CN114573043B - Positive electrode material, preparation method and application thereof - Google Patents
Positive electrode material, preparation method and application thereof Download PDFInfo
- Publication number
- CN114573043B CN114573043B CN202111671800.2A CN202111671800A CN114573043B CN 114573043 B CN114573043 B CN 114573043B CN 202111671800 A CN202111671800 A CN 202111671800A CN 114573043 B CN114573043 B CN 114573043B
- Authority
- CN
- China
- Prior art keywords
- equal
- less
- positive electrode
- complexing agent
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 70
- 239000011164 primary particle Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 58
- 239000002243 precursor Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002019 doping agent Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000005056 compaction Methods 0.000 abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 16
- 230000014759 maintenance of location Effects 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 20
- 238000009826 distribution Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000001186 cumulative effect Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 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 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/36—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
- H01M4/54—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of silver
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 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 invention relates to the field of positive electrode materials of lithium ion batteries, and discloses a positive electrode material, a preparation method and application thereof. The method comprisesAverage particle diameter d of primary particles of positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d, d 50 ≤40μm，d σ ≥0.25μm，0.7≤d 50 /d σ Less than or equal to 120; the chemical formula of the positive electrode material is Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is more than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba; j is at least one element selected from S, si, F and Cl. The positive electrode material provided by the invention has good compaction performance, and the lithium ion battery prepared by adopting the positive electrode material has higher initial discharge specific capacity and cycle capacity retention rate.
Description
Technical Field
The invention relates to the field of positive electrode materials of lithium ion batteries, in particular to a positive electrode material, a preparation method thereof and application of the positive electrode material in lithium ion batteries.
Background
Aiming at the defects of the current lithium ion battery, the market provides higher requirements for the lithium ion battery, and the lithium ion battery has the advantages of high energy density, high safety, long cycle life, good thermal stability, low cost and the like, and becomes a key performance index for evaluating the power battery. The nickel cobalt lithium manganate ternary positive electrode material combines the excellent performances of lithium nickelate, lithium cobaltate and lithium manganate, has the characteristics of high specific capacity, long cycle life, environmental friendliness and the like, and is one of the most widely applied lithium ion battery materials at present. The common nickel cobalt lithium manganate positive electrode material in the market mainly comprises agglomerated secondary spherical particles, and the secondary spherical particles nickel cobalt lithium manganate polycrystalline positive electrode material has the problems of low compressive strength, easiness in pulverization in the circulation process, intolerance to a high-voltage system and the like, so that the positive electrode material with high safety, high compaction and high circulation stability gradually becomes a research hot spot in recent years.
The problems of unstable structure, low gas production, low compaction and the like of the polycrystalline positive electrode material are gradually highlighted, and the positive electrode material not only can effectively improve the defects of the polycrystalline material, but also has the advantages of high structural mechanical strength, high compaction density and difficult crushing of particles; the gaps are few, the interfaces of primary particles are few, the contact area between the material and the electrolyte is reduced, and the side reaction is greatly reduced; smooth surface, uniform particles, full contact with conductive agent, and easy lithium ion transmission.
CN109516509a is pre-sintered and crushed by a precursor to prepare a large-particle ternary oxide and a small-particle ternary oxide respectively, and then the large-particle ternary oxide and the small-particle ternary oxide are mixed and sintered by adding lithium according to a certain proportion to improve the compaction density of the material, but the process is complex, the production cost is higher, and meanwhile, the product performance difference cannot be explained from the angle of primary particles.
CN105355911a adopts the processes of primary sintering, doping, secondary sintering and liquid phase cladding of alumina to prepare ternary material, and the shape of ternary material is controlled to further improve the tap density, but the liquid phase cladding process adopted after secondary sintering is more complex, and the subsequent product production process has no cost performance competitive advantage.
CN106910882a describes a method for preparing a large layered cathode material for lithium ion batteries, which prepares a large layered cathode material with an average particle diameter D 50 3.0-8.0 μm, but the improvement of the compaction density is not obvious, and the circulation improvement effect is poor.
The prior art has many methods for preparing the positive electrode material, but lacks a method for evaluating the high-pressure solid positive electrode material by the primary particle size, and the compaction density of the positive electrode material determines the volume energy density of the battery, the cycle safety of the battery and other performances, so that the method for simply and effectively evaluating the compaction density of the positive electrode material is urgent.
Disclosure of Invention
The invention aims to solve the problem of poor pressure resistance of a positive electrode material in the prior art, and provides the positive electrode material, a preparation method thereof and application of the positive electrode material in a lithium ion battery. The positive electrode material has high compaction performance.
In order to achieve the above object, a first aspect of the present invention provides a positive electrode material having an average particle diameter d of primary particles of the positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d, d 50 ≤40μm，d σ ≥0.25μm，0.7≤d 50 /d σ ≤120；
The chemical formula of the positive electrode material is Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is more than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba; j is at least one element selected from S, si, F and Cl.
In a second aspect, the present invention provides a method for preparing a positive electrode material, the method comprising the steps of:
(1) Providing a mixed salt solution containing nickel salt, cobalt salt and manganese salt; providing a precipitant solution containing a precipitant; providing a complexing agent solution I containing a first complexing agent and providing a complexing agent solution II containing a second complexing agent; wherein the concentration of the complexing agent solution I is less than the concentration of the complexing agent solution II;
(2) First mixing the mixed salt solution, the precipitator solution and the complexing agent solution I, and then second mixing the obtained mixture with the complexing agent solution II to obtain precursor slurry;
(3) Performing solid-liquid separation, washing and drying on the precursor slurry to obtain a precursor;
(4) Thirdly mixing the precursor, the lithium source and the doping agent containing M, and roasting to obtain a roasting product; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba;
(5) Fourth mixing the roasting product with an additive containing J, and then performing heat treatment to obtain the positive electrode material; wherein J is at least one element selected from S, si, F and Cl.
A third aspect of the invention provides the use of the positive electrode material according to the first aspect or the positive electrode material prepared according to the method according to the second aspect in a lithium ion battery.
