CN106395920A - Element co-doping modified ternary lithium ion battery cathode material, and preparation method thereof - Google Patents
Element co-doping modified ternary lithium ion battery cathode material, and preparation method thereof Download PDFInfo
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- CN106395920A CN106395920A CN201610737994.4A CN201610737994A CN106395920A CN 106395920 A CN106395920 A CN 106395920A CN 201610737994 A CN201610737994 A CN 201610737994A CN 106395920 A CN106395920 A CN 106395920A
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- lithium
- ion
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- anode material
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000010406 cathode material Substances 0.000 title abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 62
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000005253 cladding Methods 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 26
- 239000010405 anode material Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- -1 Zn2+ Chemical compound 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 230000008569 process Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 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
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 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
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 9
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [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
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 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
- FZRNJOXQNWVMIH-UHFFFAOYSA-N lithium;hydrate Chemical class [Li].O FZRNJOXQNWVMIH-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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 compound 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052752 metalloid 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
- 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
- 230000008439 repair process Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an element co-doping modified ternary lithium ion battery cathode material, and a preparation method thereof. According to the preparation method, compounds of two kinds of metals Me<1> and Me<2> are respectively selected based on the difference of ion radiuses of lithium ion and transition metal ions in the lithium nickel cobalt manganese ternary material, and are subjected to high temperature sintering with a nickel cobalt manganese precursor, wherein the ion radius of the metal Me<1> ion is close to that of lithium ion, and the metal Me<1> ion is one or a mixture of ions selected from Zn2+ and Zr4+, the radius of the metal Me<2> ion is close to that of transition metal ion Co3+ or Mn4+, and the metal Me<2> is one or a mixture of ions selected from Al3+, V5+, and Ge4+; and then a primary product obtained via high temperature sintering is subjected to second cladding so as to obtain the element co-doping modified ternary lithium ion battery cathode material. The element co-doping modified ternary lithium ion battery cathode material is capable of achieving synergistic effects of two metal elements fully, and improving cycle performance of lithium ion batteries effectively.
Description
Technical field
The invention belongs to technical field of lithium ion, it is related to a kind of element codoping modified ternary lithium ion cell positive
Material and preparation method.
Background technology
Lithium nickel cobalt manganese ternary material has higher energy density, less expensive cost and relatively reliable safety because of it
Become a kind of common electrokinetic cell positive electrode.Different from LiFePO4 olivine structural, lithium nickel cobalt manganese ternary material has
Stratiform α-NaFeO2Structure, belongs to RM space group, oxonium ion cubic closest packing forms octahedra basic framework, lithium ion and mistake
Cross the gap that metal ion occupies oxygen octahedra, and be arranged alternately into lithium layer and transition metal layer along (111) crystal face.
Furthermore, Li in ternary material+Radius is 0.076 nm, t in Co ion2gThree tracks are full up, egTwo
Sky is the most stable entirely for individual track, Ni ion egTwo tracks are occupied by two electronics respectively, manganese ion egTwo tracks are entirely empty, so
Overall electronic structure is the most stable, so Co, Ni, Mn ion is 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 in ternary material, metal ion radius divides two classes (to put aside Ni2+), the larger lithium ion of radius ratio and radius ratio are relatively
Little transition metal ionss (Co3+Or Mn4+).The patent of Application No. CN201510072192 is by tertiary cathode material and La2O3
Mixing secondary high-temperature sintering obtains the La that adulterates3+Ternary material；The patent of Application No. CN201510672398 discloses a step and burns
Knot preparation doping Ca2+The method of ternary material, is burnt by nickeliferous, cobalt, manganese, the compound of calcium and lithium source are ground further high temperature
Knot is obtained, and above patent passes through high temperature sintering it is difficult to ensure that having the La of larger ionic radius3+Or Ca2+(radius is respectively
For 0.1032 nm, 0.1 nm) smoothly, be evenly distributed in bulk structure.The patent side of Application No. CN201510234496
Overweight the Al close with transition metal ionss radius using coprecipitation preparation doping3+Improve bulk density and the cyclicity of material
Energy.Because lithium layer is arranged alternately along (111) crystal face with transition metal layer, single introducing is close with lithium ion radius
Me1Ion or the Me close with transition metal ionss radius2Ion, all can lead to the disproportionate change of cell parameter, cause lattice
Structural aberration, the performance of impact material.
