doped ions radius and ternary material
It is close, more, faster, more uniformly it can be incorporated in high-temperature sintering process in bulk structure, so as to be circulated throughout in electrochemistry
Lattice structure is supported in journey, reduces the risk that three-dimensional structure collapses；Secondly, the present invention disposably introduce two kinds of metal from
Son carries out the doping of diverse location, cell parameter collaborative variation, distortion of lattice does not occur while expanding lithium ion transport passage,
The unapproachable effect of other one or more kinds of metal ion mixings is realized, while is formed and protected on surface by secondary processes
Layer, suppresses the erosion of electrolyte, and collective effect lifts the multiplying power and cycle performance of material.
Brief description of the drawings
Fig. 1 is the modification tertiary cathode material stereoscan photograph (SEM) prepared according to embodiment in the present invention 1.
Fig. 2 is the tertiary cathode material electricity prepared according to embodiment in the present invention 1 and comparative example 1, comparative example 2, comparative example 3
Chemical cycle performance discharge specific capacity comparison diagram；
Fig. 3 is the tertiary cathode material electricity prepared according to embodiment in the present invention 1 and comparative example 1, comparative example 2, comparative example 3
Chemical cycle property retention rate comparison diagram.
Embodiment
The present invention is expanded on further below by way of specific implementation example, but this is not limitation of the present invention, this area
Technical staff according to the present invention basic thought, various modifications may be made or improve, without departing from the present invention it is basic
Thought, within the scope of the present invention.
Embodiment 1
Weigh 50 g Ni0.5Co0.2Mn0.3(OH)2, 20.9212 g lithium carbonates, 0.6754 g zirconium dioxides, 1.1115 g
Boehmite, ball milling in mixing tank is added together and is mixed.The material mixed is then fitted into crucible and inserts height in Muffle furnace
Temperature sintering, using air atmosphere, 900 °C of 10 h of sintering.The material block for sintering completion is crushed and obtains Al, Zr Uniform Doped once
Product.
60 °C of constant temperature stirrings of absolute ethyl alcohol that 0.7570 g aluminium isopropoxides are added to 50 mL are weighed, treat that aluminium isopropoxide is complete
A substandard products obtained in the previous step are added after dissolving, continue stirring until solvent be evaporated completely, be transferred in 110 °C of baking ovens dry
10 h, then 700 °C of 6 h of sintering in Muffle furnace are placed in, material crosses 300 mesh sieves and obtains modified ternary material after sintering.
The stereoscan photograph (SEM) of above-mentioned positive electrode is as shown in Figure 1.
Meanwhile the ternary material and carbon black, Kynoar in mass ratio 90 for preparing this:5:5 are fabricated to positive plate,
2032 type button cells are assembled into metal lithium sheet, barrier film, electrolyte.100 circle charge and discharge cycles tests choose voltage window and are
2.8-4.25 V, current density 1C/1C, result of the test are as shown in Figure 2.
Embodiment 2
Weigh 50 g Ni0.35Co0.35Mn0.30(OH)2, 20.9212 g lithium carbonates, 1.7532 g tetrahydrated zirconium sulfates,
1.8526 g aluminum sulfate octadecahydrates, ball milling in mixing tank is added together and is mixed.Then the material mixed loading crucible is inserted
Muffle furnace high temperature sinters, using air atmosphere, 1000 °C of 10 h of sintering.The material block completed will be sintered, and broken to obtain Al, Zr equal
One substandard products of even doping.
60 °C of constant temperature 10 min of stirring of absolute ethyl alcohol that 0.7099 g butyl titanates are added to 50 mL are weighed again, then
Add a substandard products obtained in the previous step, continue stirring until solvent be evaporated completely, be transferred in 110 °C of baking ovens dry 10 h, then
It is placed in Muffle furnace 850 °C of 5 h of sintering, material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Embodiment 3
First weigh 0.6309 g zirconium-n-butylates, 0.3785 g aluminium isopropoxides are put into 100 mL absolute ethyl alcohols, 60 °C plus
The min of thermal agitation 20, add 50 g Ni0.35Co0.35Mn0.30(OH)2, continue constant temperature and be stirred, until be evaporated, and it is rearmounted
10 h are dried in 100 °C of baking ovens.Take the dry material finished and 13.5624 g lithium hydroxide ball milling mixings uniform.Mix
Above-mentioned material is placed in high temperature furnace with 950 °C of 12 h of sintering of air atmosphere after finishing.To sinter the material block completed it is broken obtain Al,
One substandard products of Zr Uniform Dopeds.