According to the technical scheme, the method provided by the invention prepares the precursor required by the positive electrode material through the liquid phase coprecipitation reaction, in the precursor preparation process, the concentration of the complexing agent solution I is controlled to be smaller than that of the complexing agent solution II to obtain the precursor with specific particle size distribution, then the precursor, the lithium source and the doping agent containing M are mixed and baked, finally the baked product is mixed with the doping agent containing J and then subjected to heat treatment, and the average particle diameter d of primary particles of the positive electrode material is obtained 50 And standard deviation of particle diameter d σ The method meets the following conditions: d, d 50 ≤40μm，d σ ≥0.25μm，0.7≤d 50 /d σ Less than or equal to 120; the chemical formula of the positive electrode material is Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is more than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba; j is at least one element selected from S, si, F and Cl. Average particle diameter d of primary particles of the positive electrode material 50 The ion migration process path in the material is overlong due to oversized primary particles of the positive electrode material and the influence on the power performance of the material is avoided; further, the average particle diameter d of primary particles of the positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is more than or equal to 0.7 50 /d σ The particle distribution of the positive electrode material is not more than 120, and the particle distribution of the positive electrode material can be effectively restrained from being too wide and too narrow. The positive electrode material provided by the invention has high compaction performance, and the lithium ion battery prepared by adopting the positive electrode material has higher initial discharge specific capacity and cycle capacity retention rate.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the precursor prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the precursor prepared in comparative example 2;
fig. 4 is a Scanning Electron Microscope (SEM) image of the positive electrode material prepared in comparative example 2.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a positive electrode material having an average particle diameter d of primary particles of the positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d, d 50 ≤40μm，d σ ≥0.25μm，0.7≤d 50 /d σ ≤120；
The chemical formula of the positive electrode material is Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is more than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba; j is at least one element selected from S, si, F and Cl.
In the present invention, the primary particles of the positive electrode material have an average particle diameter d 50 And standard deviation of particle diameter d σ Obtained by Scanning Electron Microscopy (SEM) image of primary particles (test conditions were 10kV, 3000 x, calculated by particle size measurement software). Wherein the average particle diameter d 50 The average value of the primary particles is calculated to extract more than 200 particles, and the standard deviation d of the particle diameter σ Standard deviation for all primary particle sizes.
In the positive electrode material, primary particles are too narrow in distribution, on one hand, the inter-particle gaps are too large, and the inter-particle contact area is small, so that the migration efficiency of electrons and ions in the material is affected, and the material impedance is increased; on the other hand, gaps among particles in the preparation process of the battery pole piece are larger, mutual support of the particles is less, the particles are seriously pulverized after rolling, and after repeated circulation, the particles are further aggravated due to expansion and shrinkage caused by charge and discharge, so that long-term circulation is influenced; furthermore, the primary particles are too narrowly distributed, and the compacted density of the material is low, so that the volumetric energy density of the positive electrode material is not improved; the primary particles are too wide in distribution, the particle size difference is large, the large difference of the charge and discharge depth of the material is caused by the particles with the large size, the expansion and contraction of the material are different, the pulverization of the material is aggravated in the circulation process, and the circulation capacity retention rate of the material is influenced.
According to some embodiments of the invention, the primary particles of the positive electrode material have an average particle diameter d 50 The ion migration process path in the material is overlong due to oversized primary particles of the positive electrode material and the influence on the power performance of the material is avoided; average particle diameter d of primary particles of the positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is more than or equal to 0.7 50 /d σ And the particle distribution in the positive electrode material is effectively restrained from being too wide and too narrow and the positive electrode material has high compaction performance, so that the first discharge specific capacity and the cycle capacity retention rate of the lithium ion battery are improved.
According to some embodiments of the invention, it is preferable that the positive electrode material has an average particle diameter d 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is more than or equal to 0.4 mu m 50 Less than or equal to 35 mu m; and/or, d σ More than or equal to 0.5 mu m; and/or, 1.ltoreq.d 50 /d σ ≤116。
For example, the average particle diameter d of the positive electrode material 50 Including but not limited to, satisfying: d is more than or equal to 0.5 mu m 50 ≤30μm、0.7μm≤d 50 ≤25μm、0.9μm≤d 50 ≤20μm、1.0μm≤d 50 ≤15μm、1.2μm≤d 50 ≤10μm、1.3μm≤d 50 Less than or equal to 8 mu m or less than or equal to 1.4 mu m and less than or equal to d 50 Less than or equal to 7 mu m, etc.;
and/or, the standard deviation d of the particle diameter of the positive electrode material σ Including but not limited to d σ ≥0.5μm、d σ ≥0.7μm、d σ Not less than 1.0 μm or d σ More than or equal to 0.3 mu m, etc.;
and/or, 1.0.ltoreq.d 50 /d σ ≤100、1.1≤d 50 /d σ ≤70、1.2≤d 50 /d σ ≤50、1.3≤d 50 /d σ ≤25、1.4≤d 50 /d σ ≤15、1.5≤d 50 /d σ D is more than or equal to 10 or 1.5 50 /d σ Less than or equal to 5, etc.
More preferably, the average particle diameter d of the positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is less than or equal to 1.5 mu m 50 Less than or equal to 5 mu m; and/or, d σ More than or equal to 0.5 mu m; and/or, 1.5.ltoreq.d 50 /d σ ≤4。
According to some embodiments of the invention, the positive electrode material has the chemical formula Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is more than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba; j is at least one element selected from S, si, F and Cl.
Preferably, in the chemical formula of the positive electrode material, a is more than or equal to 1 and less than or equal to 1.2,0.5, b is more than or equal to 0.8,0.1, c is more than or equal to 0.4, d is more than or equal to 0.1 and less than or equal to 0.4,0.04, e is more than or equal to 0.3,1.99, f is more than or equal to 1.999,0.001, j is more than or equal to 0.01, and a+b+c+d+e=2;
more preferably, in the chemical formula of the positive electrode material, b is more than or equal to 0.5 and less than or equal to 0.6,0.15 and less than or equal to c is more than or equal to 0.3,0.15 and less than or equal to d is more than or equal to 0.3,0.04 and less than or equal to e is more than or equal to 0.1,1.995 and less than or equal to 1.997,0.003 and less than or equal to j is more than or equal to 0.005, and b+c+d+e=1.
According to some embodiments of the invention, preferably, the positive electrode material is a single crystal positive electrode material.
According to some embodiments of the invention, preferably, M is selected from at least one element of Al, zr, W, mg, sr and Ba, more preferably at least one element of Mg, sr and Ba.
According to some embodiments of the invention, preferably J is selected from at least one element of S, F and Si, more preferably F and/or Si.