Content of the invention
Present invention aims to the feature of lithium nickel cobalt manganese ternary material lattice structure, targetedly select respectively
The Me close with lithium ion radius1Ion and the close Me of transition metal ionss radius2Ion co-doped, and pass through secondary working
Skill forms protective layer on surface, thus preparation has the ternary material of 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 is Liα(NixCoyMnz)1-a-bMe1 a
Me2 bNcO2, metal Me in chemical formula1Ion is close with the radius of lithium ion, selected from Zn2+、Zr4+At least one；Metal Me2
Ion is close with the radius of transition metal ionss, selected from Al3+、V5+、Ge4+One or more, N is the cladding being distributed in top layer
Element, selected from Al, Zr, Ti one or more.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, comprises 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, contain Me1The compound of ion and
Containing Me2The compound of ion is sufficiently mixed, and is placed in a high-temperature calcination in sintering furnace after the completion of batch mixing, sinters the material block completing and leads to
Cross crushing process and obtain the Me that adulterates1And Me2Substandard products；
2) the doping Me secondly previous step being obtained1And Me2Substandard products and the compound containing N to press formula mixed in molar ratio equal
Even, subsequent mixed material enters stove double sintering, obtains the ternary lithium ion anode material of modification.
Described nickel cobalt manganese presoma, can be to include the oxide of nickel, cobalt and manganese element, hydroxide, carbonate
One or more；Described lithium source, can be Lithium hydrate, the lithium carbonate including elemental lithium；Described Me1Ion combination
Thing, can be to include Zn2+、Zr4+Oxide, acetate, sulfate, nitrate, one or more of ester salt；Described
Me2The compound of ion, can be to include Al3+、V5+、Ge4+Oxide, hydroxide, sulfate, nitrate, ammonium salt,
Alkoxide, ester salt, one or more of mineral；Described compound containing N, can be include Al, Zr, Ti element oxide,
Hydroxide, alkoxide, one or more of ester salt.
Processing step 1）Described in 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 be 4 ~ 8 h.
The tertiary cathode material of the present invention and preparation technology compare tool advantages below：
The codoping modified ternary anode material for lithium-ion batteries being prepared by the method for the present invention, has excellent electrochemistry circulation
Performance.Reason is that currently preferred dopant ion radius is connect with lithium ion in ternary material or transition metal ionss radius
Closely, in high-temperature sintering process can more, faster, more uniformly incorporate in bulk structure, thus in electrochemistry cyclic process
Middle support lattice structure, reduces the risk that three dimensional structure collapses；Secondly, the present invention disposably introduces two kinds of metal ion
Carry out the doping of diverse location, cell parameter collaborative variation, while expanding lithium ion transport passage, distortion of lattice does not occur, real
One or more unapproachable effects of other metal ion mixings existing, pass through secondary processes simultaneously and form protection on surface
Layer, the erosion of suppression electrolyte, collective effect lifts multiplying power and the cycle performance of material.
Brief description
Fig. 1 is the modified tertiary cathode material stereoscan photograph (SEM) according to embodiment in the present invention 1 preparation.
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 electrochemistry prepared according to embodiment in the present invention 1 and comparative example 1, comparative example 2, comparative example 3
Cycle performance conservation rate comparison diagram.
Specific embodiment
The present invention is expanded on further below by way of being embodied as example, but this is not limitation of the present invention, this area
Technical staff according to the basic thought of the present invention, various modifications may be made or improves, basic without departing from the present invention
Thought, all within the scope of the present invention.