A substandard products obtained in the previous step are placed in Muffle furnace with 0.3377 g zirconium oxide ball milling mixings and sintered, sintering temperature
900 °C, the h of sintering time 4.Material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Embodiment 4
Weigh 50 g Ni0.35Co0.35Mn0.30CO3, 13.5625 g lithium hydroxides, 0.6754 g zirconium dioxides, 0.4463
G vanadic anhydrides, ball milling in mixing tank is added together and is mixed.The material mixed is then fitted into crucible and inserts height in Muffle furnace
Temperature sintering, using air atmosphere, 890 °C of 15 h of sintering.The material block for sintering completion is crushed and obtains Zr, V Uniform Doped once
Product.
A substandard products obtained in the previous step are placed in Muffle furnace with 0.3377 g zirconium oxide ball milling mixings and sintered, sintering temperature
900 °C, the h of sintering time 4.Material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Embodiment 5
Weigh 50 g Ni0.5Co0.2Mn0.3(OH)2, 21.7259 g lithium carbonates, the water zirconium nitrates of 0.1412 g five, 0.0288g
Germanium dioxide, ball milling in mixing tank is added together and is mixed.The material mixed loading crucible is then inserted into Muffle furnace high temperature
Sintering, using air atmosphere, 940 °C of 10 h of sintering.The material block for sintering completion is crushed and obtains Zr, Ge Uniform Doped once
Product.
A substandard products obtained in the previous step are placed in Muffle furnace with 0.0378 g aluminum oxide ball milling mixings and sintered, sintering temperature
750 °C, the h of sintering time 5.Material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Embodiment 6
Weigh 57.2466 g nickel sulfate hexahydrates, 30.6172 g cobalt sulfates, 32.8878 g anhydrous manganous sulfates,
23.1340 g lithium carbonates, 0.5217 g zirconium oxides, 0.5782g aluminium hydroxides add ball milling in mixing tank and mixed together.Then will
The material mixed loads crucible and inserts Muffle furnace high temperature sintering, using air atmosphere, 10500 °C of 8 h of sintering.It will sinter
Into material block broken obtain a substandard products of Zr, Al Uniform Doped.
A substandard products obtained in the previous step are mixed to be placed in Muffle furnace with 0.0834 g titanium dioxide ball millings and sintered, sintering temperature
600 °C of degree, the h of sintering time 5.Material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Embodiment 7
First weigh 1.0996 g white vitriols, 0.5741 g ammonium metavanadates are put into 80 mL deionized waters, 80 °C
The min of heating stirring 30, add 50 g Ni0.50Co0.25Mn0.25(OH)2, continue constant temperature and be stirred, until being evaporated, then
It is placed in 120 °C of baking ovens and dries 12 h.Take the dry material finished and 22.1282 g lithium carbonate ball milling mixings uniform.Mix
Above-mentioned material is placed in high temperature furnace with 980 °C of 10 h of sintering of air atmosphere after finishing.To sinter the material block completed it is broken obtain Zn,
One substandard products of V Uniform Dopeds.
A substandard products obtained in the previous step are placed in Muffle furnace with 0.4337 g aluminium hydroxide ball milling mixings and sintered, 800 °C
Sinter 6 h.Material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Embodiment 8
Weigh 50 g Ni0.6Co0.2Mn0.2(OH)2, 13.0408 g lithium hydroxides, 0.3357 g zinc acetate dihydrates,
0.2161 g germanium dioxides, ball milling in mixing tank is added together and is mixed.The material mixed loading crucible is then inserted into Muffle
Stove high temperature sinters, using air atmosphere, 800 °C of 10 h of sintering.The material block for sintering completion is crushed and obtains Zn, Ge Uniform Doped
A substandard products.
60 °C of constant temperature 10 min of stirring of absolute ethyl alcohol that 0.2103 g zirconium-n-butylates are added to 50 mL are weighed again, are then added
Enter a substandard products obtained in the previous step, continue stirring until solvent is evaporated completely, be transferred in 110 °C of baking ovens and dry 10 h, then put
400 °C of 8 h of sintering in Muffle furnace, material crosses 300 mesh sieves and obtains modified ternary material after sintering.
Comparative example 1
The preparation method of a sample and secondary sample in embodiment 1 is copied, is simply added without zirconium oxide and the soft aluminium of a water
Stone, obtain the modification ternary material of independent Al claddings.
And button cell manufacture craft assembled battery in embodiment 1 is copied, characterize the electrification of the ternary material this time prepared
Cycle performance is learned, and is contrasted with the material of embodiment 1, as a result as shown in Figure 2.