In a second aspect, the present invention provides a method for preparing a positive electrode material, the method comprising the steps of:
(1) Providing a mixed salt solution containing nickel salt, cobalt salt and manganese salt; providing a precipitant solution containing a precipitant; providing a complexing agent solution I containing a first complexing agent and providing a complexing agent solution II containing a second complexing agent; wherein the concentration of the complexing agent solution I is less than the concentration of the complexing agent solution II;
(2) First mixing the mixed salt solution, the precipitator solution and the complexing agent solution I, and then second mixing the obtained mixture with the complexing agent solution II to obtain precursor slurry;
(3) Performing solid-liquid separation, washing and drying on the precursor slurry to obtain a precursor;
(4) Thirdly mixing the precursor, the lithium source and the doping agent containing M, and roasting to obtain a roasting product; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba;
(5) Fourth mixing the roasting product with an additive containing J, and then performing heat treatment to obtain the positive electrode material; wherein J is at least one element selected from S, si, F and Cl.
According to some embodiments of the invention, in step (1), the concentration of the complexing agent solution I is less than the concentration of the complexing agent solution II.
According to some embodiments of the invention, the complexing agent solution I preferably has a concentration of 4.5-6.9mol/L, preferably 5.2-6.2mol/L.
According to some embodiments of the invention, the complexing agent solution II preferably has a concentration of 7-11.2mol/L, preferably 9.5-10.3mol/L.
According to the inventionIn some embodiments, by controlling the concentration of complexing agent solution I to be less than the concentration of complexing agent solution II, and combining steps (1), (2), and (3), a precursor having a particular particle size distribution can be obtained. Preferably, the particle size D of the precursor 5 、D 50 、D 95 And degree of particle size dispersion K 95 The method meets the following conditions: k (K) 95 ＝(D 95 -D 5 )/D 50 ，0.9≤K 95 Less than or equal to 2.5; more preferably, 0.9.ltoreq.K 95 And is less than or equal to 2. In the invention, the particle size dispersion degree K of the precursor 95 When the above-defined range is satisfied, the degree of particle size dispersion of the precursor is not particularly large, and deterioration of uniformity of the material due to large difference in size particle reaction during the subsequent firing process is prevented. Meanwhile, the particle size dispersion degree is not concentrated, so that the problem that the positive electrode material has low compaction density due to poor filling of gaps of the material because the particles are too uniform in the subsequent roasting processing process is solved.
In the invention, D 5 The particle size corresponding to the cumulative particle size distribution number of the positive electrode material measured by using a Mastersizer2000 laser particle sizer reaches 5%, namely, the particles with the particle size smaller than (or larger than) the particle size account for 5%; d (D) 50 The particle size corresponding to the cumulative particle size distribution number of the positive electrode material measured by using a Mastersizer2000 laser particle sizer reaches 50%, namely, particles with the particle size smaller than (or larger than) the particle size account for 50%; d (D) 95 The positive electrode material is measured by a Mastersizer2000 laser particle sizer, and the cumulative particle size distribution of the positive electrode material reaches 95%, i.e., the particles having a particle size less than (or greater than) 95% of the particle size.
According to some embodiments of the present invention, the kind of the mixed salt is not particularly limited, and one skilled in the art may select according to practical needs of the application. Preferably, the mixed salt is selected from at least one of a nickel salt, a cobalt salt and a manganese salt, more preferably a nickel salt, a cobalt salt and a manganese salt. By combining the advantages of three elements of nickel, cobalt and manganese and designing different molar ratios of nickel, cobalt and manganese, the anode material can better reach the balance of electric properties in all aspects.
According to some embodiments of the present invention, the nickel salt may be selected from a wide range of types, and any soluble nickel salt commonly used in the art may be used. Preferably, the nickel salt is selected from at least one of nickel sulfate, nickel nitrate and nickel acetate, more preferably nickel sulfate.
According to some embodiments of the present invention, the cobalt salts may be selected from a wide range of species, and any soluble cobalt salt commonly used in the art may be used. Preferably, the cobalt salt is selected from at least one of cobalt sulfate, cobalt nitrate and cobalt acetate, more preferably cobalt sulfate.
According to some embodiments of the present invention, the selection of the type of manganese salt is wide, and any soluble manganese salt commonly used in the art may be used. Preferably, the manganese salt is selected from at least one of manganese sulfate, manganese nitrate and manganese acetate, more preferably manganese sulfate.
According to some embodiments of the present invention, the types of the precipitants may be selected from a wide range, and any precipitants commonly used in the art may be used. Preferably, the precipitant is selected from sodium hydroxide and/or potassium hydroxide, more preferably sodium hydroxide.
According to some embodiments of the present invention, the types of the first complexing agent and the second complexing agent may be selected from a wide range, and any complexing agent commonly used in the art may be used. Preferably, the first complexing agent and the second complexing agent are the same or different, and are each independently selected from at least one of ammonia water, disodium edetate, ammonium nitrate and ammonium sulfate; more preferably, the first complexing agent is the same as the second complexing agent; further preferably, the first complexing agent and the second complexing agent are both ammonia water.
According to some embodiments of the invention, preferably, in step (1), the mixed salt solution has a concentration of 1 to 3mol/L, preferably 1.7 to 2.3mol/L, based on the total molar amount of metal elements. The concentration of the mixed salt solution is within the above-defined range, which is advantageous in that the mixed salt is sufficiently uniformly fused and crystallized.
According to some embodiments of the invention, the concentration of the precipitant solution is preferably 7-9.5mol/L, preferably 7.6-8.3mol/L. The concentration of the precipitant solution within the above-defined range is advantageous for stabilizing the precipitation rate, so that precipitation unevenness is not caused too fast and productivity is too low.
According to some embodiments of the invention, preferably, the molar ratio of the mixed salt, the precipitant, the first complexing agent and the second complexing agent is 1: (2-7): (2-4.5): (3.7-7), more preferably 1: (3-5.5): (2.2-3.6): (4.1-6), wherein the mixed salt is based on the total molar amount of the metal elements. In the invention, the molar ratio of the mixed salt to the precipitant to the first complexing agent to the second complexing agent is in the above-defined range, which is favorable for fully and uniformly fusing and crystallizing the mixed salt, and stabilizing the precipitation speed to achieve proper precursor particle size distribution.
According to some embodiments of the invention, in step (2), the mixed salt solution, the precipitant solution and the complexing agent solution I are first mixed, and then the resulting mixture is second mixed with the complexing agent solution II to obtain the precursor slurry.
According to some embodiments of the invention, the mixed salt solution, the precipitant solution and the complexing agent solution I are preferably fed in cocurrent to a reaction vessel for a first mixing, during which a coprecipitation reaction takes place. More preferably, the first mixing is performed under stirring conditions, which may be referred to conventional in the art, for example, stirring speed may be 600rpm.
According to some embodiments of the invention, preferably, the first mixing conditions include: a pH of 10 to 13, preferably 11 to 12.5; the temperature is 40-70deg.C, preferably 50-60deg.C; the time is 10-30 hours, preferably 15-25 hours.