Embodiment 1
Weigh 50 g Ni0.5Co0.2Mn0.3(OH)2, 20.9212 g lithium carbonate, 0.6754 g zirconium dioxide, 1.1115 g mono- water
Softening aluminium stone, adds ball milling in mixing tank to mix together.Then the material mixing loading crucible is inserted Muffle furnace high temperature to burn
Knot, using air atmosphere, 900 °C of sintering 10 h.The material block that sintering is completed crushes the substandard products obtaining Al, Zr Uniform Doped.
Weigh 60 °C of constant temperature stirrings of dehydrated alcohol that 0.7570g aluminum isopropylate. is added to 50mL, treat that aluminum isopropylate. is completely molten
Add substandard products obtained in the previous step after solution, continue stirring until solvent is evaporated completely, be transferred in 110 °C of baking ovens and be dried 10
H, then be placed in Muffle furnace 700 °C of sintering 6 h, after sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
The stereoscan photograph (SEM) of above-mentioned positive electrode is as shown in Figure 1.
Meanwhile, by the ternary material of this preparation and white carbon black, Kynoar in mass ratio 90:5:5 are fabricated to positive plate,
It is assembled into 2032 type button cells with metal lithium sheet, barrier film, electrolyte.100 circle charge and discharge cycles tests are chosen voltage window and are
2.8 4.25 V, electric current density is 1C/1C, and result of the test is as shown in Figure 2.
Embodiment 2
Weigh 50 g Ni0.35Co0.35Mn0.30(OH)2, 20.9212 g lithium carbonate, 1.7532 g tetrahydrated zirconium sulfates, 1.8526 g
Aluminum sulfate octadecahydrate, adds ball milling in mixing tank to mix together.Then the material mixing loading crucible is inserted in Muffle furnace
High temperature sintering, using air atmosphere, 1000 °C of sintering 10 h.The material block that sintering is completed crushes and obtains Al, Zr Uniform Doped
One substandard products.
Weigh 60 °C of constant temperature stirring 10 min of dehydrated alcohol that 0.7099 g butyl titanate is added to 50 mL again, then
Add substandard products obtained in the previous step, continue stirring until solvent is evaporated completely, be transferred in 110 °C of baking ovens and 10 hs are dried, then
It is placed in Muffle furnace 850 °C of sintering 5 h, after sintering, material is crossed 300 mesh sieves and obtained modified ternary material.
Embodiment 3
First weigh 0.6309 g zirconium-n-butylate, 0.3785 g aluminum isopropylate. is put in 100 mL dehydrated alcohol, 60 °C of heating are stirred
Mix 20 min, add 50 g Ni0.35Co0.35Mn0.30(OH)2, continuing constant temperature stirring mixing, until being evaporated, being then placed in
10 hs are dried in 100 °C of baking ovens.Take the material that drying finishes uniform with 13.5624 g Lithium hydrate ball milling mixings.Mixing finishes
Afterwards above-mentioned material is placed in high temperature furnace with 950 °C of sintering 12 h of air atmosphere.The material block that sintering is completed crushes and obtains Al, Zr
One substandard products of Uniform Doped.
Substandard products obtained in the previous step and 0.3377 g zirconium oxide ball milling mixing are placed in sintering, sintering temperature in Muffle furnace
900 °C, sintering time 4 h.After sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
Embodiment 4
Weigh 50 g Ni0.35Co0.35Mn0.30CO3, 13.5625 g Lithium hydrates, 0.6754 g zirconium dioxide, 0.4463 g five
V 2 O, adds ball milling in mixing tank to mix together.Then the material mixing loading crucible is inserted Muffle furnace high temperature
Sintering, using air atmosphere, 890 °C of sintering 15 h.The material block that sintering is completed crushes the substandard products obtaining Zr, V Uniform Doped.
