WO2023155215A1 - 正极材料及其制备方法、锂离子电池 - Google Patents
正极材料及其制备方法、锂离子电池 Download PDFInfo
- Publication number
- WO2023155215A1 WO2023155215A1 PCT/CN2022/077289 CN2022077289W WO2023155215A1 WO 2023155215 A1 WO2023155215 A1 WO 2023155215A1 CN 2022077289 W CN2022077289 W CN 2022077289W WO 2023155215 A1 WO2023155215 A1 WO 2023155215A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating layer
- positive electrode
- electrode material
- phosphate
- lithium
- Prior art date
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 174
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 144
- 239000011163 secondary particle Substances 0.000 claims abstract description 102
- 239000011164 primary particle Substances 0.000 claims abstract description 86
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 69
- 239000010452 phosphate Substances 0.000 claims abstract description 69
- -1 phosphate compound Chemical class 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 42
- 239000011574 phosphorus Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000013543 active substance Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 60
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 49
- 239000002245 particle Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 229910001463 metal phosphate Chemical class 0.000 claims description 22
- 239000010410 layer Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000010406 cathode material Substances 0.000 claims description 20
- 150000002642 lithium compounds Chemical class 0.000 claims description 20
- 238000005253 cladding Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 229910052788 barium Inorganic materials 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 229910052721 tungsten Inorganic materials 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 10
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 8
- 150000003016 phosphoric acids Chemical class 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 229940048084 pyrophosphate Drugs 0.000 claims description 6
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052789 astatine Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 35
- 239000000047 product Substances 0.000 description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 29
- 239000003792 electrolyte Substances 0.000 description 11
- 239000011149 active material Substances 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 230000007774 longterm Effects 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005341 metaphosphate group Chemical group 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015355 LiMgPO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 241001302239 Mycobacterium tuberculosis complex Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- H01M4/624—Electric conductive fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the technical field of cathode materials, in particular, to cathode materials, preparation methods thereof, and lithium-ion batteries.
- Lithium-ion batteries are widely used in electric vehicles and consumer electronics due to their advantages such as high energy density, high output power, long cycle life and low environmental pollution. How to improve the rate performance, thermal stability and cycle stability of lithium batteries has always been the research direction of researchers. After a long cycle of existing high-nickel cathode materials, the particle cracking makes the internal structure easy to be directly exposed, which affects the long-term cycle stability of the cathode material and affects the rate performance of the lithium battery.
- the present application proposes a positive electrode material, a preparation method thereof, and a lithium-ion battery, which can improve coating uniformity, accurately control the coating amount, improve the rate performance, thermal stability, and cycle stability of the lithium battery, and reduce production costs.
- the embodiment of the present application provides a positive electrode material
- the positive electrode material includes:
- M is selected from at least one of Mn and Al;
- R is doped miscellaneous metals; and
- a coating layer includes a first coating layer and a second coating layer, the first coating layer is formed on the surface of the primary particle, the second coating layer is formed on the two the surface of the secondary particle, the first coating layer and the second coating layer both contain a phosphoric acid compound;
- the single-point phosphorus content a' at any point on the surface of the positive electrode material satisfies the following relationship with the average phosphorus content a on the surface of the positive electrode material:
- R in the Li b Ni x Co y M z R w O 2 includes Co, Mn, Al, Ti, Zr, Sr, Mg, Ca, Y, At least one of Ba, Cu, W, Nb, La, Ce, Mo and Sn.
- the positive electrode material satisfies at least one of the following conditions a to k:
- the secondary particles are spherical or spherical;
- the average particle diameter of the primary particles is 200nm to 1000nm, and the average particle diameter of the secondary particles is 3 ⁇ m to 20 ⁇ m;
- the phosphoric acid compound includes at least one of Li 3 PO 4 and LiR k (PO 4 ) r , 0 ⁇ k ⁇ 2, 0 ⁇ r ⁇ 2, R includes Co, Mn, Al, Ti, Zr, Sr , at least one of Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo and Sn;
- the raw materials for the preparation of the phosphoric acid compound of the first cladding layer include phosphoric acid metal salt and lithium compound
- the raw materials for the preparation of the phosphoric acid compound of the second cladding layer include phosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, pyro At least one of phosphoric acid, hypophosphorous acid, soluble phosphate, soluble metaphosphite, soluble phosphite, soluble metaphosphite, soluble pyrophosphate, and soluble hypophosphite;
- the phosphate content of the phosphate compound in the first coating layer is 0.03wt% to 0.3wt% of the total mass of the secondary particles;
- the phosphate content of the phosphate compound in the second coating layer is 0.1wt% to 0.7wt% of the total mass of the secondary particles and the first coating layer;
- the crystallized phosphate content of the phosphoric acid compound in the first coating layer or the second coating layer is 5wt%-50wt% of the total mass of phosphate radicals;
- the thickness of the first coating layer is 0.005 ⁇ m to 0.05 ⁇ m;
- the thickness of the second cladding layer is 0.02 ⁇ m to 0.2 ⁇ m;
- the powder conductivity of the positive electrode material under a pressure of 4kN/ cm2 is greater than 0.02S/cm;
- the specific surface area of the positive electrode material is 0.2m 2 /g ⁇ 2.0m 2 /g.
- crystallized phosphate group refers to the phosphate group in the phosphate group-containing compound existing in the form of crystals.
- the present application provides a method for preparing a positive electrode material, the method comprising the following steps:
- the sintered product includes a plurality of primary particles and a first coating layer forming the surface of the primary particles,
- the first coating layer comprises a phosphoric acid compound, and the average particle size of the metal phosphoric acid salt is less than 0.5 ⁇ m;
- the positive electrode material includes secondary particles and a second coating layer forming the surface of the secondary particles , the secondary particles are aggregates of primary particles, and the second coating layer contains a phosphoric acid compound.
- the method satisfies at least one of the following conditions a to f:
- the addition amount of the lithium compound is: so that the molar content ratio of the sum of the molar content of metal elements in Ni, Co, M and the metal phosphate to the molar content of Li is 1: (0.95 ⁇ 1.10);
- the lithium compound includes at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium oxalate;
- the metal element of the metal phosphate is selected from at least one of Co, Mn, Al, Ti, Zr, Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo and Sn ;
- the phosphate content in the metal phosphate salt is 0.03wt% to 0.3wt% of the total mass of the mixture;
- the mixing conditions for obtaining the mixture are: solid phase mixing at 10°C to 50°C for 0.3h to 2h;
- the sintering condition for obtaining the sintered product is: sintering at 650° C. to 850° C. for 6 hours to 20 hours in an oxygen-containing atmosphere.
- the method satisfies at least one of the following conditions a to b:
- the solvent includes water and non-aqueous substances, and the non-aqueous substances include phosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, pyrophosphoric acid, hypophosphorous acid, soluble phosphate, soluble metaphosphoric acid, soluble phosphite, At least one of soluble metaphosphite, soluble pyrophosphate and soluble hypophosphite;
- the phosphate content in the solvent is 0.1wt%-0.7wt% of the total mass of the sintered product.
- the method satisfies at least one of the following conditions a to f:
- the washing temperature is 10°C to 50°C;
- the slurry concentration (sinter (g)/solvent (L)) composed of the sinter and the solvent is 500g/L ⁇ 2000g/L;
- the washing time is 10min to 120min;
- the drying temperature is 80°C to 200°C;
- the drying time is 5h-48h.