According to some embodiments of the present invention, the complexing agent solution II is preferably introduced into the reaction vessel in cocurrent flow, and the mixture obtained by the first mixing is subjected to a second mixing to obtain a precursor slurry. Co-precipitation reactions also occur during this process. More preferably, the second mixing is performed under stirring conditions, which may be referred to conventional in the art, for example, stirring speed may be 600rpm.
According to some embodiments of the invention, preferably, the conditions of the second mixing include: a pH of 11 to 13, preferably 11.5 to 13; the temperature is 40-60deg.C, preferably 45-55deg.C; the time is 10-30 hours, preferably 15-25 hours.
According to some embodiments of the invention, in step (3), the precursor slurry is subjected to solid-liquid separation, washing and drying to obtain a precursor. The mode of the solid-liquid separation is not particularly limited, and the present invention can be carried out with reference to the prior art. For example, the solid-liquid separation can be performed by suction filtration. Preferably, step (3) is carried out under inert atmosphere protection. The inert atmosphere may be provided by an inert gas such as argon, nitrogen, or the like.
According to some embodiments of the invention, in step (4), the precursor, the lithium source and the dopant comprising M are subjected to a third mixing and, after calcination, a calcination product is obtained.
According to some embodiments of the present invention, the selection range for the kind of the lithium source is wide, and any lithium source commonly used in the art may be used. Preferably, the lithium source is LiOH and/or Li 2 CO 3 LiOH is preferred.
According to some embodiments of the invention, preferably, the M-containing dopant is selected from at least one of M-containing carbonates, oxides and hydroxides, more preferably M-containing carbonates. Wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba. Preferably, M is selected from at least one element of Al, zr, W, mg, sr and Ba, and further preferably, M is selected from at least one element of Mg, sr and Ba.
According to some embodiments of the invention, preferably, the M-containing dopant is selected from BaCO 3 、MgCO 3 、SrCO 3 、Al 2 O 3 、ZrO 2 And WO 3 At least one of (a) and (b); more preferably, the M-containing dopant is selected from BaCO 3 、MgCO 3 And SrCO 3 At least one of them. In the invention, the adoption of the metal doping elements of the specific types is beneficial to improving the cycling stability and capacity of the positive electrode material.
According to some embodiments of the invention, preferably, in step (4), the molar amount of the precursor and the lithium source is such that: and n (Li)/[ n (Ni) +n (Co) +n (Mn) ] is less than or equal to 1.2.
According to some embodiments of the invention, preferably, the molar amounts of the precursor and the dopant containing M are such that: [ n (Ni) +n (Co) +n (Mn) ]/[ n (M) ]=1: (0.04-0.67). The molar amounts of the precursor and the M-containing dopant are within the above-mentioned limit, which is advantageous for preventing the lithium ion channel from being blocked due to too large molar amount, so that the capacity cannot be exerted, and in this limit, the cycling stability of the positive electrode material can be improved while the capacity is taken into consideration.
According to some embodiments of the invention, preferably, in step (4), the roasting conditions include: the temperature is 800-1200 ℃, preferably 900-1100 ℃; the time is 10-30 hours, preferably 15-20 hours. The roasting temperature is within the limit, so that the primary particle size of the positive electrode material is controlled, undersize of the primary particle size with too low temperature is prevented, and oversize of the primary particle size with too high temperature is avoided. More preferably, the firing is performed in an oxygen atmosphere or an air atmosphere.
According to some embodiments of the invention, preferably, the calcined product has the formula Li a Ni b Co c Mn d M e O 2 Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than 0.4, and a+b+c+d+e=2; more preferably, in the formula, a is more than or equal to 1 and less than or equal to 1.2,0.5, b is more than or equal to 0.8,0.1, c is more than or equal to 0.4, d is more than or equal to 0.1 and less than or equal to 0.4,0.04, e is more than or equal to 0.3, and a+b+c+d+e=2; further preferably, in the formula, b is more than or equal to 0.5 and less than or equal to 0.6,0.15, c is more than or equal to 0.3,0.15, d is more than or equal to 0.3,0.04 and e is more than or equal to 0.1, and b+c+d+e=1.
According to some embodiments of the invention, preferably, the calcined product has a single crystal structure.
According to some embodiments of the invention, preferably, step (4) further comprises the step of crushing and sieving the calcined product.
According to some embodiments of the present invention, in order to repair the damage of the baked product obtained in the step (4) during the preparation process, the structure of the positive electrode material is more stable during the subsequent charge and discharge process, and in the step (5), the baked product is subjected to fourth mixing with the additive containing J, and then heat treatment is performed, so as to obtain the positive electrode material. The J-containing additive can form a protective isolation effect on the surface of the positive electrode material, provide a surface protection effect for the positive electrode material, and reduce the occurrence of side reactions of the positive electrode material and electrolyte.
According to some embodiments of the invention, preferably the J-containing additive is selected from J-containing oxides and/or metal salts, more preferably J-containing oxides. Wherein J is at least one element selected from S, si, F and Cl, further preferably J is at least one element selected from S, F and Si, preferably F and/or Si.
According to some embodiments of the invention, preferably, the J-containing additive is LiF and/or SiO 2 。
According to some embodiments of the invention, preferably, in step (5), the molar amounts of the calcined product and the J-containing additive are such that: [ n (Ni) +n (Co) +n (Mn) +n (M) ]/[ n (J) ]=1: (0.001-0.01); preferably, the following are satisfied: [ n (Ni) +n (Co) +n (Mn) +n (M) ]/[ n (J) ]=1: (0.003-0.005). The molar amount of the roasting product and the additive containing J is in the limit range, so that the additive can form a protection and isolation effect on the surface of the positive electrode material, the occurrence of side reactions of the positive electrode material and the electrolyte is reduced, the coverage is insufficient due to too little, the effective protection cannot be formed, and the capacity of the positive electrode material is difficult to develop due to too much.
According to some embodiments of the invention, preferably, the heat treatment conditions include: the temperature is 400-700 ℃, preferably 500-600 ℃; the time is 2-8 hours, preferably 3-7 hours. More preferably, the heat treatment is performed in an oxygen atmosphere or an air atmosphere.
According to some embodiments of the present invention, it is preferable that the primary particles of the positive electrode material prepared by the method have an average particle diameter d 50 And standard deviation of particle diameter d σ The method meets the following conditions: d, d 50 ≤40μm，d σ ≥0.25μm，0.7≤d 50 /d σ ≤120；
The chemical formula of the positive electrode material is Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is less than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2.