Comparative example 2
The preparation method of a sample and secondary sample in embodiment 1 is copied, is simply added without zirconium oxide, obtains that Al is mono- to be mixed
The modification ternary material of miscellaneous and Al claddings.
And button cell manufacture craft assembled battery in embodiment 1 is copied, characterize the electrification of the ternary material this time prepared
Cycle performance is learned, and is contrasted with the material of embodiment 1, as a result as shown in Figure 2.
Comparative example 3
The preparation method of a sample and secondary sample in embodiment 1 is copied, boehmite is simply added without, obtains Zr
Single doping and the modification ternary material of Al claddings.
And button cell manufacture craft assembled battery in embodiment 1 is copied, characterize the electrification of the ternary material this time prepared
Cycle performance is learned, and is contrasted with the material of embodiment 1, as a result as shown in Figure 2.
Above example and the modification tertiary cathode material XRD spectrum of comparative example synthesis use Topas software refine lattices
Parametric results are as shown in table 1
Table 1
It can be seen that from upper table data and compared with the sample c/a values of comparative example 1 without any doping, comparative example 2 and 3 is single
Solely doping Al or Zr can diminish, it is meant that individually doping Al or Zr causes structure cell excessively to extend in a direction, causes
Unit cell distortion.And in embodiment 1-8 c/a values substantially and comparative example 1 be equal, illustrate co-doped respectively with lithium ion radius, mistake
Two similar metalloid ions of metal ion radius are crossed, because ionic radius is close to each other, two class ions of codope can be more
Facilitate evenly into the similar layer of ionic radius, so that cell parameter collaborative variation, while expanding lithium ion transport passage
Distortion of lattice does not occur, realizes the unapproachable effect of other one or more kinds of metal ion mixings.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (11)
1. a kind of codoping modified ternary anode material for lithium-ion batteries of element, formula Liα(NixCoyMnz)1-a- bMe1 aMe2 bNcO2, the metal Me in chemical formula1The radius of ion and lithium ion approaches, selected from Zn2+、Zr4+At least one；Gold
Belong to Me2Ion and transitional metal ion Co3+Or Mn4+Radius approach, selected from Al3+、V5+、Ge4+One or more, N for distribution
Cladding element on top layer, the one or more selected from Al, Zr, Ti；Wherein 0.90≤α≤1.15,0.25≤x≤0.65,
0.15≤y≤0.40,0.15≤z≤0.40, x+y+z=1,0.0004≤a≤0.01,0.0004≤b≤0.01,0.0004≤
c≤0.005。
2. a kind of preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 1, its
It is characterised by that described method comprises the following steps：
Be first according in chemical formula each element mol ratio by the presoma of nickel and cobalt containing manganese, lithium source, containing Me1The compound of ion and contain
Me2The compound of ion is sufficiently mixed, and a high-temperature calcination in sintering furnace is placed in after the completion of batch mixing, and the material block for sintering completion passes through
Crushing process obtains adulterating Me1And Me2A substandard products；
Secondly doping Me previous step obtained1And Me2A substandard products and the compound containing N by formula mixed in molar ratio it is uniform,
Subsequent mixed material enters stove double sintering, obtains modified ternary lithium ion anode material.
3. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Described nickel cobalt manganese presoma, include the oxide, hydroxide, one kind or more of carbonate of nickel, cobalt and manganese element
Kind.
4. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Described lithium source is to include lithium hydroxide, the lithium carbonate of elemental lithium.
5. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Described Me1Ionic radius approaches with lithium ion, including Zn2+、Zr4+At least one.
6. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Described Me1The compound of ion, include the oxide of above-mentioned ion, acetate, sulfate, nitrate, the one of ester salt
Kind is a variety of.
7. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Described Me2Ionic radius approaches with transition metal ions, including Al3+、V5+、Ge4+One or more.
8. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：The Me2The compound of ion, include oxide, hydroxide, sulfate, nitrate, ammonium salt, the alcohol of above-mentioned ion
Salt, ester salt, the one or more of mineral.
9. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Described is once sintered, 800~1100 DEG C of sintering temperature, 5~15h of sintering time.
10. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exist
In：Compound containing N, include the oxide of Al, Zr, Ti element, hydroxide, alkoxide, the one or more of ester salt.
11. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element described in claim 2, its feature exist
In：Described secondary high-temperature sintering, 400~900 DEG C of sintering temperature, 4~8h of sintering time.
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