- the method further includes:
- the washed and dried sintered product is heat-treated at 150° C. to 600° C. for 4 hours to 10 hours in an oxygen-containing atmosphere to obtain the positive electrode material.
- the method satisfies at least one of the following conditions a to f:
- the metal phosphate salt reacts with the lithium compound at high temperature to form the first coating layer of the primary particles
- the phosphoric acid compound includes at least one of Li 3 PO 4 and LiR k (PO 4 ) r , 0 ⁇ k ⁇ 2, 0 ⁇ r ⁇ 2, R is selected from Co, Mn, Al, Ti, Zr, At least one of Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo, Sn;
- the crystallized phosphate content of the phosphoric acid compound in the first coating layer or the second coating layer is 5wt%-50wt% of the total mass of phosphate radicals;
- the average particle diameter of the primary particles is 200nm-1000nm, and the thickness of the first coating layer is 0.005 ⁇ m-0.05 ⁇ m;
- the average particle size of the secondary particles is 3 ⁇ m-20 ⁇ m, and the thickness of the second coating layer is 0.02-0.2 ⁇ m.
- the present application provides a lithium ion battery, comprising the positive electrode material as described in the first aspect or the positive electrode material prepared by the method for preparing a positive electrode material as described in the second aspect.
- the positive electrode material provided by the present application includes secondary particles formed by a plurality of primary particles tightly combined, the primary particles have a first coating layer, the secondary particles have a second coating layer, the first coating layer and the second coating layer
- the material of the coating layer is all phosphoric acid compounds.
- the second coating layer on the surface of the secondary particle can not only protect the surface of the secondary particle from being corroded by the electrolyte, improve thermal stability, but also increase the diffusion rate of lithium ions, so that the obtained positive electrode material has both high rate performance and high thermal stability.
- the first cladding layer also has the above characteristics. Moreover, since the first coating layer forms a phosphate compound coating layer with high ion conductivity at the grain boundary between the primary particles, the transport resistance of the grain boundary is reduced, which is beneficial to improving the rate performance of the positive electrode material.
- the relationship between the single-point phosphorus content a' at any point on the surface of the positive electrode material and the average phosphorus content a on the surface of the positive electrode material satisfies 0.9a ⁇ a' ⁇ 1.1a, indicating that the single-point phosphorus content at each position on the surface of the positive electrode material is close to
- the average phosphorus content on the surface of the positive electrode material and the uniform distribution of phosphorus content in the coating layer can suppress the loss of lattice lithium on the surface of the positive electrode material (that is, the lithium ions existing in the lattice), reduce the free lithium content on the surface of the material, and improve its performance. rate performance, while suppressing the side reaction between the material and the electrolyte, improving the cycle stability of the material, and enabling the positive electrode material to obtain good processing performance and safety.
- the preparation method of the positive electrode material provided by this application through high-temperature primary sintering, the phosphate is uniformly diffused on the surface of the material, and the primary particle coating of the positive electrode material is realized, and the doping of metal cations is realized at the same time.
- the solvent of the water substance washes the sintered material below 50°C (including 50°C), so that phosphate is uniformly precipitated on the surface of the secondary particle of the material, forming a uniform phosphate compound coating layer, and improving the structural stability and thermal stability of the positive electrode material performance, safety, rate performance, long cycle performance and processing performance.
- Fig. 1 is the schematic structural representation of the cathode material that the embodiment of the present application provides;
- Fig. 2 is the process flow diagram of the preparation method of the positive electrode material provided by the embodiment of the present application.
- Fig. 3 a and Fig. 3 b are the scanning electron microscope pictures of the cathode material of embodiment 1 under different magnifications
- Fig. 4a and Fig. 4b are scanning electron microscope pictures of the positive electrode material of comparative example 1 under different magnifications
- Fig. 5 is the rate performance figure of the positive electrode material of embodiment 1 and comparative example 1;
- FIG. 6 is a differential scanning thermal curve (DSC) of the positive electrode materials of Example 1 and Comparative Example 1.
- DSC differential scanning thermal curve
- an embodiment of the present application provides a positive electrode material.
- the coating layer includes a first coating layer 111 and a second coating layer 101, the first coating layer 111 is formed on the surface of the primary particle 11, and the second coating layer 101 is formed on the surface of the secondary particle 10 On the surface, both the first cladding layer 111 and the second cladding layer 101 contain phosphoric acid compound;
- the single-point phosphorus content a' at any point on the surface of the positive electrode material satisfies the following relationship with the average phosphorus content a on the surface of the positive electrode material:
- the positive electrode material provided by the present application includes secondary particles formed by a plurality of primary particles tightly combined, the primary particles have a first coating layer, the secondary particles have a second coating layer, the first coating layer and the second coating layer
- the materials are all phosphoric acid compounds, and the relationship between the single-point phosphorus content a' at any point on the surface of the positive electrode material and the average phosphorus content a on the surface of the positive electrode material satisfies 0.9a ⁇ a' ⁇ 1.1a, indicating that each position on the surface of the positive electrode material The difference in phosphorus content distribution is small, and the coating layer is evenly distributed.
- This coating method of simultaneous internal and surface coating is conducive to the formation of a high lithium ion conductivity network, which improves the lithium ion conductivity of the material and reduces the battery impedance.
- the second coating layer on the surface of the secondary particle can not only protect the surface of the secondary particle from being corroded by the electrolyte, improve thermal stability, but also increase the diffusion rate of lithium ions, so that the obtained positive electrode material has both high rate performance and high thermal stability.
- the first cladding layer also has the above-mentioned characteristics.
- the first cladding layer forms a phosphate compound cladding layer with high ion conductivity at the grain boundary between the primary particles, which reduces the grain boundary transmission impedance and has It is beneficial to improve the rate performance of the positive electrode material. Therefore, this combined internal and external coating method synergistically improves the structural stability, thermal stability, safety, rate performance, long-term cycle performance and processability of the cathode material.
- the value of b may be, for example, 0.95, 0.98, 1.01, 1.03, 1.05, or 1.10.
- the value of x can be, for example, 0.8, 0.83, 0.88, 0.91, 0.94, 0.98, or 0.99.
- the value of y+z+w can be 0.02, 0.06, 0.09, 0.12, 0.17 or 0.2, etc.
- the value of w can be 0.0001, 0.0005, 0.0010, 0.0015, 0.0020, 0.0025 or 0.0030, etc., for example. It is not limited here.
- R in the Li b Ni x Co y M z R w O 2 includes Co, Mn, Al, Ti, Zr, Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, At least one of Ce, Mo and Sn.
- each element in the active material Li b Ni x Co y M z R w O 2 can be determined by known instruments such as ICP and ICP-MS for qualitative and/or quantitative analysis of each element.
- the primary particle is a single fine grain
- the secondary particle is a particle formed after the primary particle is agglomerated.
- the secondary particle is an aggregate of the primary particle, and the inside of the secondary particle is compact, and the secondary particle is spherical or quasi-spherical .
- the average particle diameter D50 of the primary particle of the active material is 200nm to 1000nm, for example, it can be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm or 1000nm.
- the average particle size of the secondary particles is 3 ⁇ m to 20 ⁇ m, such as 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 15 ⁇ m or 20 ⁇ m, etc.
- the average particle size of the secondary particles is 10 ⁇ m-13 ⁇ m. The applicant has found through many tests that when the average particle size of the secondary particles is controlled within the range of 3 ⁇ m to 20 ⁇ m, the problem of cracking of the secondary particles during the cycle can be avoided, which is conducive to improving the structural stability of the secondary particles , thermal stability and long-term cycle stability.