According to some embodiments of the present invention, more preferably, the positive electrode material has an average particle diameter d 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is more than or equal to 0.4 mu m 50 Less than or equal to 35 mu m; and/or, d σ More than or equal to 0.5 mu m; and/or, 1.ltoreq.d 50 /d σ And is less than or equal to 116. Further preferably, the average particle diameter d of the positive electrode material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is less than or equal to 1.5 mu m 50 Less than or equal to 5 mu m; and/or, d σ More than or equal to 0.5 mu m; and/or, 1.5.ltoreq.d 50 /d σ ≤4。
More preferably, according to some embodiments of the invention, in the chemical formula of the positive electrode material, a is more than or equal to 1 and less than or equal to 1.2,0.5, b is more than or equal to 0.8,0.1, c is more than or equal to 0.4, d is more than or equal to 0.1 and less than or equal to 0.4,0.04, e is more than or equal to 0.3,1.99 and less than or equal to 1.999,0.001, j is more than or equal to 0.01, and a+b+c+d+e=2. Further preferably, in the chemical formula of the positive electrode material, b is more than or equal to 0.5 and less than or equal to 0.6,0.15 and less than or equal to c is more than or equal to 0.3,0.15 and less than or equal to d is more than or equal to 0.3,0.04 and less than or equal to e is more than or equal to 0.1,1.995 and less than or equal to 1.997,0.003 and less than or equal to j is more than or equal to 0.005, and b+c+d+e=1.
According to some embodiments of the invention, preferably, the positive electrode material is a single crystal positive electrode material.
A third aspect of the invention provides the use of the positive electrode material according to the first aspect or the positive electrode material prepared according to the method according to the second aspect in a lithium ion battery.
The present invention will be described in detail by examples.
In the following examples and comparative examples, the raw materials used were all commercially available.
The surface morphology of the material was characterized by Scanning Electron Microscopy (SEM). The model of the scanning electron microscope is S-4800 (manufacturer is Hitachi, japan), and the test conditions of the scanning electron microscope are as follows: acceleration voltage is 10kV, and magnification is 3000 times. One of the positive electrode materialsAverage particle diameter d of secondary particles 50 And standard deviation of particle diameter d σ And the method is obtained through scanning electron microscope picture measurement and calculation.
(1) Particle size testing
Testing was performed using a Mastersizer2000 laser particle sizer. Modifying the sample test time and background test time of the test frequency item in the measurement in the software to be 6s; the number of cycles of the measurement cycle term was 3, the delay time was 5s, and clicks created an average result record from the measurement. Secondly, clicking the start to automatically measure the background; after the automatic measurement is completed, 40 milliliters of sodium pyrophosphate is added, then a small amount of sample is added by a medicine spoon until the shading degree reaches 1/2 of the visual 10-20% area, the start is clicked, and the three results and the average value are finally recorded.
(2) Compacted bulk Density P test
Compacted bulk density P: and testing by a compaction density tester of MCP-PD51 model. Weighing 4g of sample to be tested, placing the sample into an installed mould, carrying out pressurizing test, stopping pressurizing when the pressure reaches 20KN for 30min plus or minus 2min, stabilizing the pressure for 30s, if the pressure drops, supplementing the pressure back to 20K, then clicking a start key in software to start testing the sample, clicking a test software interface to generate a report, and recording compaction density in the report.
(3) Initial impedance testing
The prepared button cell was used to set the current density to 0.25mA/cm relative to the positive electrode 2 Charging until the cutoff voltage reaches 4.4V, and standing for 0.2 hr to obtain a current density of 2.5mA/cm 2 Discharge, recording discharge initial 0s and 23s voltage, (0 s voltage-23 s voltage)/2.5 mA, gives initial impedance.
Examples 1 to 9 illustrate positive electrode materials and methods of preparing the same
Example 1
S1: the molar ratio of the nickel, cobalt and manganese elements is 60:20:20, dissolving nickel sulfate, cobalt sulfate and manganese sulfate in water to obtain a mixed salt solution with the concentration of 2mol/L; dissolving sodium hydroxide in water to obtain a precipitant solution with the concentration of 8 mol/L; ammonia water is dissolved in water to obtain complexing agent solution I with the concentration of 5.2mol/L and complexing agent solution II with the concentration of 10.3mol/L.
S2: the molar ratio of the mixed salt (based on the total molar amount of metal elements), the precipitant, the first complexing agent and the second complexing agent is 1:4:2.6:5.15, introducing 100L of mixed salt solution, precipitator solution and complexing agent solution I into a reaction kettle in a parallel flow mode, carrying out first mixing for 18h under the conditions of pH value of 12.2, temperature of 55 ℃ and stirring rotation speed of 600rpm, then introducing complexing agent solution II into the reaction kettle in a parallel flow mode, and carrying out second mixing for 18h under the conditions of pH value of 12.86, temperature of 50 ℃ and stirring rotation speed of 600rpm, thus obtaining precursor slurry.
S3: filtering and washing the precursor slurry under the protection of nitrogen atmosphere, drying the obtained filter cake at 120 ℃ and sieving to obtain the catalyst with a chemical formula of Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 The precursor of (2) is used for testing the granularity of the precursor by using a Markov laser granularity meter to obtain granularity D 5 、D 50 、D 95 Calculating the particle size dispersion degree K of the precursor 95 ＝(D 95 -D 5 )/D 50 The results are shown in Table 1.
S4: mixing the precursor prepared by S3 with LiOH and BaCO 3 According to Li/(ni+co+mn)/ba=1.10: 1.00: mixing at a molar ratio of 0.1, roasting at a temperature of 940 ℃ from room temperature in an oxygen atmosphere, preserving heat for 18h, cooling, crushing and sieving to obtain the product with a chemical formula of LiNi 0.55 Co 0.18 Mn 0.18 Ba 0.09 O 2 And a calcined product having a single crystal structure.
S5: mixing the calcined product prepared by S4 with SiO 2 According to (ni+co+mn+m)/si=1: fourth mixing at a molar ratio of 0.003, heating from room temperature to 550deg.C in air atmosphere, maintaining for 5 hr, and naturally cooling to obtain LiNi 0.55 Mn 0.18 Co 0.18 Ba 0.09 O 1.997 Si 0.003 A single crystal positive electrode material Z1 of (a).