Substandard products obtained in the previous step and 0.3377 g zirconium oxide ball milling mixing are placed in sintering, sintering temperature in Muffle furnace
900 °C, sintering time 4 h.After sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
Embodiment 5
Weigh 50 g Ni0.5Co0.2Mn0.3(OH)2, 21.7259 g lithium carbonate, 0.1412 g five water zirconium nitrate, 0.0288g dioxy
Change germanium, add ball milling in mixing tank to mix together.Then the material mixing loading crucible is inserted Muffle furnace high temperature sintering,
Using air atmosphere, 940 °C of sintering 10 h.The material block that sintering is completed crushes the substandard products obtaining Zr, Ge Uniform Doped.
Substandard products obtained in the previous step and 0.0378 g aluminium oxide ball milling mixing are placed in sintering, sintering temperature in Muffle furnace
750 °C, sintering time 5 h.After sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
Embodiment 6
Weigh 57.2466 g nickel sulfate hexahydrates, 30.6172 g cobalt sulfates, 32.8878 g anhydrous manganous sulfates, 23.1340 g
Lithium carbonate, 0.5217 g zirconium oxide, 0.5782g aluminium hydroxide add ball milling in mixing tank to mix together.Then will mix
Material loads crucible and inserts Muffle furnace high temperature sintering, using air atmosphere, 10500 °C of sintering 8 h.The material block that sintering is completed
The broken substandard products obtaining Zr, Al Uniform Doped.
Substandard products obtained in the previous step are mixed with 0.0834 g titanium dioxide ball milling and is placed in sintering in Muffle furnace, sintering temperature
600 °C of degree, sintering time 5 h.After sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
Embodiment 7
First weigh 1.0996 g zinc sulphate heptahydrate, 0.5741 g ammonium metavanadate is put in 80 mL deionized waters, 80 °C of heating
Stir 30 min, add 50 g Ni0.50Co0.25Mn0.25(OH)2, continuing constant temperature stirring mixing, until being evaporated, being then placed in
12 hs are dried in 120 °C of baking ovens.Take the material that drying finishes uniform with 22.1282 g lithium carbonate ball milling mixings.After mixing finishes
Above-mentioned material is placed in high temperature furnace with 980 °C of sintering 10 h of air atmosphere.The material block that completes of sintering is crushed to obtain Zn, V equal
One substandard products of even doping.
Substandard products obtained in the previous step and 0.4337 g aluminium hydroxide ball milling mixing are placed in Muffle furnace and sinter, 800 °C
Sinter 6 h.After sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
Embodiment 8
Weigh 50 g Ni0.6Co0.2Mn0.2(OH)2, 13.0408 g Lithium hydrates, 0.3357 g zinc acetate dihydrate, 0.2161 g
Germanium dioxide, adds ball milling in mixing tank to mix together.Then the material mixing loading crucible is inserted Muffle furnace high temperature
Sintering, using air atmosphere, 800 °C of sintering 10 h.The material block that sintering is completed crushes and obtains Zn, Ge Uniform Doped once
Product.
Weigh 0.2103 g zirconium-n-butylate again and be added to 60 °C of constant temperature of dehydrated alcohol of 50 mL and stir 10 min, then plus
Enter substandard products obtained in the previous step, continue stirring until solvent is evaporated completely, be transferred in 110 °C of baking ovens and 10 hs are dried, then put
400 °C of sintering 8 h in Muffle furnace, after sintering, material is crossed 300 mesh sieves and is obtained modified ternary material.
Comparative example 1
Copy the preparation method of a sample and secondary sample in embodiment 1, be simply added without zirconium oxide and boehmite, obtain
Modified ternary material to independent Al cladding.
And copy button cell processing technology assembled battery in embodiment 1, characterize the electrification of this time ternary material of preparation
Learn cycle performance, and contrasted with embodiment 1 material, result is as shown in Figure 2.
Comparative example 2
Copy the preparation method of a sample and secondary sample in embodiment 1, be simply added without zirconium oxide, obtain the mono- doping of Al simultaneously
The modified ternary material of Al cladding.