- the thickness of the first coating layer is 0.005 ⁇ m to 0.05 ⁇ m, for example, 0.005 ⁇ m, 0.01 ⁇ m, 0.015 ⁇ m, 0.02 ⁇ m, 0.025 ⁇ m, 0.03 ⁇ m, 0.035 ⁇ m, 0.04 ⁇ m, 0.045 ⁇ m or 0.05 ⁇ m.
- the thickness of the first cladding layer can also be other values within the above range, which is not limited here.
- the thickness of the second cladding layer is 0.02 ⁇ m to 0.2 ⁇ m, for example, 0.02 ⁇ m, 0.03 ⁇ m, 0.05 ⁇ m, 0.08 ⁇ m, 0.1 ⁇ m, 0.13 ⁇ m, 0.15 ⁇ m, 0.18 ⁇ m or 0.2 ⁇ m .
- the thickness of the first cladding layer can also be other values within the above range, which is not limited here.
- the phosphoric acid compound includes at least one of Li 3 PO 4 and LiR k (PO 4 ) r , 0 ⁇ k ⁇ 2, 0 ⁇ r ⁇ 2, R is selected from Co, Mn, Al , Ti, Zr, Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo and Sn at least one.
- the phosphoric acid compound not only has high lithium ion conductivity, but also can reduce the residual alkali on the surface of the positive electrode material.
- This coating method of coating the inside and the surface at the same time is conducive to the formation of a coating layer with high lithium ion conductivity and an all-round isolation of the active material and the electrolyte.
- the raw materials for the preparation of the phosphoric acid compound of the first coating layer include a metal phosphoric acid salt and a lithium compound, which is a phosphoric acid compound formed by the high-temperature reaction of a metal phosphoric acid salt and a lithium compound. Phosphate compound coating and metal cation doping are performed.
- the raw materials for the preparation of the phosphoric acid compound of the second coating layer include phosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, pyrophosphoric acid, hypophosphorous acid, soluble phosphate, soluble metaphosphate, soluble phosphite, soluble metaphosphite, At least one of soluble pyrophosphate and soluble hypophosphite;
- the second coating layer is a phosphate compound formed by the reaction of non-aqueous substances added during the washing process with residual lithium on the surface of the sintered product, and the phosphate compound at least contains Li m PO n of ionic conductivity, 1 ⁇ m ⁇ 3, 1 ⁇ n ⁇ 4.
- the phosphate content in the first coating layer is 0.03wt% to 0.3wt% of the total mass of the secondary particles, preferably, the phosphate content is 0.075wt% to 0.175wt%, for example, it may be 0.075 wt%, 0.1 wt%, 0.125 wt%, 0.15 wt%, or 0.175 wt%.
- the phosphate content in the second coating layer is 0.1wt%-0.7wt% of the total mass of the secondary particles and the first coating layer, preferably, the phosphate content is 0.3wt%-0.5 wt%, for example, can be 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt% or 0.5wt%.
- the applicant has found through many tests that controlling the phosphate radical within the above range enables the primary particles or secondary particles to obtain a good coating effect without reducing the capacity of the positive electrode material.
- the primary coating is the first coating treatment of the positive electrode material
- the secondary coating is the second coating treatment of the positive electrode material
- the second coating layer on the surface of the secondary particle can not only protect the surface of the secondary particle from being corroded by the electrolyte, improve thermal stability, but also increase the diffusion rate of lithium ions and reduce the residual alkali on the surface, so that the obtained positive electrode material has high rate performance , high thermal stability, good processing performance and safety.
- the first coating layer on the surface of the primary particles also has the above-mentioned characteristics.
- the first coating layer can also prevent the primary particles inside the positive electrode material from directly contacting the electrolyte when the secondary particles are cracked, thereby suppressing side reactions. It is beneficial to improve the structural stability, thermal stability and long-term cycle stability of the secondary particles.
- the phosphate compound coating layer with high ion conductivity is formed at the grain boundary between the primary particles, the grain boundary transmission impedance is reduced. It is beneficial to improve the rate performance of the positive electrode material.
- the combination of internal and external coating methods synergistically improves the structural stability, thermal stability, safety, rate performance, long-term cycle performance and processing performance of the cathode material.
- the content of crystallized phosphate in the phosphate compound coating layer is 5wt% to 50wt% of the total mass of phosphate, for example, it can be 5wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt% %.
- the positive electrode material is a ternary positive electrode material.
- the powder conductivity of the positive electrode material under 4kN/cm 2 pressure is greater than 0.02S/cm, which can effectively improve the discharge capacity at high rates.
- the specific surface area of the positive electrode material is 0.2m 2 /g to 2.0m 2 /g.
- the specific surface area of the positive electrode material is 0.3m 2 /g ⁇ 0.8m 2 /g, for example, 0.3m 2 /g, 0.4m 2 /g, 0.5m 2 /g, 0.6m 2 /g, 0.7m 2 /g, 0.8m 2 /g, etc.
- the present application also provides a method for preparing a positive electrode material, as shown in Figure 2, the method includes the following steps S100-S200:
- the primary particles of the positive electrode material are coated with phosphate compounds and doped with metal cations during the calcination process; while the primary particle coating can prevent the cracking of the secondary particles, the primary particles inside the positive electrode material directly In contact with the electrolyte, side reactions are suppressed, which is beneficial to improve the structural stability, thermal stability and long-term cycle stability of the secondary particles.
- Layer which reduces the grain boundary transmission impedance, is conducive to improving the rate performance of the cathode material.
- the lithium compound is added in an amount such that the ratio of the sum of the molar contents of Ni, Co, M and metal elements in the metal phosphate to the molar contents of Li is 1: (0.95-1.10). Within this range, the mixing degree of Li/Ni cations can be reduced, and the excessive lithium residual on the surface of the sintered product can be prevented from affecting the processability and safety performance.
- the lithium compound includes at least one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate and lithium oxalate.
- the lithium compound is lithium hydroxide.
- the average particle size of the metal phosphate salt is less than 0.5 ⁇ m, for example, 0.001 ⁇ m, 0.01 ⁇ m, 0.05 ⁇ m, 0.1 ⁇ m, 0.15 ⁇ m, 0.2 ⁇ m, 0.25 ⁇ m, 0.3 ⁇ m, 0.35 ⁇ m, 0.4 ⁇ m or 0.45 ⁇ m.
- the metal element of the phosphate metal salt is selected from at least one of Co, Mn, Al, Ti, Zr, Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo and Sn.
- Typical but non-limiting examples of the combination include: a combination of SrHPO 4 and Zr(HPO 4 ) 2 , a combination of MgHPO 4 and Al(H 2 PO 4 ) 3 , and the like.
- the phosphate content in the metal phosphate salt is 0.03wt%-0.3wt% of the total mass of the mixture.
- it can be 0.03wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, or 0.3wt%.
- the phosphate content in the metal phosphate salt is 0.075wt%-0.175wt% of the total mass of the mixture. The applicant has found through many tests that controlling the phosphate content within this range can not only obtain a good primary particle coating effect, but also not reduce the capacity of the positive electrode material.
- the mixing time is 0.3h to 2.0h, for example, it can be 0.3h, 0.4h, 0.5h, 0.7h, 0.8h, 1.0h, 1.2h, 1.5h or 2.0h, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
- the mixing temperature is 10°C-50°C, such as 10°C, 15°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C, etc.