Fig. 1 is a Scanning Electron Microscope (SEM) image of the precursor prepared in example 1, and it can be seen from fig. 1 that the particle size distribution of the precursor is wider, and the particles with different sizes cooperate with each other so that the grading performance of the precursor is better. Fig. 2 is a Scanning Electron Microscope (SEM) image of the positive electrode material Z1 prepared in example 1, and as can be seen from fig. 2, the primary particles of the positive electrode material are widely distributed, and the particles with different sizes cooperate with each other, so that the grading performance of the positive electrode material is better, and the compaction performance of the positive electrode material is more beneficial to improvement.
Measuring the average primary particle diameter d of the positive electrode material by adopting a scanning electron microscope method 50 And standard deviation of particle diameter d σ The results are shown in Table 1.
The positive electrode material was subjected to powder compaction under 20kN conditions, and the compacted bulk density P of the positive electrode material under the conditions was measured, and the results are shown in table 2.
Examples 2 to 9
The positive electrode materials were prepared according to the method of example 1, the raw material ratios and specific process conditions are shown in table 1, and single crystal positive electrode materials Z2 to Z9 were prepared, and the corresponding chemical formulas are shown in table 1. Wherein, the roasting products obtained in the step S4 of the examples 2-9 all have single crystal structures, and the corresponding chemical formulas are shown in the table 1.
Comparative examples 1 to 2
The positive electrode materials were prepared according to the method of example 1, the raw material ratios and specific process conditions are shown in Table 1, and the positive electrode materials D1 to D2 were prepared, and the corresponding chemical formulas are shown in Table 1. Wherein, the roasting products obtained in the step S4 of the comparative examples 1-2 all have single crystal structures, and the corresponding chemical formulas are shown in the table 1.
Fig. 3 is a Scanning Electron Microscope (SEM) image of the precursor prepared in comparative example 2, and it can be seen from fig. 3 that the particle size of the precursor is relatively uniform, the particle distribution is relatively narrow, and the gradation property is relatively poor.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the positive electrode material D2 prepared in comparative example 2, and as can be seen from fig. 4, the primary particles of the positive electrode material are relatively uniform in size, and the primary particles are relatively narrow in distribution, which is disadvantageous for improving the compaction performance thereof.
TABLE 1 (note: mole ratio of raw materials) * For mixing the salt, the precipitant, the first complexing agent and the second complexing agent, wherein the mixed solution is calculated by the total mole of metal elements
/>
Table 1 (subsequent)
/>
Table 1 (subsequent)
/>
/>
Application example
(1) Positive electrode fabrication
The positive electrode materials obtained in examples 1 to 9 and comparative examples 1 to 2 were each used as a positive electrode active material, 93% by weight of the positive electrode active material, 5% by weight of a conductive additive (carbon black), 2% by weight of a binder (polyvinylidene fluoride (PVDF)) and an appropriate amount of a slurry viscosity adjusting solvent (N-methyl-2-pyrrolidone (NMP)) were mixed to prepare a positive electrode active material slurry, the obtained positive electrode active material slurry was coated on an aluminum foil (thickness: 20 μm) as a current collector, dried at 120℃for 5 minutes, and then compression-molded by a roll press machine to prepare a positive electrode active material layer having a single-sided coating amount of 20mg/cm 2 Positive electrodes A1 to A9 and DA1 to DA2.
(2) Button cell fabrication
In a glove box under an argon atmosphere, the positive electrodes A1 to A9 and DA1 to DA2 were punched into disk shapes with diameters of 14mm, respectively, to prepare positive electrode sheets for button cell units. The metal lithium is punched into a disc shape with the diameter of 15mm, and the negative electrode plate for the button cell is manufactured. In addition, as an electrolyte, 1.0M LiPF was prepared 6 A solution obtained by dissolving in a mixed solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (EC: DMC volume ratio 1:1). The positive electrode and the negative electrode were stacked with a separator (material: polypropylene; thickness: 23 μm) interposed therebetween, and placed in a button cell container, and an electrolyte was injected and covered with a cap, thereby producing a button cell for evaluation. The fabricated button cell was left to stand for 24 hours, and after the open circuit voltage (OCV: open Circuit Voltage) had stabilized, the current density relative to the positive electrode was set to 0.25mA/cm 2 The initial charge capacity was obtained by charging up to a cutoff voltage of 4.4V, and the initial discharge capacity was obtained by discharging up to a cutoff voltage of 3.0V after standing for 0.2 hours. Then, the current density of the opposite positive electrode was set to 2.5mA/cm 2 The charge and discharge were performed 80 times in a cycle, and the cycle capacity retention rate of the battery after 80 times in the cycle was calculated to evaluate the cycle durability.
Test case
The electrochemical performance of the button cell units prepared using the positive electrode materials of examples 1 to 9 and comparative examples 1 to 2, respectively, was tested, and the results are shown in table 2.
TABLE 2
The results in tables 1 and 2 show that:
the positive electrode materials prepared in examples 1-3 and examples 4-9 preferably have a compacted bulk density, a specific capacity for initial discharge, and a retention of cyclic capacity that are superior to those of examples 4-6, and have a lower initial resistance.
In the examples 1 to 6,primary particles of the positive electrode material have an average particle diameter d as the firing temperature increases 50 Gradually increasing.
Compared with the embodiment 1 and the embodiment 7, the concentration of the complexing agent solution I and the concentration of the complexing agent solution II are in the preferable range, which is more favorable for improving the compacted volume density, the first discharge specific capacity and the circulating capacity retention rate of the positive electrode material and reducing the initial impedance.
The time and temperature of the first and second mixing within the preferred ranges are more advantageous for improving the compacted bulk density, the specific capacity for first discharge and the cyclic capacity retention rate of the positive electrode material, and for reducing the initial resistance, compared to example 1 and example 8.
Example 1 is more advantageous in improving the compacted bulk density, the first discharge specific capacity and the cyclic capacity retention rate of the positive electrode material and reducing the initial resistance when the firing temperature and time are within the preferred ranges than in example 9.
Example 1 BaCO of example 1 compared with comparative example 1 3 CeO of comparative example 1 2 For improving the compacted volume density, the first discharge specific capacity and the cyclic capacity retention rate of the positive electrode material and reducing the initial impedance, the specific doping agent containing M is more beneficial to improving the compacted volume density, the first discharge specific capacity and the cyclic capacity retention rate of the positive electrode material obviously, and reducing the initial impedance.