And copy button cell processing technology assembled battery in embodiment 1, characterize the electrification of this time ternary material of preparation
Learn cycle performance, and contrasted with embodiment 1 material, result is as shown in Figure 2.
Comparative example 3
Copy the preparation method of a sample and secondary sample in embodiment 1, be simply added without boehmite, obtain that Zr is mono- to be mixed
The modified ternary material that miscellaneous and Al coats.
And copy button cell processing technology assembled battery in embodiment 1, characterize the electrification of this time ternary material of preparation
Learn cycle performance, and contrasted with embodiment 1 material, result is as shown in Figure 2.
The modified tertiary cathode material XRD spectrum of above example and comparative example synthesis adopts Topas software refine lattice
Parametric results are as shown in table 1
Table 1
Can be seen that from upper table data and compare with the comparative example 1 sample c/a value not having any doping, comparative example 2 and 3 is individually mixed
Miscellaneous Al or Zr can diminish it is meant that individually doping Al or Zr causes structure cell in a direction excessively extension, causes structure cell
Distortion.And c/a value is basic and comparative example 1 is equal in embodiment 1-8, illustrate that co-doped is golden with lithium ion radius, transition respectively
Belong to the two metalloid ions that ionic radius is similar to, because ionic radius is close to each other, two class ions of codope can be more convenient
Evenly into the similar layer of ionic radius, so that cell parameter collaborative variation, do not send out while expanding lithium ion transport passage
Raw distortion of lattice, realizes one or more unapproachable effects of other metal ion mixings.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (11)
1. the codoping modified ternary anode material for lithium-ion batteries of a kind of element, formula is Liα(NixCoyMnz)1-a-bMe1 a
Me2 bNcO2, metal Me in chemical formula1Ion is close with the radius of lithium ion, selected from Zn2+、Zr4+At least one；Metal Me2
Ion and transition metal ionss (Co3+Or Mn4+) radius close, selected from Al3+、V5+、Ge4+One or more, N be distributed in
The cladding element on top layer, selected from Al, Zr, Ti one or more；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. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of a kind of element as claimed in claim 1, its
The method being characterised by described comprises the steps：
Be first according in chemical formula each element mol ratio by the presoma of nickel and cobalt containing manganese, lithium source, contain Me1The compound of ion and containing
Me2The compound of ion is sufficiently mixed, and is placed in a high-temperature calcination in sintering furnace after the completion of batch mixing, sinters the material block completing and passes through
Crushing process obtains the Me that adulterates1And Me2Substandard products；
Secondly doping Me previous step being obtained1And Me2Substandard products and the compound containing N to press formula mixed in molar ratio equal
Even, subsequent mixed material enters stove double sintering, obtains the ternary lithium ion anode material of modification.
3. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature exists
In：Described nickel cobalt manganese presoma, includes the oxide of nickel, cobalt and manganese element, hydroxide, one kind of carbonate or many
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 exists
In：Described lithium source is to include Lithium hydrate, 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 exists
In：Described Me1Ionic radius is close 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
It is, described Me1The compound of ion, include the oxide of above-mentioned ion, acetate, sulfate, nitrate, the one of ester salt
Plant or multiple.
7. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature
It is：Described Me2Ionic radius is close with transition metal ionss, 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
It is, described Me2The compound of ion, include the oxide of above-mentioned ion, hydroxide, sulfate, nitrate, ammonium salt,
Alkoxide, ester salt, 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
It is：Described is once sintered, 800 ~ 1100 °C of sintering temperature, sintering time 5 ~ 15 h.
10. the preparation method of the codoping modified ternary anode material for lithium-ion batteries of element as claimed in claim 2, its feature
It is：Compound containing N, include the oxide of Al, Zr, Ti element, hydroxide, alkoxide, one or more of ester salt.
The preparation method of the codoping modified ternary anode material for lithium-ion batteries of the element described in 11. claim 2, its feature exists
In：Described secondary high-temperature sintering, 400 ~ 900 °C of sintering temperature, sintering time 4 ~ 8 h.
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