- the mixing temperature is 10°C-40°C.
- the sintered product is an active material with a first coating layer
- M is selected from at least one of Mn or Al
- R includes Co, Mn, Al, Ti, Zr , Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo and Sn at least one.
- the first coating layer is a phosphoric acid compound
- the phosphoric acid compound includes at least one of Li 3 PO 4 and LiR k (PO 4 ) r , 0 ⁇ k ⁇ 2, 0 ⁇ r ⁇ 2, R is selected from Co, Mn , Al, Ti, Zr, Sr, Mg, Ca, Y, Ba, Cu, W, Nb, La, Ce, Mo and Sn at least one.
- the mixture is sintered at 650°C to 850°C for 6h to 20h under an oxygen-containing atmosphere, crushed and sieved to obtain a sintered product, the sintered product includes a plurality of primary particles, and the primary particles have a first coating layer .
- the average particle diameter D50 of the primary particles is 200 nm to 1000 nm, for example, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm or 1000 nm.
- the metal phosphate salt reacts with the lithium compound at a high temperature to form the first coating layer of the primary particle
- the thickness of the first coating layer is 0.005 ⁇ m to 0.05 ⁇ m, for example, 0.005 ⁇ m, 0.01 ⁇ m, 0.015 ⁇ m, 0.02 ⁇ m, 0.025 ⁇ m, 0.03 ⁇ m, 0.035 ⁇ m, 0.04 ⁇ m, 0.045 ⁇ m or 0.05 ⁇ m.
- the thickness of the first cladding layer can also be other values within the above range, which is not limited here.
- the content of crystallized phosphate in the first coating layer is 5wt%-50wt% of the total mass of phosphate, such as 5wt%, 10wt%, 15wt%, 20wt%, 30wt%, 40wt% or 50wt%.
- the oxygen content in the oxygen-containing atmosphere is ⁇ 95%.
- the sintering temperature can be, for example, 650°C, 700°C, 720°C, 730°C, 750°C, 770°C, 780°C, 800°C or 850°C.
- the sintering The temperature is 720° C. to 800° C., but it is not limited to the listed values, and other unlisted values within this range are also applicable.
- the applicant has found through many experiments that sufficient oxygen can promote the oxidation of divalent nickel to trivalent nickel, reduce the mixing of Li/Ni cations, and increase the capacity of the positive electrode material. At the same time, this temperature range is conducive to the formation of a layered structure without causing cause the material to decompose.
- the sintering time may be, for example, 6h, 8h, 10h, 12h, 15h, 18h or 20h, etc., but is not limited to the listed values, and other unlisted values within this range are also applicable.
- the applicant has found through multiple tests that the above sintering time can effectively form a layered structure and a uniform primary particle coating layer, thereby taking into account various performance indicators of the positive electrode material.
- the particle size of the metal phosphate salt it is beneficial to form a uniform first coating layer on the surface of the primary particles, and the content of crystallized phosphate in the first coating layer is controlled at 5wt% to 50wt% so that the coating
- the combination of the coating and the surface of the positive electrode material is more stable, and the primary particle coating can prevent the cracking of the secondary particles.
- the primary particles inside the positive electrode material directly contact the electrolyte, the side reaction is suppressed, and it is also conducive to improving the structural stability of the secondary particles. Thermal stability and long-term cycle stability.
- the transport resistance of the grain boundary is reduced, which is conducive to improving the rate performance of the positive electrode material.
- the preparation method of the positive electrode material realizes the primary particle coating and metal cation doping of the active material during the sintering process, and then uses the solvent containing non-aqueous substances to wash the sintered material, and realizes the positive electrode material during the washing process.
- the secondary particle coating can inhibit the loss of lattice lithium on the surface of the positive electrode material, thereby improving its rate performance, thermal stability and cycle stability.
- the solvent includes water and a non-aqueous substance, that is, the non-aqueous substance is dissolved in an aqueous solution to obtain a solvent.
- the non-aqueous substances include phosphoric acid, metaphosphoric acid, phosphorous acid, metaphosphorous acid, pyrophosphoric acid, hypophosphorous acid, soluble phosphate, soluble metaphosphate, soluble phosphite, soluble metaphosphite, soluble pyrophosphate and soluble At least one of hypophosphite; preferably, the non-aqueous substance includes H 3 PO 4 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , (NH 4 ) 3 PO 4 , NaH 2 PO 4 , Na 2 HPO 4 and Na 3 PO 4 at least one.
- the content of phosphate in the solvent is 0.1wt%-0.7wt% of the total mass of the sintered product.
- it can be 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt% or 0.7 wt%.
- the phosphate content in the solvent is 0.3wt%-0.5wt% of the total mass of the sintered product. The applicant has found through many tests that controlling the phosphate radical within this range can obtain a good secondary particle coating effect without reducing the capacity of the positive electrode material.
- the coating layer has high lithium ion conductivity, which can not only improve the rate performance, and can effectively reduce the corrosion degree of the positive electrode material surface by electrolyte corrosion, which is conducive to improving the cycle performance of the positive electrode material.
- the washing temperature is 10°C to 50°C, specifically 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C or 50°C, etc. , but not limited to the listed values, other unlisted values within this range are also applicable.
- the washing time is 10min to 120min, specifically 10min, 20min, 30min, 60min, 90min or 120min, etc., but it is not limited to the listed values, other values not listed within the range values are also applicable.
- the concentration of the slurry composed of the sinter and the solvent (sinter (g)/solvent (L)) is 500g/L-2000g/L, specifically 500g/L , 800g/L, 1000g/L, 1250g/L or 2000g/L.
- the slurry concentration is too high, the amount of solvent used is insufficient, which is not conducive to the removal of lithium content on the surface of the material, and the free lithium content on the surface of the positive electrode material is too high, which will easily lead to serious gas production and increased surface impedance.
- washing temperature in a reasonable range is conducive to controlling the lithium content on the surface of the material, taking into account the problem of gas production and processing performance, washing temperature, slurry concentration and washing time.
- These three conditions affect each other, and synergistic control of these three conditions is conducive to protecting the surface structure of the positive electrode material particles, improving the corrosion resistance of the particle surface, controlling the lithium content on the surface of the material, and reducing gas production, so as to effectively balance the discharge capacity, thermal stability, rate performance, Safety performance and cycle performance.
- the drying is performed under a nitrogen atmosphere.
- the drying may also be performed with other protective gases, such as argon.
- the drying temperature is 80°C to 200°C, specifically 80°C, 100°C, 120°C, 150°C, 180°C or 200°C, etc., but not limited to the listed values , other unlisted values within this value range are also applicable.
- the drying time is 5h to 48h, specifically 5h, 10h, 12h, 15h, 18h, 20h, 24h, 28h, 32h, 36h, 40h, 44h or 48h, etc., but not Not limited to the listed values, other unlisted values within the range of values are also applicable.
- the average particle size of the secondary particles is 3 ⁇ m to 20 ⁇ m, such as 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, 10 ⁇ m, 11 ⁇ m, 12 ⁇ m, 13 ⁇ m, 15 ⁇ m or 20 ⁇ m, etc.
- the average particle size of the secondary particles is 10 ⁇ m-13 ⁇ m. The applicant has found through many tests that when the average particle size of the secondary particles is controlled within the range of 3 ⁇ m to 20 ⁇ m, the problem of cracking of the secondary particles during the cycle can be avoided, which is conducive to improving the structural stability of the secondary particles , thermal stability and long-term cycle stability.