Example 1 and comparative example 2 when the concentration of complexing agent solution I in comparative example 2 is equal to the concentration of complexing agent solution II, precursor K is prepared 95 Smaller, narrower particle size distribution, d of the resulting positive electrode material σ The specific method has the advantages that the concentration of the complexing agent solution I is controlled to be smaller than that of the complexing agent solution II, so that the compacted volume density, the first discharge specific capacity and the cyclic capacity retention rate of the positive electrode material can be remarkably improved, and the initial impedance can be reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (19)
1. A method of preparing a positive electrode material, comprising the steps of:
(1) Providing a mixed salt solution containing nickel salt, cobalt salt and manganese salt; providing a precipitant solution containing a precipitant; providing a complexing agent solution I containing a first complexing agent and providing a complexing agent solution II containing a second complexing agent; wherein the concentration of the complexing agent solution I is 4.5-6.9mol/L; the concentration of the complexing agent solution II is 7-11.2mol/L;
(2) First mixing the mixed salt solution, the precipitator solution and the complexing agent solution I, and then second mixing the obtained mixture with the complexing agent solution II to obtain precursor slurry; wherein, the mole ratio of the mixed salt, the precipitator, the first complexing agent and the second complexing agent is 1: (2-7): (2-4.5): (3.7-7) the mixed salt based on the total molar amount of the metal element;
(3) Performing solid-liquid separation, washing and drying on the precursor slurry to obtain a precursor; wherein the particle size D of the precursor 5 、D 50 、D 95 And degree of particle size dispersion K 95 The method meets the following conditions: k (K) 95 ＝(D 95 -D 5 )/D 50 ，0.9≤K 95 ≤2.5；
(4) Thirdly mixing the precursor, the lithium source and the doping agent containing M, and roasting to obtain a roasting product; wherein M is at least one element selected from Ti, zr, nb, W, al, mg, V, ca, sr, cr, fe, ga, in, mo, Y, sn, cu, ag, zn, na and Ba;
(5) Fourth mixing the roasting product with an additive containing J, and then performing heat treatment to obtain a positive electrode material; wherein J is at least one element selected from S, si, F and Cl;
wherein, the positive electrode material prepared by the methodAverage particle diameter d of primary particles of the material 50 And standard deviation of particle diameter d σ The method meets the following conditions: d, d 50 ≤40μm，d σ ≥0.25μm，0.7≤d 50 /d σ ≤120。
2. The method of claim 1, wherein the positive electrode material has a chemical formula of Li a Ni b Co c Mn d M e O f J j Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than or equal to 0.4,1 and less than or equal to f is less than or equal to 2, j is more than 0 and less than or equal to 1, a+b+c+d+e=2, and f+j=2.
3. The method according to claim 1, wherein the positive electrode material obtained by the method has an average particle diameter d 50 And standard deviation of particle diameter d σ The method meets the following conditions: d is more than or equal to 0.4 mu m 50 Less than or equal to 35 mu m; and/or, d σ More than or equal to 0.5 mu m; and/or, 1.ltoreq.d 50 /d σ ≤116。
4. A method according to claim 2 or 3, wherein the positive electrode material produced by the method is a single crystal positive electrode material; and/or
In the chemical formula of the positive electrode material prepared by the method, a is more than or equal to 1 and less than or equal to 1.2,0.5, b is more than or equal to 0.8,0.1, c is more than or equal to 0.4, d is more than or equal to 0.1 and less than or equal to 0.4,0.04, e is more than or equal to 0.3,1.99, f is more than or equal to 1.999,0.001, j is more than or equal to 0.01, and a+b+c+d+e=2.
5. The method according to claim 4, wherein the positive electrode material has a chemical formula, b is more than or equal to 0.5 and less than or equal to 0.6,0.15, c is more than or equal to 0.3,0.15, d is more than or equal to 0.3,0.04, e is more than or equal to 0.1,1.995, f is more than or equal to 1.997,0.003, j is more than or equal to 0.005, and b+c+d+e=1.
6. A process according to any one of claims 1 to 3, wherein in step (1) the complexing agent solution I has a concentration of 5.2 to 6.2mol/L; and/or
The concentration of the complexing agent solution II is 9.5-10.3mol/L;
and/or, in the step (3),particle size D of the precursor 5 、D 50 、D 95 And degree of particle size dispersion K 95 The method meets the following conditions: k is more than or equal to 0.9 95 ≤2；
And/or, in step (4), the roasting conditions include: the temperature is 800-1200 ℃ and the time is 10-30h.
7. The method of claim 6, wherein in step (4), the firing conditions include: the temperature is 900-1100 ℃ and the time is 15-20h.
8. A method according to any one of claims 1-3, wherein the nickel salt is selected from at least one of nickel sulphate, nickel nitrate and nickel acetate;
and/or the cobalt salt is selected from at least one of cobalt sulfate, cobalt nitrate and cobalt acetate;
and/or the manganese salt is selected from at least one of manganese sulfate, manganese nitrate and manganese acetate;
and/or the precipitant is selected from sodium hydroxide and/or potassium hydroxide;
and/or the first complexing agent and the second complexing agent are the same or different and are each independently selected from at least one of ammonia water, disodium ethylenediamine tetraacetate, ammonium nitrate and ammonium sulfate;
and/or the lithium source is LiOH and/or Li 2 CO 3 ；
And/or the dopant containing M is selected from at least one of carbonate, oxide and hydroxide containing M;
and/or the J-containing additive is selected from an oxide and/or a metal salt containing J.
9. The method of claim 8, wherein the nickel salt is nickel sulfate;
and/or, the cobalt salt is cobalt sulfate;
and/or the manganese salt is manganese sulfate;
and/or, the precipitant is sodium hydroxide;
and/or, the first complexing agent is the same as the second complexing agent;
and/or, the lithium source is LiOH.
10. The method of claim 9, wherein the first complexing agent and the second complexing agent are both aqueous ammonia.
11. The method of claim 8, wherein the dopant containing M is selected from BaCO 3 、MgCO 3 、SrCO 3 、Al 2 O 3 、ZrO 2 And WO 3 At least one of them.
12. The method of claim 8, wherein the J-containing additive is LiF and/or SiO 2 。
13. A method according to any one of claims 1 to 3, wherein in step (1), the mixed salt solution has a concentration of 1 to 3mol/L based on the total molar amount of the metal element;
and/or the concentration of the precipitant solution is 7-9.5mol/L;
and/or, in the step (2), the molar ratio of the mixed salt, the precipitator, the first complexing agent and the second complexing agent is 1: (3-5.5): (2.2-3.6): (4.1-6), wherein the mixed salt is based on the total molar amount of the metal elements;
and/or, the conditions of the first mixing include: the pH is 10-13, the temperature is 40-70 ℃ and the time is 10-30h;
and/or, the conditions of the second mixing include: the pH is 11-13, the temperature is 40-60 ℃ and the time is 10-30h.