- the thickness of the second coating layer is 0.02 ⁇ m ⁇ 0.2 ⁇ m, for example, 0.02 ⁇ m, 0.03 ⁇ m, 0.05 ⁇ m, 0.08 ⁇ m, 0.1 ⁇ m, 0.13 ⁇ m, 0.15 ⁇ m, 0.18 ⁇ m or 0.2 ⁇ m.
- the thickness of the second cladding layer can also be other values within the above range, which is not limited here.
- the non-aqueous substance in the solvent reacts with the residual lithium on the surface of the sintered product to form the second coating layer, and the content of crystallized phosphate in the second coating layer is 5 wt% to 50wt%. Specifically, it can be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt% or 50wt%.
- the method further includes:
- the washed and dried sintered product is heat-treated at 150° C. to 600° C. for 4 hours to 10 hours in an oxygen-containing atmosphere to obtain the positive electrode material.
- the heat treatment temperature can be 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 550°C or 600°C, etc.; the heat treatment time can be 4h, 5h, 6h, 7h, 8h, 9h Or 10h, etc., but not limited to the listed values, other unlisted values within this range are also applicable.
- the phosphoric acid compound can be more uniformly and firmly coated on the surface of the sintered product. , to form a phosphoric acid compound with high lithium ion conductivity, which is beneficial to control the content of crystallized phosphate in the coating layer of secondary particles, improve processing performance and rate performance, and prevent the sintered material from decomposing and lithium precipitation.
- the mixing method used in this embodiment may be mechanical mixing, such as a high mixer or a VC mixer.
- the preparation method of the positive electrode material provided by this application realizes the primary particle coating and metal cation doping of the positive electrode material during the sintering process, and realizes the coating of the secondary particle of the positive electrode material during solvent washing; it can form a uniform
- the coating layer can better suppress the loss of lattice lithium on the surface of the positive electrode material, thereby improving its rate performance, thermal stability and cycle stability.
- the embodiment of the present application further provides a lithium ion battery, including the above-mentioned positive electrode material or the positive electrode material prepared by the above-mentioned method for preparing the positive electrode material.
- the preparation method of positive electrode material comprises the following steps:
- the positive electrode material was sintered at 200° C. for 8 hours in an atmosphere with an oxygen content ⁇ 95%, crushed and sieved to obtain a phosphoric compound-coated positive electrode material Li 1.05 Ni 0.88 Co 0.09 Al 0.03 Sr 0.0026 O 2 .
- the positive electrode material obtained in this embodiment includes a plurality of secondary particles, and the secondary particles are a plurality of aggregates of primary particles; a first coating layer is formed on the surface of the primary particles, and a second coating layer is formed on the surface of the secondary particles.
- the average particle size of the primary particles is 0.6 ⁇ m
- the average particle size of the secondary particles is 12 ⁇ m
- the material of the primary particles is Li 1.05 Ni 0.88 Co 0.09 Al 0.03 Sr 0.0026 O 2
- the thickness of the first coating layer is 0.04 ⁇ m
- the material of the first coating layer is Li 3 PO 4 and LiSrPO 4
- the secondary particles are aggregates of the primary particles coated with the first coating layer, and the thickness of the second coating layer is 0.06 ⁇ m
- the second coating layer The material of the layer is Li 3 PO 4 and Li 3 Al(PO 4 ) 2
- the average phosphorus content a on the surface of the positive electrode material is 0.231wt%
- the minimum phosphorus content a' at any point on the surface of the positive electrode material is The value is 0.209 wt%, and the maximum value is 0.245 wt%.
- Table 1 shows the performance test results of the positive electrode material S1 prepared in this example.
- the preparation method of positive electrode material comprises the following steps:
- the positive electrode material obtained in this embodiment includes a plurality of secondary particles, and the secondary particles are a plurality of aggregates of primary particles; a first coating layer is formed on the surface of the primary particles, and a second coating layer is formed on the surface of the secondary particles.
- the average particle size of the primary particles is 0.7 ⁇ m
- the average particle size of the secondary particles is 11.5 ⁇ m
- the material of the primary particles is Li 1.03 Ni 0.83 Co 0.11 Mn 0.06 Zr 0.0009 O 2
- the thickness of the first coating layer is 0.02 ⁇ m
- the material of the first coating layer is Li 3 PO 4 and Li 2 Zr(PO 4 ) 2
- the secondary particles are aggregates of primary particles coated with the first coating layer, and the thickness of the second coating layer is 0.10 ⁇ m
- the substance of the second coating layer is Li 3 PO 4
- the average phosphorus content a on the surface of the positive electrode material is measured to be 0.135wt%
- the minimum value of the single-point phosphorus content a' of 10 arbitrary points on the surface of the positive electrode material is 0.125wt%, with a maximum of 0.142wt%.
- Table 1 shows the performance test results of the cathode material S2 prepared in this example.
- the preparation method of positive electrode material comprises the following steps:
- the positive electrode material obtained in this embodiment includes a plurality of secondary particles, and the secondary particles are a plurality of primary particle aggregates; a first coating layer is formed on the surface of the primary particles, and a second coating layer is formed on the surface of the secondary particles; wherein , the average particle size of the primary particles is 0.3 ⁇ m, the average particle size of the secondary particles is 12 ⁇ m, the material of the primary particles is LiNi 0.88 Co 0.09 Al 0.03 Mg 0.0009 Zr 0.0004 O 2 ; the thickness of the first cladding layer is 0.01 ⁇ m, The material of the first coating layer is Li 3 PO 4 , LiMgPO 4 and Li 2 Zr(PO 4 ) 2 ; the secondary particles are aggregates of the primary particles coated with the first coating layer, and the second coating layer The thickness is 0.15 ⁇ m; the substance of the second coating layer is Li 3 PO 4 , the average phosphorus content a on the surface of the positive electrode material is measured to be 0.069wt%, and the minimum phosphorus
- Table 1 shows the performance test results of the cathode material S3 prepared in this example.
- the preparation method of positive electrode material comprises the following steps:
- the positive electrode material was sintered at 500° C. for 5 hours in an atmosphere with an oxygen content ⁇ 95%, crushed and sieved to obtain the positive electrode material LiNi 0.88 Co 0.09 Al 0.03 Sr 0.0003 O 2 coated with phosphate compound.
- the positive electrode material obtained in this embodiment includes a plurality of secondary particles, and the secondary particles are a plurality of primary particle aggregates; a first coating layer is formed on the surface of the primary particles, and a second coating layer is formed on the surface of the secondary particles; wherein , the average particle size of the primary particles is 0.6 ⁇ m, the average particle size of the secondary particles is 11 ⁇ m, the material of the primary particles is LiNi 0.88 Co 0.09 Al 0.03 Sr 0.0003 O 2 , the thickness of the first coating layer is 0.008 ⁇ m, the first The materials of the coating layer are Li 3 PO 4 and LiSrPO 4 ; the secondary particles are aggregates of the primary particles coated with the first coating layer, and the thickness of the second coating layer is 0.18 ⁇ m; The substances are Li 3 PO 4 and Li 2 Zr(PO 4 ) 2 , the average phosphorus content a on the surface of the positive electrode material is measured to be 0.039wt%, and the minimum value of the single-point phosphorus content a'
- Table 1 shows the performance test results of the positive electrode material S4 prepared in Example 4.
- Example 1 Using the preparation method and process steps of Example 1, the difference between Comparative Example 1 and Example 1 is that no SrHPO 4 is added in step (1), and the solvent used in step (3) is pure water.
- Table 1 shows the performance test results of the positive electrode material D1 prepared in Comparative Example 1.
- the average phosphorus content a on the surface of the positive electrode material D1 prepared by this comparative example is 0wt%, and the single-point phosphorus content a' of 10 arbitrary points on the surface of the positive electrode material D1 is 0wt%.
- Table 1 shows the performance test results of the positive electrode material D2 prepared in Comparative Example 2.
- the average phosphorus content a on the surface of the positive electrode material D2 prepared by this comparative example is 0.092wt%, and the minimum value of the single-point phosphorus content a' of 10 arbitrary points on the surface of the positive electrode material D2 is 0.075wt%, and the maximum value is 0.116wt%. %.
- Table 1 shows the performance test results of the positive electrode material D3 prepared in Comparative Example 3.
- the average phosphorus content a on the surface of the positive electrode material D3 prepared by this comparative example is 0.154wt%, and the minimum value of the single-point phosphorus content a' of 10 arbitrary points on the surface of the positive electrode material D3 is 0.135wt%, and the maximum value is 0.173wt%. %.
- the difference between Comparative Example 4 and Example 1 is that the average particle size of SrHPO 4 added in step (1) is 10 ⁇ m.
- Table 1 shows the performance test results of the positive electrode material D4 prepared in Comparative Example 4.
- the average phosphorus content a on the surface of the positive electrode material D4 prepared by this comparative example is 0.245wt%, and the minimum value of the single-point phosphorus content a' of 10 arbitrary points on the surface of the positive electrode material D4 is 0.183wt%, and the maximum value is 0.302wt%. %.
- Comparative Example 5 Using the preparation method and process steps of Example 1, the difference between Comparative Example 5 and Example 1 is that during solvent washing, the washing temperature is 80° C., and the washing time is 60 min.
- Table 1 shows the performance test results of the positive electrode material D5 prepared in Comparative Example 5.
- the average phosphorus content a on the surface of the positive electrode material D5 prepared by this comparative example is 0.198wt%, and the minimum value of the single-point phosphorus content a' of 10 arbitrary points on the surface of the positive electrode material D5 is 0.152wt%, and the maximum value is 0.226wt%. %.
- a scanning electron microscope is used to analyze the morphology of the cathode material, and a scanning electron microscope picture thereof is obtained.
- the energy dispersive X-ray spectrometer (EDS) attached to the scanning electron microscope is used to perform point scanning to test the single-point phosphorus content a' on the surface of the positive electrode material.
- the energy dispersive X-ray spectrometer (EDS) attached to the scanning electron microscope was used to scan the surface to measure the average phosphorus content a on the surface of the positive electrode material.
- a button half-cell was used to evaluate the electrochemical performance of the prepared positive electrode material.
- a lithium sheet with a diameter of 16mm is used as the negative electrode sheet, a Celgard polypropylene PP film is used as the separator, and a solution of carbonate (diethyl carbonate DEC/ethylene carbonate EC volume ratio 1:1) of LiPF 6 with a concentration of 1mol/L is electrolyte, the coin half-cells were assembled in an argon-filled glove box.
- the capacity, first coulombic efficiency, and rate performance were tested at 25°C and 3.0V to 4.3V.
- the reference capacity was set to 200mA/g, and the current density corresponding to 1C was 200mA/g.
- a potentiometric titrator is used to test the total amount of lithium compounds on the surface of the positive electrode material, specifically titrated with hydrochloric acid, and then converted into the amount of lithium compounds by the amount of hydrochloric acid consumed.
- the positive electrode material particles are cut with an ion beam cutter, and then the element line scanning is performed on the cross section of the cut particles with a high-precision electron spectrometer, so that the distribution position of the phosphoric acid compound coating layer is calculated according to the line scanning element distribution curve.
- the thermal stability test of the electrode material was carried out in a closed high-pressure crucible at 5°C/min under a nitrogen atmosphere using a Neitz differential scanning calorimeter, and a differential scanning thermal curve was obtained.
- the above electrode material was cycled at 0.1C. Active material scraped from the fully charged electrode sheet after 2.5 weeks.
- Bruker X-ray diffractometer was used to measure the structure and composition of the cathode material, and then the content of crystallized phosphate in the phosphoric acid compound in the coating layer was obtained through refined calculation of the X-ray diffraction pattern.
- the positive electrode material obtained in Example 1 forms a uniform coating layer on the surface of the secondary particles, and the gaps between the primary particles are filled with phosphoric acid compounds, so that the contact at the grain boundaries is very close, and The coating layer is very closely combined with the positive electrode material.
- the surface of the secondary particles of the positive electrode material obtained in Comparative Example 1 is relatively smooth without a coating layer; at the same time, the gap between the primary particles is large, and the electrolyte is easy to penetrate into the interior of the secondary particles.
- the rate performance of the positive electrode material obtained in Example 1 is better than that of Comparative Example 1, indicating that the rate performance of the positive electrode material without phosphate compound coating on the primary particles is significantly worse.
- Example 6 the decomposition temperature and heat release of the positive electrode material in Example 1 are better than those in Comparative Example 1, indicating that coating the primary and secondary particles of the positive electrode material with phosphate compounds is beneficial to improve the thermal stability of the positive electrode material.
- the electrochemical properties of the positive electrode materials prepared in Examples 1 to 5 of the present application are all excellent, the discharge capacity is above 209mAh/g, the first Coulombic efficiency can reach about 90%, the rate performance is good, and the long cycle performance is outstanding. , the surface free lithium content is low.
- Example 1 From the comparison of the data of Example 1 and Comparative Example 2 in Table 1, it can be seen that when the primary particle or the secondary particle is not coated with a phosphoric acid compound, the surface residual alkali of the prepared positive electrode material is relatively high, and the rate performance, discharge Capacity and cycle performance are greatly affected. Comparing the data of Example 1 and Comparative Example 2, it can be seen that when the secondary coating is not washed with a solvent containing non-aqueous substances, the residual alkali on the surface of the obtained positive electrode material is seriously high, and cannot pass the processability test.
- Example 1 The comparison of the data of Example 1 and Comparative Example 3 and Comparative Example 4 shows that metal phosphate salt (SrHPO 4 ) is not added during the primary coating, or when the particle size of the metal phosphate salt added is too large, it is not conducive to the metal phosphate salt in the primary coating.
- a uniform first coating layer is formed on the surface of the particles, and the surface residual alkali of the prepared positive electrode material is relatively high, and the rate performance, discharge capacity, and cycle performance are greatly affected.
- Example 1 The comparison of the data of Example 1 and Comparative Example 5 shows that if the washing temperature is too high, it will easily lead to an increase in the free lithium content on the surface, and it will also easily lead to an uneven coating layer on the surface of the active material, thereby affecting the rate performance, discharge capacity, and cycle performance of the battery. .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
Claims (10)
- 一种正极材料,其特征在于,所述正极材料包括:二次粒子,所述二次粒子包括多个一次粒子,所述一次粒子包含活性物质,所述活性物质的化学通式为Li bNi xCo yM zR wO 2,其中,0.95≤b≤1.10,0.8≤x<1,0<y+z+w≤0.2,x+y+z+w=1,0.0001≤w≤0.003;M选自Mn及Al中的至少一种;R为掺杂金属;及包覆层,所述包覆层包括第一包覆层和第二包覆层,所述第一包覆层形成于所述一次粒子的表面,所述第二包覆层形成于所述二次粒子的表面,所述第一包覆层和第二包覆层均包含磷酸化合物;所述正极材料表面的任意一点处的单点磷含量a’,与所述正极材料表面的平均磷含量a之间满足以下关系:0.9a≤a’≤1.1a;其中,a’和a通过以下测试方法获得:在用扫描电子显微镜观察所述正极材料的情况下,对所述正极材料表面的任意一点进行EDS点扫描测试磷含量,得到a’,对扫描电子显微镜的视野中任意选取的边长为100μm的四边形区域进行EDS面扫描测试磷含量,得到a。
- 根据权利要求1所述的正极材料,其特征在于,所述Li bNi xCo yM zR wO 2中的R包括Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo及Sn中的至少一种。
- 根据权利要求1或2所述的正极材料,其特征在于,其满足以下条件a~k的至少一者:a.所述二次粒子呈球形或者类球形;b.所述一次粒子的平均粒径为200nm~1000nm,所述二次粒子的平均粒径为3μm~20μm;c.所述磷酸化合物包括Li 3PO 4及LiR k(PO 4) r中的至少一种,0<k≤2,0<r≤2,R包括Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo及Sn中的至少一种;d.所述第一包覆层的磷酸化合物的制备原料包括磷酸金属盐和锂化合物,所述第二包覆层的磷酸化合物的制备原料包括磷酸、偏磷酸、亚磷酸、偏亚磷酸、焦磷酸、次磷酸、可溶性磷酸盐、可溶性偏磷酸盐、可溶性亚磷酸盐、可溶性偏亚磷酸盐、可溶性焦磷酸盐和可溶性次磷酸盐中的至少一种;e.所述第一包覆层中的磷酸化合物的磷酸根含量为所述二次粒子的总质量的0.03wt%~0.3wt%;f.所述第二包覆层中的磷酸化合物的磷酸根含量为所述二次粒子和所述第一包覆层的总质量的0.1wt%~0.7wt%;g.所述第一包覆层或所述第二包覆层中的磷酸化合物的晶化磷酸根含量为磷酸根总质量的5wt%~50wt%;h.所述第一包覆层的厚度为0.005μm~0.05μm;i.所述第二包覆层的厚度为0.02μm~0.2μm;j.所述正极材料在4kN/cm 2加压下的粉体电导率大于0.02S/cm;k.所述正极材料的比表面积为0.2m 2/g~2.0m 2/g。
- 一种正极材料的制备方法,其特征在于,所述方法包括以下步骤:将Ni aCo bM cO或Ni aCo bM c(OH) 2、锂化合物以及磷酸金属盐混合,得到混合物,将所述混合物烧结,得到烧结物,其中,a+b+c=1,0.8≤a<1,0<b+c≤0.2,M选自Mn或Al中的至少一种,所述烧结物包括多个一次粒子及形成所述一次粒子表面的第一包覆层,所述第一包覆层包含磷酸化合物,所述磷酸金属盐的平均粒径小于0.5μm;及将所述烧结物在50℃以下(包含50℃)通过溶剂洗涤、干燥,得到所述正极材料,其中,所述正极材料包括二次粒子及形成所述二次粒子表面的第二包覆层,所述二次粒子是一次粒子的聚集体,所述第二包覆层包含磷酸化合物。
- 根据权利要求4所述的制备方法,其特征在于,其满足以下条件a~f的至少一者:a.所述锂化合物的添加量为:使得Ni、Co、M及所述磷酸金属盐中金属元素的摩尔含量总和与Li的摩尔含量比值为1:(0.95~1.10);b.所述锂化合物包括碳酸锂、氢氧化锂、醋酸锂、硝酸锂及草酸锂中的至少一种;c.所述磷酸金属盐的金属元素选自Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo及Sn中的至少一种;d.所述磷酸金属盐中的磷酸根含量为所述混合物总质量的0.03wt%~0.3wt%;e.得到所述混合物的混合条件为:在10℃~50℃下固相混合0.3h~2h;f.得到所述烧结物的烧结条件为:于含氧气氛下于650℃~850℃烧结6h~20h。
- 根据权利要求4所述的制备方法,其特征在于,其满足以下条件a~b的至少一者:a.所述溶剂包括水和非水物质,所述非水物质包括磷酸、偏磷酸、亚磷酸、偏亚磷酸、焦磷酸、次磷酸、可溶性磷酸盐、可溶性偏磷酸盐、可溶性亚磷酸盐、可溶性偏亚磷酸盐、可溶性焦磷酸盐和可溶性次磷酸盐中的至少一种;b.所述溶剂中的磷酸根含量为所述烧结物总质量的0.1wt%~0.7wt%。
- 根据权利要求4或6所述的制备方法,其特征在于,其满足以下条件a~f的至少一者:a.所述洗涤的温度为10℃~50℃;b.由所述烧结物和所述溶剂组成的浆料浓度(烧结物(g)/溶剂(L))为500g/L~2000g/L;c.所述洗涤时间为10min~120min;d.所述干燥是在氮气气氛条件下进行;e.所述干燥的温度为80℃~200℃;f.所述干燥的时间为5h~48h。
- 根据权利要求4所述的制备方法,其特征在于,在将所述烧结物通过溶剂洗涤、干燥之后,所述方法还包括:将洗涤、干燥后的所述烧结物置于含氧气氛下于150℃~600℃热处理4h~10h,得到所述正极材料。
- 根据权利要求4所述的制备方法,其特征在于,其满足以下条件a~f的至少一 者:a.所述磷酸金属盐与所述锂化合物高温反应形成所述一次粒子的第一包覆层;b.所述溶剂中的磷酸根离子与所述烧结物表面残余锂反应形成所述二次粒子的第二包覆层;c.所述磷酸化合物包括Li 3PO 4及LiR k(PO 4) r中的至少一种,0<k≤2,0<r≤2,R选自Co、Mn、Al、Ti、Zr、Sr、Mg、Ca、Y、Ba、Cu、W、Nb、La、Ce、Mo、Sn中的至少一种;d.所述第一包覆层或所述第二包覆层中的磷酸化合物的晶化磷酸根含量为磷酸根总质量的5wt%~50wt%;e.所述一次粒子的平均粒径为200nm~1000nm,所述第一包覆层的厚度为0.005μm~0.05μm;f.所述二次粒子的平均粒径为3μm~20μm,所述第二包覆层的厚度为0.02~0.2μm。
- 一种锂离子电池,其特征在于,包括如权利要求1-3任一项所述正极材料或如权利要求4~9任一项所述正极材料的制备方法制备的正极材料。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/548,868 US20240162425A1 (en) | 2022-02-16 | 2022-02-22 | Cathode material and method for preparing the same, lithium ion battery |
JP2022516738A JP2024511238A (ja) | 2022-02-16 | 2022-02-22 | 正極材料、その製造方法、及びリチウムイオン電池 |
EP22926535.0A EP4290615A1 (en) | 2022-02-16 | 2022-02-22 | Positive electrode material and preparation method therefor, and lithium-ion battery |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210142538.0 | 2022-02-16 | ||
CN202210142538.0A CN114583153B (zh) | 2022-02-16 | 2022-02-16 | 正极材料及其制备方法、锂离子电池 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023155215A1 true WO2023155215A1 (zh) | 2023-08-24 |
Family
ID=81770347
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2022/077289 WO2023155215A1 (zh) | 2022-02-16 | 2022-02-22 | 正极材料及其制备方法、锂离子电池 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20240162425A1 (zh) |
EP (1) | EP4290615A1 (zh) |
JP (1) | JP2024511238A (zh) |
CN (1) | CN114583153B (zh) |
WO (1) | WO2023155215A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117727914B (zh) * | 2024-02-07 | 2024-05-14 | 晶科储能科技有限公司 | 正极材料及其制备方法、二次电池 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102881911A (zh) * | 2012-09-29 | 2013-01-16 | 中南大学 | 一种液相沉淀法去除锂离子电池富镍材料表面锂残渣的方法 |
CN110190254A (zh) * | 2019-05-15 | 2019-08-30 | 华南理工大学 | 一种磷酸锂包覆锂离子电池三元正极材料的制备方法 |
CN112382741A (zh) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | 高镍正极材料及其制备方法、锂离子二次电池 |
CN112447966A (zh) * | 2019-09-02 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | 正极活性材料、正极极片及锂离子二次电池 |
US20210126256A1 (en) * | 2019-10-29 | 2021-04-29 | Samsung Sdi Co., Ltd. | Cathode active material for lithium secondary battery, preparation method thereof, cathode including cathode active material, and lithium secondary battery including cathode |
CN114050255A (zh) * | 2021-09-30 | 2022-02-15 | 深圳市贝特瑞纳米科技有限公司 | 正极活性材料及其制备方法、锂离子电池 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7283387B2 (ja) * | 2018-03-22 | 2023-05-30 | Tdk株式会社 | 負極及びリチウムイオン二次電池 |
CN109244439B (zh) * | 2018-11-27 | 2020-11-03 | 宁波容百新能源科技股份有限公司 | 一种多级层包覆的锂离子电池三元正极材料及其制备方法以及锂离子电池 |
CN109994728A (zh) * | 2019-03-29 | 2019-07-09 | 宁波容百新能源科技股份有限公司 | 一具有均匀包覆层的高镍正极材料及其制备方法 |
CN112786860B (zh) * | 2021-01-25 | 2021-11-16 | 上海电气集团股份有限公司 | 复合正极材料及其制备方法、正极浆料、正极极片与全固态电池 |
-
2022
- 2022-02-16 CN CN202210142538.0A patent/CN114583153B/zh active Active
- 2022-02-22 WO PCT/CN2022/077289 patent/WO2023155215A1/zh active Application Filing
- 2022-02-22 US US18/548,868 patent/US20240162425A1/en active Pending
- 2022-02-22 JP JP2022516738A patent/JP2024511238A/ja active Pending
- 2022-02-22 EP EP22926535.0A patent/EP4290615A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102881911A (zh) * | 2012-09-29 | 2013-01-16 | 中南大学 | 一种液相沉淀法去除锂离子电池富镍材料表面锂残渣的方法 |
CN110190254A (zh) * | 2019-05-15 | 2019-08-30 | 华南理工大学 | 一种磷酸锂包覆锂离子电池三元正极材料的制备方法 |
CN112447966A (zh) * | 2019-09-02 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | 正极活性材料、正极极片及锂离子二次电池 |
US20210126256A1 (en) * | 2019-10-29 | 2021-04-29 | Samsung Sdi Co., Ltd. | Cathode active material for lithium secondary battery, preparation method thereof, cathode including cathode active material, and lithium secondary battery including cathode |
CN112382741A (zh) * | 2020-10-12 | 2021-02-19 | 深圳市贝特瑞纳米科技有限公司 | 高镍正极材料及其制备方法、锂离子二次电池 |
CN114050255A (zh) * | 2021-09-30 | 2022-02-15 | 深圳市贝特瑞纳米科技有限公司 | 正极活性材料及其制备方法、锂离子电池 |
Also Published As
Publication number | Publication date |
---|---|
JP2024511238A (ja) | 2024-03-13 |
EP4290615A1 (en) | 2023-12-13 |
CN114583153B (zh) | 2024-01-26 |
CN114583153A (zh) | 2022-06-03 |
US20240162425A1 (en) | 2024-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022078300A1 (zh) | 正极材料及其制备方法、锂离子二次电池 | |
CN110504432B (zh) | 镍钴锰酸锂复合材料及其制备方法、锂电池正极及其制备方法、锂电池和供电装置 | |
US20220216507A1 (en) | Solid electrolyte material for lithium secondary battery, electrode, and battery | |
EP3930051B1 (en) | Positive electrode material and application thereof | |
Wang et al. | Improving the electrochemical performances of spherical LiNi0. 5Mn1. 5O4 by Fe2O3 surface coating for lithium-ion batteries | |
Song et al. | CuGaS 2 nanoplates: a robust and self-healing anode for Li/Na ion batteries in a wide temperature range of 268–318 K | |
US20230382763A1 (en) | Fast ionic conductor coated lithium-transition metal oxide material and preparation method thereof | |
CN110679018A (zh) | 非水系电解质二次电池用正极活性物质和其制造方法、非水系电解质二次电池用正极复合材料糊剂和非水系电解质二次电池 | |
CN113611856B (zh) | 正极材料及其制备方法、锂离子电池 | |
WO2019039567A1 (ja) | 非水系電解質二次電池用正極活物質とその製造方法、非水系電解質二次電池用正極合材ペーストおよび非水系電解質二次電池 | |
JP2016143527A (ja) | 被覆リチウム−ニッケル複合酸化物粒子の製造方法 | |
Madram et al. | Effect of Na+ and K+ co-doping on the structure and electrochemical behaviors of LiFePO 4/C cathode material for lithium-ion batteries | |
WO2023155215A1 (zh) | 正极材料及其制备方法、锂离子电池 | |
Cheng et al. | Optimizing surface residual alkali and enhancing electrochemical performance of LiNi0. 8Co0. 15Al0. 05O2 cathode by LiH2PO4 | |
CN112670487A (zh) | 一种多重致密包覆的动力用高镍正极材料及制备方法 | |
KR20150064320A (ko) | 리튬 이차 전지용 양극 활물질 및 이의 제조 방법 | |
CN116805680A (zh) | 一种复合正极材料及其制备方法和应用 | |
Xue et al. | Improved Li-storage performance of Mg2+-doped LiVPO4F@ C cathode material synthesized by a fast carbothermal reduction reaction | |
Zhou et al. | Enhanced stability of vanadium-doped Li 1.2 Ni 0.16 Co 0.08 Mn 0.56 O 2 cathode materials for superior Li-ion batteries | |
CN113540435A (zh) | 高镍三元材料表面含磷化合物的修饰方法与锂离子电池 | |
KR102125766B1 (ko) | 양극활물질 표면처리용 조성물, 이의 제조방법 및 이에 의하여 표면 처리된 양극활물질 | |
JP7439473B2 (ja) | リチウムイオン二次電池用正極活物質、その製造方法、およびリチウムイオン二次電池 | |
KR102602699B1 (ko) | Al 도핑 전극활물질의 제조방법 | |
KR102214599B1 (ko) | 이차전지 양극활물질용 리튬-니켈 복합 산화물의 제조방법 | |
WO2024032550A1 (zh) | 电池材料及其制备方法、和二次电池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2022516738 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022926535 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 18548868 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2022926535 Country of ref document: EP Effective date: 20230829 |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22926535 Country of ref document: EP Kind code of ref document: A1 |