14. The method according to claim 13, wherein in the step (1), the mixed salt solution has a concentration of 1.7 to 2.3mol/L based on the total molar amount of the metal element.
15. The method of claim 13, wherein in step (1), the concentration of the precipitant solution is 7.6-8.3mol/L.
16. The method of claim 13, wherein in step (2), the first mixing conditions comprise: the pH is 11-12.5, the temperature is 50-60 ℃ and the time is 15-25h.
17. A method according to any one of claims 1 to 3, wherein in step (4), the molar amounts of the precursor and the lithium source are such that: not less than 1 [ n (Li) ]/[ n (Ni) +n (Co) +n (Mn) ] +.1.2;
and/or the molar amounts of the precursor and the dopant containing M are such that: [ n (Ni) +n (Co) +n (Mn) ]/[ n (M) ]=1: (0.04-0.67);
and/or the chemical formula of the roasting product is Li a Ni b Co c Mn d M e O 2 Wherein a is more than or equal to 0.8 and less than or equal to 1.2, b is more than or equal to 0 and less than 1, c is more than 0 and less than 0.5, d is more than 0 and less than 0.5, e is more than 0 and less than 0.4, and a+b+c+d+e=2;
and/or, in step (5), the molar amounts of the calcined product and the J-containing additive are such that: [ n (Ni) +n (Co) +n (Mn) +n (M) ]/[ n (J) ]=1: (0.001-0.01);
and/or, the conditions of the heat treatment include: the temperature is 400-700 ℃ and the time is 2-8h.
18. The method of claim 17, wherein in step (5), the molar amounts of the calcined product and the J-containing additive are such that: [ n (Ni) +n (Co) +n (Mn) +n (M) ]/[ n (J) ]=1: (0.003-0.005).
19. The method of claim 17, wherein in step (5), the heat treatment conditions include: the temperature is 500-600 ℃ and the time is 3-7h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111671800.2A CN114573043B (en) | 2021-12-31 | 2021-12-31 | Positive electrode material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111671800.2A CN114573043B (en) | 2021-12-31 | 2021-12-31 | Positive electrode material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114573043A CN114573043A (en) | 2022-06-03 |
| CN114573043B true CN114573043B (en) | 2023-12-22 |
Family
ID=81772193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111671800.2A Active CN114573043B (en) | 2021-12-31 | 2021-12-31 | Positive electrode material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114573043B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072802B (en) * | 2022-06-30 | 2023-07-25 | 北京当升材料科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| CN116525814B (en) * | 2023-06-29 | 2023-11-28 | 宁波容百新能源科技股份有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and sodium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109721109A (en) * | 2018-12-07 | 2019-05-07 | 北京理工大学 | A kind of lithium battery nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof and the positive electrode being prepared |
| WO2019131194A1 (en) * | 2017-12-27 | 2019-07-04 | パナソニック株式会社 | Positive electrode active material for secondary cell having non-aqueous electrolyte, positive electrode for secondary cell having non-aqueous electrolyte, and secondary cell having non-aqueous electrolyte |
| CN110993936A (en) * | 2019-12-02 | 2020-04-10 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN112591805A (en) * | 2020-12-14 | 2021-04-02 | 荆门市格林美新材料有限公司 | Method for improving particle size distribution width of nickel-cobalt-manganese ternary precursor |
-
2021
- 2021-12-31 CN CN202111671800.2A patent/CN114573043B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019131194A1 (en) * | 2017-12-27 | 2019-07-04 | パナソニック株式会社 | Positive electrode active material for secondary cell having non-aqueous electrolyte, positive electrode for secondary cell having non-aqueous electrolyte, and secondary cell having non-aqueous electrolyte |
| CN111033829A (en) * | 2017-12-27 | 2020-04-17 | 松下电器产业株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery, positive electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| CN109721109A (en) * | 2018-12-07 | 2019-05-07 | 北京理工大学 | A kind of lithium battery nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof and the positive electrode being prepared |
| CN110993936A (en) * | 2019-12-02 | 2020-04-10 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN112591805A (en) * | 2020-12-14 | 2021-04-02 | 荆门市格林美新材料有限公司 | Method for improving particle size distribution width of nickel-cobalt-manganese ternary precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114573043A (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN111170377B (en) | Preparation method of lithium-rich manganese-based positive electrode material | |
| CN108269970B (en) | Novel lithium ion battery gradient cathode material and preparation method thereof | |
| US8383270B2 (en) | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery | |
| EP1117145B1 (en) | Nonaqueous electrolyte secondary cell | |
| CN109516509B (en) | High-compaction single crystal ternary positive electrode material and preparation method and application thereof | |
| CN108878794B (en) | Spinel-structured lithium ion battery anode material with composite coating layer and preparation method thereof | |
| CN111446444B (en) | Lithium-rich manganese-based material and preparation method and application thereof | |
| CN109461893B (en) | Novel lithium ion battery anode material and preparation method thereof | |
| CN114573043B (en) | Positive electrode material, preparation method and application thereof | |
| KR20110044936A (en) | Process for the production of lithium-manganese double oxide for lithium ion batteries and lithium-manganese double oxide for lithium ion batteries made by the same, and lithium ion batteries cotaining the same | |
| GB2617726A (en) | Lithium transition metal oxide material coated with fast ion conductor and preparation method therefor | |
| WO2024066892A1 (en) | Manganese-rich oxide precursor, preparation method therefor, and use thereof | |
| CN110649230B (en) | Nanometer rivet core-shell structure anode material and preparation method thereof | |
| WO2023221625A1 (en) | Large-particle-size single-crystal ternary positive electrode material, and preparation method therefor and use thereof | |
| CN116789185A (en) | Positive active material for lithium secondary battery and method for preparing the same | |
| CN116986572A (en) | Modified lithium iron manganese phosphate positive electrode material, preparation method thereof and lithium ion battery | |
| CN114094095B (en) | Spinel type positive electrode material, preparation method thereof and lithium ion battery positive electrode sheet | |
| CN115188941A (en) | Multi-element anode material, preparation method thereof and lithium ion battery | |
| CN113707873A (en) | Lithium ion battery positive electrode material using eutectic lithium salt and preparation method thereof | |
| CN115084457A (en) | High-compaction long-life ternary cathode material and preparation method thereof | |
| CN113161526A (en) | Positive electrode material and preparation method and application thereof | |
| CN114068911A (en) | Modified high-nickel cathode material and preparation method thereof | |
| CN116247197B (en) | Spherical high-voltage lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery | |
| CN114477311B (en) | Cobalt composite hydroxide, preparation method thereof, lithium ion battery anode material and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |