CN111430700A - Quaternary positive electrode material for lithium ion battery, preparation method of quaternary positive electrode material and lithium ion battery - Google Patents
Quaternary positive electrode material for lithium ion battery, preparation method of quaternary positive electrode material and lithium ion battery Download PDFInfo
- Publication number
- CN111430700A CN111430700A CN201910959426.2A CN201910959426A CN111430700A CN 111430700 A CN111430700 A CN 111430700A CN 201910959426 A CN201910959426 A CN 201910959426A CN 111430700 A CN111430700 A CN 111430700A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- equal
- quaternary
- electrode material
- lithium
- 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.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims description 119
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 93
- 239000010405 anode material Substances 0.000 claims abstract description 50
- 239000011247 coating layer Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910005518 NiaCobMnc Inorganic materials 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 60
- 238000005245 sintering Methods 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000002019 doping agent Substances 0.000 claims description 21
- 239000011883 electrode binding agent Substances 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000010955 niobium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 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
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000007580 dry-mixing Methods 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- FYWUVDVZWURZJH-UHFFFAOYSA-E [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] FYWUVDVZWURZJH-UHFFFAOYSA-E 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 nickel-cobalt-manganese-aluminum Chemical compound 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- H01M4/36—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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
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)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a quaternary anode material for a lithium ion battery, a preparation method thereof and the lithium ion battery, wherein the quaternary anode material comprises an inner core and a coating layer, the coating layer is formed on at least part of the surface of the inner core, the quaternary anode material has the composition shown in the formula (I), L IxNiaCobMncAldMyO2(I) In the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, M is selected from the second main groupAt least one of elements, elements of the third main group, elements of the fourth main group, elements of the fifth main group, elements of the fourth subgroup and elements of the fifth subgroup. According to the quaternary anode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a quaternary anode material for a lithium ion battery, a preparation method of the quaternary anode material and the lithium ion battery.
Background
Lithium ion batteries are widely used in electric vehicles, hybrid vehicles and energy storage systems due to their high capacity and high energy density, and the positive electrode material, which is one of the core components of lithium ion batteries, has a significant impact on the performance of lithium ion batteries.
Researchers find that high-nickel cathode materials have the advantages of high capacity and low price and are gradually replacing L iCoO2The cycle performance of the cathode material is poor, but the cycle performance of the high-nickel cathode material is poor. In order to improve the performance of the battery, the residual alkali content on the surface of the cathode material needs to be reduced, otherwise, the cathode material is gelatinized in the homogenizing process, and the industrial application of the cathode material is hindered. In addition, the anode material in the battery is in contact with the electrolyte, and the anode material is easy to generate chemical reaction with the electrolyte, so that the transition metal in the anode material is dissolved into the electrolyte, thereby increasing the interface impedance of the anode material and reducing the capacity and cycle performance of the battery. Therefore, the existing lithium ion battery cathode material still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a quaternary positive electrode material for a lithium ion battery, a method for preparing the same, and a lithium ion battery. According to the quaternary anode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
In one aspect of the invention, a quaternary positive electrode material for a lithium ion battery is presented. According to the embodiment of the invention, the quaternary positive electrode material comprises an inner core and a coating layer, wherein the coating layer is formed on at least part of the surface of the inner core, the quaternary positive electrode material has the composition shown in the formula (I),
LixNiaCobMncAldMyO2(I)
in the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, and M is at least one selected from the group consisting of second main group elements, third main group elements, fourth main group elements, fifth main group elements, fourth subgroup elements and fifth subgroup elements.
The quaternary positive electrode material for the lithium ion battery according to the embodiment of the invention has a core-shell structure comprising an inner core and a coating layer, wherein the inner core can be obtained by doping an M element with a nickel-cobalt-manganese-aluminum quaternary material (NCMA material), and simultaneously has the coating layer, and the whole quaternary positive electrode material has the composition shown in the formula (I). According to the quaternary anode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
In addition, the quaternary positive electrode material according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the invention, M is at least one selected from Mg, Ba, B, Al, Si, P, Ti, Zr, Nb.
In some embodiments of the invention, M is Al, Zr, B.
In some embodiments of the invention, M is Al, Ti, Nb.
In some embodiments of the invention, M is Al, Mg, Ti.
In another aspect of the present invention, the present invention provides a method of preparing the quaternary positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material; (2) carrying out first sintering treatment on the first mixed material to obtain a quaternary anode material core; (3) mixing the quaternary positive electrode material core with a first coating agent to obtain a second mixed material; (4) carrying out second sintering treatment on the second mixed material to obtain a primary coated product; (5) mixing the primary coated product with a second coating agent to obtain a third mixed material; and (6) calcining the third mixed material to obtain the quaternary positive electrode material. The method is simple and convenient to operate and easy to implement industrially, and the prepared quaternary anode material can improve the thermal stability and the cycle performance of the material while keeping the high nickel capacity of the material.
In addition, the method for preparing the quaternary positive electrode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the quaternary positive electrode material precursor has a composition as shown in formula (II), NiaCobMncAld(OH)2(II). In the formula (II), a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01 and less than or equal to 0.03, and a + b + c + d is 1;
in some embodiments of the invention, the lithium source comprises at least one selected from the group consisting of lithium nitrate, lithium carbonate, lithium hydroxide monohydrate.
In some embodiments of the present invention, the dopant comprises at least one selected from the group consisting of zirconium hydroxide, zirconium oxide, titanium oxide, magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium nitrate, barium hydroxide, aluminum oxide, aluminum hydroxide, aluminum oxyhydroxide, zinc oxide, niobium pentoxide, and the like;
in some embodiments of the present invention, the first coating agent comprises at least one selected from the group consisting of alumina, aluminum hydroxide, aluminum nitrate, aluminum oxyhydroxide, and the like;
in some embodiments of the present invention, the second coating agent comprises at least one selected from boric acid, boron oxide, lithium phosphate, lithium niobate, and the like.
In some embodiments of the invention, in the step (1), the molar ratio of the quaternary positive electrode material precursor to the lithium element in the lithium source is 1 (1.00-1.05); the mass ratio of the quaternary positive electrode material precursor to the doping elements in the dopant is 1 (0.001-0.003).
In some embodiments of the invention, in the step (3), the mass ratio of the quaternary positive electrode material core to the coating element in the first coating agent is 1 (0.0005-0.001).
In some embodiments of the invention, in the step (5), the mass ratio of the primary coating product to the coating element in the second coating agent is 1 (0.001-0.01).
In some embodiments of the present invention, the first sintering treatment is performed at 700 to 820 ℃ for 8 to 20 hours.
In some embodiments of the present invention, the second sintering treatment is performed at 600-700 ℃ for 6-15 h.
In some embodiments of the invention, the calcination treatment is performed at 300-600 ℃ for 8-18 h.
In some embodiments of the present invention, step (5) is preceded by: and carrying out water washing treatment and drying treatment on the primary coated product.
In some embodiments of the invention, the mass ratio of the primary coating product to the water in the water washing treatment is (1-2): 1, and the water washing treatment is carried out at a stirring speed of 500-800 rpm for 30-600 s.
In some embodiments of the present invention, the drying process is performed at 100 to 180 ℃ for 3 to 20 hours.
In yet another aspect of the present invention, a lithium ion battery is presented. According to an embodiment of the present invention, the lithium ion battery includes: a positive electrode, a negative electrode, a separator and an electrolyte; wherein the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the positive electrode active material is the quaternary positive electrode material described in the above embodiment. The negative electrode includes: an anode current collector and an anode material supported on the anode current collector, the anode material comprising: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
The lithium ion battery according to the embodiment of the invention has all the features and advantages described above for the quaternary positive electrode material by using the quaternary positive electrode material of the above embodiment as the positive electrode active material, and thus, the description thereof is omitted. In general, the lithium ion battery has higher capacity and better cycle stability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow diagram of a method of making a quaternary positive electrode material according to one embodiment of the invention;
fig. 2 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in example 1 according to the present invention;
fig. 3 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in comparative example 1 according to the present invention;
fig. 4 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material according to the present invention, which was prepared in comparative example 2;
fig. 5 is a graph showing the first charge and discharge curves of a battery fabricated using the quaternary positive electrode material prepared in comparative example 3 according to the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a quaternary positive electrode material for a lithium ion battery is presented. According to the embodiment of the invention, the quaternary positive electrode material comprises an inner core and a coating layer, wherein the coating layer is formed on at least part of the surface of the inner core, the quaternary positive electrode material has the composition shown in the formula (I),
LixNiaCobMncAldMyO2(I)
in the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, and M is at least one selected from the group consisting of second main group elements, third main group elements, fourth main group elements, fifth main group elements, fourth subgroup elements and fifth subgroup elements.
The quaternary positive electrode material for the lithium ion battery according to the embodiment of the invention has a core-shell structure comprising an inner core and a coating layer, wherein the inner core can be obtained by doping an M element with a nickel-cobalt-manganese-aluminum quaternary material (NCMA material), and simultaneously has the coating layer, and the whole quaternary positive electrode material has the composition shown in the formula (I). According to the quaternary anode material, the doping elements are introduced into the core to form the coating layer, so that the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
Specifically, in formula (I), x may be 1.00, 1.01, 1.02, 1.03, 1.04, 1.05, etc., y may be 0, 0.01, 0.02, 0.03, 0.04, 0.05, etc., a may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.92, etc., b may be 0.03, 0.04, 0.05, 0.06, etc., c may be 0.01, 0.02, 0.03, etc., d may be 0.01, 0.02, 0.03, etc., and a, b, c, d satisfy a + b + c + d of 1.
Specifically, M is a doping element and/or a coating element of the NCMA material, and may be present in the core of the quaternary positive electrode material, the coating layer of the quaternary positive electrode material, or both. Therefore, the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
According to an embodiment of the present invention, M may be at least one selected from Mg, Ba, B, Al, Si, P, Ti, Zr, Nb. By doping and/or coating the NCMA material by adopting the elements, the thermal stability and the cycle performance of the material can be improved while the high nickel capacity of the material is kept.
According to a preferred embodiment of the invention, M is Zr, Al, B. The positive electrode material is characterized in that the positive electrode material comprises a positive electrode material core, a negative electrode material core and a negative electrode material core, wherein Zr is used as a doping element of the NCMA material core and can keep the material to have higher capacity, and Al and B are used as coating elements of the NCMA material core and can play a role in shielding active sites on the surface of the NCMA material core, so that the occurrence of side reactions between the positive electrode material and an electrolyte is effectively reduced, and the cycle performance and the thermal stability of the material are further improved.
According to a preferred embodiment of the invention, M is Al, Ti, Nb. The Ti is used as a doping element of the NCMA material core, so that the material can be kept to have higher capacity, and the Al and the Nb are used as coating elements of the NCMA material core, so that the NCMA material core surface active sites can be shielded, the occurrence of side reactions between the anode material and the electrolyte can be effectively reduced, and the cycle performance and the thermal stability of the material can be further improved.
According to a preferred embodiment of the invention, M is Al, Mg, Ti. The Mg and the Ti are used as doping elements of the NCMA material core, so that the material can be kept to have higher capacity, and the Al is used as a coating element of the NCMA material core, so that the NCMA material core surface active sites can be shielded, the occurrence of side reactions between the anode material and the electrolyte can be effectively reduced, and the cycle performance and the thermal stability of the material can be further improved.
The inventor finds in research that doping of elements such as Al, Mg, Zr, Ti and the like can stabilize the structure of the material, improve the electronic conductivity and the ionic conductivity, improve the capacity of the material, and improve the cycling stability and the thermal stability of the material. And can resist the corrosion of the electrolyte to the anode material through the coating effect, prevent the dissolution of metal ions in the anode material, reduce the surface impedance and improve the cycle stability and the thermal stability.
In another aspect of the present invention, the present invention provides a method of preparing the quaternary positive electrode material of the above embodiment. According to an embodiment of the invention, the method comprises: (1) mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material; (2) carrying out first sintering treatment on the first mixed material to obtain a quaternary anode material core; (3) mixing the quaternary positive electrode material core with a first coating agent to obtain a second mixed material; (4) performing second sintering treatment on the second mixed material to obtain a primary coated product; (5) mixing the primary coating product with a second coating agent to obtain a third mixed material; and (6) calcining the third mixed material to obtain the secondary coated quaternary anode material. The method is simple and convenient to operate and easy to implement industrially, and the prepared quaternary anode material can improve the thermal stability and the cycle performance of the material while keeping the high nickel capacity of the material.
The method of preparing the quaternary positive electrode material according to the embodiment of the present invention is further described in detail below. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: obtaining a first mixed material
In the step, a quaternary positive electrode material precursor, a lithium source and a dopant are mixed to obtain a first mixed material.
According to an embodiment of the present invention, the specific type of the quaternary positive electrode material precursor is not particularly limited, and those skilled in the art can select the quaternary positive electrode material precursor according to actual needs, for example, nickel cobalt manganese aluminum hydroxide is used. According to the method provided by the invention, the conventional commercial quaternary anode material precursor is doped by using the dopant, and the prepared quaternary anode material has better thermal stability and cycle performance while keeping high nickel capacity through subsequent coating. In some embodiments of the invention, the quaternary positive electrode material precursor has a composition as shown in formula (II),
NiaCobMncAld(OH)2(II)。
in the formula (II), a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01 and less than or equal to 0.03, and a + b + c + d is equal to 1. In formula (II), a may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.92, etc., b may be 0.03, 0.04, 0.05, 0.06, etc., c may be 0.01, 0.02, 0.03, etc., d may be 0.01, 0.02, 0.03, etc., and a, b, c, d satisfy a + b + c + d of 1.
According to an embodiment of the present invention, a specific kind of the above-described lithium source is not particularly limited, and a lithium source commonly used in the art for preparing a positive active material of a lithium battery may be used. According to a specific example of the present invention, the lithium source may include at least one selected from the group consisting of lithium nitrate, lithium carbonate, and lithium hydroxide monohydrate. The lithium source has wide sources, is cheap and easy to obtain, and has good compatibility with nickel, cobalt, manganese and aluminum elements and doping elements (namely M elements).
According to embodiments of the present invention, the doping element may be provided in the form of an oxide, hydroxide, chloride, etc. of M. That is, the dopant includes a dopant selected from the group consisting of zirconium hydroxide (Zr (OH)4) Zirconium oxide (ZrO)2) Titanium oxide (TiO)2) Magnesium hydroxide (Mg (OH)2) Magnesium oxide (MgO), magnesium carbonate (MgCO)3) Magnesium nitrate (Mg (NO)3)2) Barium hydroxide (Ba (OH)2) Alumina (Al)2O3) Aluminum hydroxide (Al (OH)3) Aluminum oxyhydroxide (AlOOH), zinc oxide (ZnO), niobium pentoxide (Nb)2O5) And the like. By adopting the doping agent, the required doping elements can be introduced into the quaternary anode material core, so that the thermal stability and the cycle performance of the material are improved while the high nickel capacity of the material is maintained.
According to an embodiment of the present invention, the quaternary positive electrode material precursor, the lithium source, and the doping element may be mixed in the following ratio: the molar ratio of the quaternary positive electrode material precursor to the lithium element in the lithium source is 1 (1.00-1.05), such as 1:1.00, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, and the like; the mass ratio of the quaternary positive electrode material precursor to the doping element (i.e., M element) in the dopant is 1 (0.001-0.003), for example, 1:0.001, 1:0.002, 1:0.003, and the like. Therefore, the capacity, the thermal stability and the cycle performance of the prepared quaternary anode material can be further improved.
S200: first sintering process
In the step, the first mixed material is subjected to first sintering treatment to obtain a quaternary anode material core. Specifically, the first sintering treatment may be performed in an oxygen atmosphere to introduce a doping element into the NCMA material and form a quaternary positive electrode material core.
According to the embodiment of the invention, the first sintering treatment can be completed at 700-820 ℃ for 8-20 h. Specifically, the sintering temperature can be 700 ℃, 720 ℃, 750 ℃, 790 ℃, 820 ℃ and the like, and the sintering time can be 8h, 12h, 15h, 18h, 20h and the like. By performing the first sintering treatment under the above conditions, the quality of the sintered quaternary positive electrode material core can be further improved.
According to the embodiment of the invention, after the first sintering treatment is completed, the inner core of the quaternary positive electrode material can be cooled, crushed and sieved, and the material with the average particle size of 5-20 μm is obtained for subsequent processes, wherein the specific particle size can be determined according to the particle size of the precursor of the quaternary positive electrode material.
S300: obtaining a second blend
In the step, the quaternary positive electrode material core and the first coating agent are mixed, so that the first coating agent is uniformly coated on the surface of the quaternary positive electrode material core, and the second mixed material is obtained.
According to an embodiment of the present invention, the first coating element may be provided in the form of an oxide, a hydroxide, or the like of the M element, that is, the above-mentioned first coating agent may include a material selected from alumina (Al)2O3) Aluminum hydroxide (Al (OH)3) At least one of [ sic ]. cndot.. cndot. The coating containing the M element is introduced to the surface of the quaternary positive electrode material core by using the first coating agent, so that active sites on the surface of the NCMA material can be effectively shielded, the occurrence of side reactions of the quaternary positive electrode material core and electrolyte can be reduced, and the thermal stability and the cycle performance of the material can be improved.
According to an embodiment of the present invention, the quaternary positive electrode material may be mixed with the first coating agent in the following ratio: the mass ratio of the quaternary positive electrode material core to the coating element (i.e., M element) in the first coating agent is 1 (0.0005 to 0.001), for example, 1:0.0005, 1:0.0006, 1:0.0007, 1:0.0008, 1:0.001, and the like. Therefore, the capacity, the thermal stability and the cycle performance of the prepared quaternary anode material can be further improved.
S400: second sintering treatment
In the step, the second mixed material is subjected to second sintering treatment to obtain a primary coated product. Specifically, the second sintering treatment may be performed in an oxygen atmosphere to form a stable coating layer on the surface of the quaternary positive electrode material core.
According to the embodiment of the invention, the second sintering treatment can be completed at 600-700 ℃ for 6-15 h. Specifically, the sintering temperature can be 600 ℃, 620 ℃, 680 ℃, 700 ℃ and the like, and the sintering time can be 6h, 8h, 10h, 12h, 15h and the like. By performing the second sintering treatment under the above-described conditions, the quality of the primary-coated quaternary positive electrode material obtained by sintering can be further improved.
According to the embodiment of the invention, after the second sintering treatment is completed, the quaternary positive electrode material core can be cooled, crushed and sieved to obtain the material with the average particle size of 5-20 μm, and the specific particle size can be determined according to the particle size of the precursor of the quaternary positive electrode material.
S500: obtaining a third mixed material
In the step, the primary coated product is mixed with a second coating agent, so that the second coating agent is uniformly coated on the surface of the primary coated quaternary anode material, and a third mixed material is obtained.
According to an embodiment of the present invention, the second coating element may be provided in the form of an oxide, a hydroxide, or the like of the M element, that is, the above-mentioned second coating agent may include a compound selected from boric acid (H)3BO3) Boron oxide (B)2O3) At least one of [ sic ]. cndot.. cndot. The second coating element is introduced to the surface of the primary coated quaternary positive electrode material by using the second coating agent, so that the active sites on the surface of the NCMA material can be further effectively shielded, the occurrence of side reactions between the quaternary positive electrode material core and the electrolyte can be further reduced, and the thermal stability and the cycle performance of the material can be further improved.
According to an embodiment of the present invention, the primary-coated quaternary positive electrode material may be mixed with the second coating agent in the following ratio: the mass ratio of the coating element (i.e. M element) in the primary coating product and the second coating agent is 1 (0.001-0.01), such as 1:0.001, 1:0.003, 1:0.005, 1:0.008, 1:0.01, etc. Therefore, the capacity, the thermal stability and the cycle performance of the prepared quaternary anode material can be further improved.
S600: calcination treatment
In the step, the third mixed material is calcined to obtain a secondary coated quaternary anode material. Specifically, the calcination treatment may be performed in an oxygen atmosphere in order to stably introduce the second coating element into the primary coated quaternary positive electrode material.
According to the embodiment of the invention, the calcination treatment can be completed at 300-600 ℃ for 8-18 h. Specifically, the calcination temperature can be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃ and the like, and the sintering time can be 8h, 12h, 14h, 16h, 18h and the like. By performing the calcination treatment under the above conditions, the quality of the secondary-coated quaternary positive electrode material obtained by sintering can be further improved.
According to the embodiment of the invention, after the calcination treatment is completed, the quaternary positive electrode material can be cooled, crushed and sieved to obtain a product with the average particle size of 5-20 μm, and the specific particle size can be determined according to the particle size of the precursor of the quaternary positive electrode material.
In order to further improve the quality of the resultant quaternary positive electrode material, according to an embodiment of the present invention, the primary coating product may be subjected to a water washing process and a drying process before S5002CO3、LiOH、Li2O and the like. If the impurities are not removed, the viscosity of the battery slurry is increased and even the battery slurry is in a gel or jelly shape in the battery manufacturing process, and the material cannot enter the next process.
According to the embodiment of the invention, in the water washing treatment, the mass ratio of the primary coating product to the water can be (1-2): 1, and the water washing treatment can be completed at a stirring speed of 500-800 rpm for 30-600 s.
According to the embodiment of the invention, the drying treatment is carried out at 100-180 ℃ for 3-20 h. Specifically, the drying temperature may be 100 ℃, 120 ℃, 140 ℃, 180 ℃ and the like, and the drying time may be 3 hours, 5 hours, 12 hours, 15 hours, 18 hours, 20 hours and the like. Therefore, the moisture in the material can be effectively removed, and the problems of deterioration and the like of the material due to overhigh drying temperature or drying time process can be guaranteed.
In another aspect of the present invention, a lithium ion battery is provided. According to an embodiment of the present invention, the lithium ion battery includes: a positive electrode, a negative electrode, a separator and an electrolyte; wherein, positive pole includes: the positive pole current collector and the positive pole material of load on the positive pole current collector, positive pole material includes: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; the positive electrode active material is the quaternary positive electrode material of the above embodiment. The negative electrode includes: the negative electrode comprises a negative electrode current collector and a negative electrode material loaded on the negative electrode current collector, wherein the negative electrode material comprises: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
The lithium ion battery according to the embodiment of the invention has all the features and advantages described above for the quaternary positive electrode material by using the quaternary positive electrode material of the above embodiment as the positive electrode active material, and thus, the description thereof is omitted. In general, the lithium ion battery has higher capacity and better cycle stability.
According to some embodiments of the present invention, the positive electrode material includes a positive electrode active material, a positive electrode conductive agent, and a positive electrode binder; the mass ratio of the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected according to actual needs. The positive electrode active material was the quaternary positive electrode material of the above-described embodiment. The specific types of the positive electrode conductive agent and the positive electrode binder are not particularly limited, and for example, the positive electrode conductive agent may be at least one of common positive electrode binders such as conductive carbon black SP or ECP, carbon nanotubes (CNT or WCNT), graphene, and the like; the positive electrode binder may be at least one of common positive electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. The positive electrode material may further include a common solvent (e.g., NMP) for mixing the positive electrode material, and the ratio of the solvent to the positive electrode active material, the positive electrode conductive agent, and the positive electrode binder is not particularly limited, and may be selected by those skilled in the art according to actual needs.
According to some embodiments of the present invention, the negative electrode material includes a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder; the mass ratio of the negative electrode active material, the negative electrode conductive agent, the negative electrode binder, and the thickening stabilizer is not particularly limited, and may be selected according to actual needs. The specific types of the negative electrode active material, the negative electrode conductive agent and the negative electrode binder are not particularly limited, and the negative electrode active material can be at least one of common negative electrode active materials selected from natural graphite, artificial graphite, mesophase microspheres, soft carbon, hard carbon and the like; the negative electrode conductive agent can be at least one of conductive carbon black SP or ECP, carbon nano tube (CNT or WCNT), graphene and other common negative electrode conductive agents; the negative electrode binder may be at least one of common negative electrode binders such as polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and the like. In addition, the negative electrode material may further include a common solvent (e.g., NMP, deionized water, etc.) for mixing the negative electrode material, and the solvent is not particularly limited and may be selected by those skilled in the art according to actual needs.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(1) Making quaternary precursor Ni of positive electrode materialaCobMncAld(OH)2Dry mixing (a 0.88, b 0.06, c 0.03, d 0.03), lithium source and dopant in the following proportion, wherein the anode material quaternary precursor (nickel cobalt manganese aluminum hydroxide) and L i element in lithium source (L iOH) are mixed according to the molar ratio of 1:1.035, and dopant (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And (3) sintering the dry-mixed material for 10h at 740 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the primary-sintered quaternary anode material (first product).
(2) Mixing the first product with a first coating agent (Al)2O3) And (3) uniformly mixing the first product and Al element by a dry method according to the mass ratio of 1:0.0005 to ensure that the first coating agent is uniformly coated on the surface of the first product, carrying out primary sintering on the material subjected to dry mixing for 6 hours at 600 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain a primary coated quaternary positive electrode material (second product).
(3) And mixing the second product with deionized water according to the mass ratio of 2:1, stirring at the rotating speed of 600rpm at room temperature for 60s, filtering, and carrying out vacuum drying at 150 ℃ for 8h to obtain the primary coated quaternary anode material (third product) which is washed and dried.
(4) Mixing the third product with a second coating agent (B)2O3) And uniformly mixing the third product and the element B by a dry method according to the mass ratio of 0.001:1 to ensure that the second coating agent is uniformly coated on the surface of the third product, calcining the material obtained after the dry mixing at a certain temperature of 400 ℃ in an oxygen atmosphere for 10 hours, cooling, crushing and sieving to obtain the secondary coated quaternary anode material.
Comparative example 1
(1) Making quaternary precursor Ni of positive electrode materialaCobMncAld(OH)2Dry mixing (a 0.88, b 0.06, c 0.03, d 0.03), lithium source and dopant in the following proportion, wherein the anode material quaternary precursor (nickel cobalt manganese aluminum hydroxide) and L i element in lithium source (L iOH) are mixed according to the molar ratio of 1:1.035, and dopant (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And sintering the dry-mixed material for 10 hours at 735 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the quaternary anode material product.
Comparative example 2
(1) Making quaternary precursor Ni of positive electrode materialaCobMncAld(OH)2Dry mixing (a 0.88, b 0.06, c 0.03, d 0.03), lithium source and dopant in the following proportion, wherein the anode material quaternary precursor (nickel cobalt manganese aluminum hydroxide) and L i element in lithium source (L iOH) are mixed according to the molar ratio of 1:1.035, and dopant (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003:1 and mixing. And (3) sintering the dry-mixed material for 10h at 740 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the primary-sintered quaternary anode material (first product).
(2) Mixing the first product with a first coating agent (Al)2O3) And uniformly mixing the first product and the Al element in a mass ratio of 1:0.0005 by a dry method to ensure that the first coating agent is uniformly coated on the surface of the first product, sintering the material subjected to dry mixing for 6 hours at 600 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain a primary coated quaternary anode material product.
Comparative example 3
(1) Making quaternary precursor Ni of positive electrode materialaCobMncAld(OH)2Dry mixing (a 0.88, b 0.06, c 0.03, d 0.03), lithium source and dopant in the following proportion, wherein the anode material quaternary precursor (nickel cobalt manganese aluminum hydroxide) and L i element in lithium source (L iOH) are mixed according to the molar ratio of 1:1.035, and dopant (Zr (OH)4) The mass ratio of the Zr element to the quaternary precursor is 0.003: 1. And (3) sintering the dry-mixed material for 10h at 740 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the primary-sintered quaternary anode material (first product).
(2) Mixing the first product with a first coating agent (Al)2O3) And (3) uniformly mixing the first product and Al element by a dry method according to the mass ratio of 1:0.0005 to ensure that the first coating agent is uniformly coated on the surface of the first product, sintering the material subjected to dry mixing for 6 hours at 600 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain a primary coated quaternary anode material product (second product).
(3) And mixing the second product with deionized water according to the mass ratio of 2:1, stirring at the room temperature and the rotating speed of 600rpm for 60s, filtering, and carrying out vacuum drying at 150 ℃ for 8h to obtain the primary coated quaternary anode material product after washing and drying.
Test example
(1) The quaternary positive electrode materials prepared in example 1 and comparative examples 1 to 3 were respectively used to prepare button cells for testing, a first charge-discharge curve of the button cells was obtained through testing, and the capacity retention rate after 50 weeks of cycling was tested at normal temperature, and the results are shown in fig. 2 to 5 and table 1.
(2) Differential Scanning Calorimetry (DSC) was performed on the quaternary positive electrode materials prepared in example 1 and comparative examples 1 to 3, and the results are shown in table 2.
TABLE 1 results of the cycle Performance test
TABLE 2DSC results
Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
DSC temperature | 230℃ | 199.32℃ | 203.33℃ | 209.44℃ |
The test result shows that the battery made of the secondary coated quaternary positive electrode material has higher capacity and cycle performance and better thermal stability compared with the battery made of a comparative example material. As can be seen from comparative example 1, the thermal stability of the uncoated NCMA quaternary positive electrode material was low, and the cycle performance of the fabricated battery was significantly reduced. From comparative examples 2 and 3, it can be seen that the performance of the once-coated NCMA quaternary positive electrode material is improved compared with that of comparative example 1, but is still inferior to that of example 1. In addition, the material in comparative example 2 is not washed with water and dried before being applied to the manufacture of the battery, and the performance is inferior to that in comparative example 3, which shows that impurities generated in the primary coating process can cause adverse effects on the product performance if not removed.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A quaternary positive electrode material for a lithium ion battery is characterized by comprising an inner core and a coating layer, wherein the coating layer is formed on at least part of the surface of the inner core, the quaternary positive electrode material has a composition shown in a formula (I),
LixNiaCobMncAldMyO2(I)
in the formula (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03, c is more than or equal to 0.01 and less than or equal to 0.03, a + b + c + d is 1, and M is at least one selected from the group consisting of second main group elements, third main group elements, fourth main group elements, fifth main group elements, fourth subgroup elements and fifth subgroup elements.
2. The quaternary positive electrode material according to claim 1, wherein M is at least one selected from Mg, Ba, B, Al, Si, P, Ti, Zr, Nb.
3. The quaternary positive electrode material according to claim 2, wherein M is Al, Zr, B, or M is Al, Ti, Nb, or M is Al, Mg, Ti.
4. A method of preparing the quaternary positive electrode material according to any one of claims 1 to 3, comprising:
(1) mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material;
(2) carrying out first sintering treatment on the first mixed material to obtain a quaternary anode material core;
(3) mixing the quaternary positive electrode material core with a first coating agent to obtain a second mixed material;
(4) carrying out second sintering treatment on the second mixed material to obtain a primary coated product;
(5) mixing the primary coated product with a second coating agent to obtain a third mixed material;
(6) and calcining the third mixed material to obtain the quaternary anode material.
5. The method of claim 4, wherein the quaternary positive electrode material precursor has a composition as shown in formula (II),
NiaCobMncAld(OH)2(II)
in the formula (II), a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01 and less than or equal to 0.03, and a + b + c + d is 1;
optionally, the lithium source comprises at least one selected from lithium nitrate, lithium carbonate, lithium hydroxide monohydrate;
optionally, the dopant comprises at least one selected from the group consisting of zirconium hydroxide, zirconium oxide, titanium oxide, magnesium hydroxide, magnesium oxide, magnesium carbonate, magnesium nitrate, barium hydroxide, aluminum oxide, aluminum hydroxide, aluminum oxyhydroxide, zinc oxide, niobium pentoxide;
optionally, the first coating agent comprises at least one selected from alumina, aluminum hydroxide, aluminum nitrate, aluminum oxyhydroxide;
optionally, the second coating agent comprises at least one selected from boric acid, boron oxide, lithium phosphate, lithium niobate.
6. The method according to claim 4, wherein in the step (1), the molar ratio of the quaternary positive electrode material precursor to the lithium element in the lithium source is 1 (1.00-1.05); the mass ratio of the quaternary positive electrode material precursor to the doping elements in the dopant is 1 (0.001-0.003);
optionally, in the step (3), the mass ratio of the quaternary positive electrode material core to the coating element in the first coating agent is 1 (0.0005-0.001);
optionally, in the step (5), the mass ratio of the primary coating product to the coating element in the second coating agent is 1 (0.001-0.01).
7. The method according to claim 4, wherein the first sintering treatment is carried out at 700-820 ℃ for 8-20 h;
optionally, the second sintering treatment is completed at 600-700 ℃ for 6-15 h;
optionally, the calcination treatment is carried out at 300-600 ℃ for 8-18 h.
8. The method of claim 4, further comprising, prior to step (5): and carrying out water washing treatment and drying treatment on the primary coated product.
9. The method according to claim 8, wherein in the water washing treatment, the mass ratio of the primary coating product to water is (1-2): 1, and the water washing treatment is carried out at a stirring speed of 500-800 rpm for 30-600 s;
optionally, the drying treatment is completed at 100-180 ℃ for 3-20 h.
10. A lithium ion battery, comprising: a positive electrode, a negative electrode, a separator and an electrolyte; wherein,
the positive electrode includes: a positive current collector and a positive electrode material supported on the positive current collector, the positive electrode material comprising: a positive electrode active material, a positive electrode conductive agent and a positive electrode binder; wherein the positive electrode active material is the quaternary positive electrode material according to any one of claims 1 to 3.
The negative electrode includes: an anode current collector and an anode material supported on the anode current collector, the anode material comprising: a negative electrode active material, a negative electrode conductive agent, and a negative electrode binder.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910959426.2A CN111430700B (en) | 2019-10-10 | 2019-10-10 | Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery |
PCT/CN2020/076593 WO2021068448A1 (en) | 2019-10-10 | 2020-02-25 | Quaternary positive electrode material for lithium ion battery and preparation method therefor, and lithium ion battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910959426.2A CN111430700B (en) | 2019-10-10 | 2019-10-10 | Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111430700A true CN111430700A (en) | 2020-07-17 |
CN111430700B CN111430700B (en) | 2022-07-22 |
Family
ID=71546744
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910959426.2A Active CN111430700B (en) | 2019-10-10 | 2019-10-10 | Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN111430700B (en) |
WO (1) | WO2021068448A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111422919A (en) * | 2019-12-19 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material, preparation method thereof, positive electrode and battery |
CN111916701A (en) * | 2020-07-22 | 2020-11-10 | 蜂巢能源科技有限公司 | Coated positive electrode material and preparation method and application thereof |
CN113036117A (en) * | 2021-02-26 | 2021-06-25 | 蜂巢能源科技有限公司 | Quaternary positive electrode material and preparation method thereof |
CN113540433A (en) * | 2021-06-28 | 2021-10-22 | 合肥国轩高科动力能源有限公司 | Cathode material, preparation method, lithium ion battery cathode and lithium ion battery |
CN113582253A (en) * | 2021-07-30 | 2021-11-02 | 蜂巢能源科技有限公司 | Quaternary positive electrode material and preparation method and application thereof |
CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
CN114094085A (en) * | 2021-11-24 | 2022-02-25 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
WO2022139289A1 (en) * | 2020-12-21 | 2022-06-30 | 주식회사 포스코 | Cathode active material, and lithium ion battery including same |
CN115000397A (en) * | 2022-04-19 | 2022-09-02 | 中国第一汽车股份有限公司 | Solid-state battery anode material, preparation method thereof and solid-state battery anode |
CN115196693A (en) * | 2022-08-08 | 2022-10-18 | 浙江格派钴业新材料有限公司 | LiBO 2 /LiAlO 2 Preparation method of double-layer coated modified quaternary positive electrode material of lithium ion battery |
WO2023103700A1 (en) * | 2021-12-08 | 2023-06-15 | 深圳市贝特瑞纳米科技有限公司 | Nickel-rich positive electrode material, preparation method therefor, and lithium ion battery |
CN116525816A (en) * | 2023-07-03 | 2023-08-01 | 英德市科恒新能源科技有限公司 | Ultrahigh nickel-cobalt-aluminum ternary positive electrode material and preparation method thereof |
CN116547835A (en) * | 2021-10-22 | 2023-08-04 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method, positive electrode plate, secondary battery, battery module, battery pack and power utilization device |
WO2024067685A1 (en) * | 2022-09-30 | 2024-04-04 | 宁夏中化锂电池材料有限公司 | Low-gas-production and long-cycle life single crystal ternary positive electrode material and preparation method therefor |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113292111A (en) * | 2021-04-23 | 2021-08-24 | 陕西彩虹新材料有限公司 | Cobalt-free single crystal cathode material and preparation method thereof |
CN113603156B (en) * | 2021-07-30 | 2023-05-12 | 蜂巢能源科技有限公司 | Washing sand grinding coating method for positive electrode material, preparation method, positive electrode material and battery |
CN113666430A (en) * | 2021-07-30 | 2021-11-19 | 蜂巢能源科技有限公司 | Lithium-rich cathode material, preparation method thereof and lithium ion battery |
CN114388779B (en) * | 2022-01-12 | 2024-02-02 | 万华化学(四川)有限公司 | Composite ternary positive electrode material, preparation method thereof and lithium ion battery |
CN115842113A (en) * | 2022-01-19 | 2023-03-24 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, method for producing same, secondary battery, battery module, battery pack, and electric device |
CN114864923B (en) * | 2022-04-29 | 2023-11-21 | 巴斯夫杉杉电池材料有限公司 | Boron-doped nickel-cobalt-manganese positive electrode material and preparation method thereof |
CN114914425B (en) * | 2022-05-27 | 2024-03-26 | 格林美(无锡)能源材料有限公司 | Inorganic high-molecular water purifying agent coated positive electrode material and preparation method and application thereof |
CN114772574B (en) * | 2022-05-31 | 2023-12-05 | 蜂巢能源科技股份有限公司 | Method for doping positive electrode material by using heteropolyacid and/or heteropolyacid salt, positive electrode material and application |
CN115172924B (en) * | 2022-07-22 | 2023-12-15 | 浙江大学 | Recycling and repairing method of lithium ion battery anode material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104409700A (en) * | 2014-11-20 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material for nickel-base lithium ion battery and preparation method of anode material |
WO2017096525A1 (en) * | 2015-12-08 | 2017-06-15 | 北京当升材料科技股份有限公司 | Lithium-ion battery positive electrode material, preparation method therefor, lithium-ion battery positive electrode, and lithium-ion battery |
CN108417790A (en) * | 2018-01-30 | 2018-08-17 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode material and preparation method and application thereof |
CN109473657A (en) * | 2018-12-03 | 2019-03-15 | 林奈(中国)新能源有限公司 | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4586991B2 (en) * | 2006-03-24 | 2010-11-24 | ソニー株式会社 | Positive electrode active material, method for producing the same, and secondary battery |
JP2017152294A (en) * | 2016-02-26 | 2017-08-31 | Tdk株式会社 | Positive electrode active material and lithium ion secondary battery |
CN108091830A (en) * | 2017-10-30 | 2018-05-29 | 广东邦普循环科技有限公司 | A kind of method of coated aluminum oxide and boron oxide on nickelic ternary material |
CN108847477B (en) * | 2018-05-25 | 2021-09-21 | 彩虹集团新能源股份有限公司 | Nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof |
CN110120505B (en) * | 2019-05-07 | 2020-12-11 | 厦门厦钨新能源材料股份有限公司 | Lithium ion battery positive electrode material, preparation method and lithium ion battery |
-
2019
- 2019-10-10 CN CN201910959426.2A patent/CN111430700B/en active Active
-
2020
- 2020-02-25 WO PCT/CN2020/076593 patent/WO2021068448A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104409700A (en) * | 2014-11-20 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Anode material for nickel-base lithium ion battery and preparation method of anode material |
WO2017096525A1 (en) * | 2015-12-08 | 2017-06-15 | 北京当升材料科技股份有限公司 | Lithium-ion battery positive electrode material, preparation method therefor, lithium-ion battery positive electrode, and lithium-ion battery |
CN108417790A (en) * | 2018-01-30 | 2018-08-17 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode material and preparation method and application thereof |
CN109473657A (en) * | 2018-12-03 | 2019-03-15 | 林奈(中国)新能源有限公司 | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111422919A (en) * | 2019-12-19 | 2020-07-17 | 蜂巢能源科技有限公司 | Quaternary positive electrode material, preparation method thereof, positive electrode and battery |
CN111916701A (en) * | 2020-07-22 | 2020-11-10 | 蜂巢能源科技有限公司 | Coated positive electrode material and preparation method and application thereof |
CN111916701B (en) * | 2020-07-22 | 2021-10-19 | 蜂巢能源科技有限公司 | Coated positive electrode material and preparation method and application thereof |
WO2022139289A1 (en) * | 2020-12-21 | 2022-06-30 | 주식회사 포스코 | Cathode active material, and lithium ion battery including same |
CN113036117A (en) * | 2021-02-26 | 2021-06-25 | 蜂巢能源科技有限公司 | Quaternary positive electrode material and preparation method thereof |
CN113540433A (en) * | 2021-06-28 | 2021-10-22 | 合肥国轩高科动力能源有限公司 | Cathode material, preparation method, lithium ion battery cathode and lithium ion battery |
CN113582253A (en) * | 2021-07-30 | 2021-11-02 | 蜂巢能源科技有限公司 | Quaternary positive electrode material and preparation method and application thereof |
CN116547835A (en) * | 2021-10-22 | 2023-08-04 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method, positive electrode plate, secondary battery, battery module, battery pack and power utilization device |
CN114094085A (en) * | 2021-11-24 | 2022-02-25 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
CN114094085B (en) * | 2021-11-24 | 2023-07-21 | 蜂巢能源科技有限公司 | Positive electrode material and preparation method and application thereof |
CN113851633A (en) * | 2021-11-29 | 2021-12-28 | 中南大学 | Niobium-doped high-nickel ternary cathode material coated with niobium phosphate and preparation method thereof |
WO2023103700A1 (en) * | 2021-12-08 | 2023-06-15 | 深圳市贝特瑞纳米科技有限公司 | Nickel-rich positive electrode material, preparation method therefor, and lithium ion battery |
CN115000397A (en) * | 2022-04-19 | 2022-09-02 | 中国第一汽车股份有限公司 | Solid-state battery anode material, preparation method thereof and solid-state battery anode |
CN115196693A (en) * | 2022-08-08 | 2022-10-18 | 浙江格派钴业新材料有限公司 | LiBO 2 /LiAlO 2 Preparation method of double-layer coated modified quaternary positive electrode material of lithium ion battery |
WO2024067685A1 (en) * | 2022-09-30 | 2024-04-04 | 宁夏中化锂电池材料有限公司 | Low-gas-production and long-cycle life single crystal ternary positive electrode material and preparation method therefor |
CN116525816A (en) * | 2023-07-03 | 2023-08-01 | 英德市科恒新能源科技有限公司 | Ultrahigh nickel-cobalt-aluminum ternary positive electrode material and preparation method thereof |
CN116525816B (en) * | 2023-07-03 | 2023-09-05 | 英德市科恒新能源科技有限公司 | Ultrahigh nickel-cobalt-aluminum ternary positive electrode material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111430700B (en) | 2022-07-22 |
WO2021068448A1 (en) | 2021-04-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111430700B (en) | Quaternary cathode material for lithium ion battery, preparation method of quaternary cathode material and lithium ion battery | |
KR101746187B1 (en) | Positive electrode active material for rechargable lithium battery, and rechargable lithium battery including the same | |
US20190379044A1 (en) | Nickel active material precursor for lithium secondary battery, method for producing nickel active material precursor, nickel active material for lithium secondary battery produced by method, and lithium secondary battery having cathode containing nickel active material | |
CN108155357B (en) | Nickel-based active material for lithium secondary battery, method for preparing same, and lithium secondary battery including positive electrode including same | |
JP2020105063A (en) | Doped titanium niobate and battery | |
CN113363415B (en) | High-nickel ternary composite positive electrode containing solid electrolyte and lithium ion battery | |
CN108899545B (en) | Mesoporous core-shell structure surface-coated lithium battery ternary cathode material and preparation method thereof | |
KR20130095228A (en) | Non-aqueous secondary battery having a blended cathode active material | |
CN113937286B (en) | Coated modified sodium ion battery positive electrode material, preparation method thereof and battery | |
JP2017513179A (en) | Anode active material, lithium secondary battery having the same, and method for producing the same | |
CN111584875A (en) | Graphene-coated and anion-cation co-doped ternary cathode material and preparation method and application thereof | |
JP2013225471A (en) | Cathode active material for secondary battery and method for producing the same | |
CN114094067A (en) | Ternary positive electrode material, preparation method and application thereof | |
JP2018014208A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery and method for manufacturing the same | |
CN111600014A (en) | Modified high-specific-capacity high-nickel ternary cathode material and preparation method thereof | |
CN113066980B (en) | Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material | |
CN113707870A (en) | Cobalt-free cathode material and preparation method and application thereof | |
CN113764638A (en) | Cathode material, preparation method thereof, cathode comprising cathode material and lithium ion battery | |
KR20230139301A (en) | Positive electrode sheet, battery and electronic device | |
CN113809281B (en) | Composite positive plate, preparation method thereof and lithium ion battery | |
CN111430680B (en) | Modified quaternary positive electrode material and preparation method and application thereof | |
CN115084457A (en) | High-compaction long-life ternary cathode material and preparation method thereof | |
CN111048759A (en) | Negative active material for lithium battery, and preparation method and application thereof | |
US20170324085A1 (en) | Precursor for Producing Lithium-rich Cathode Active Material, and Lithium-rich Cathode Active Material Produced Thereby | |
CN110600723A (en) | Ca3Co4O9Nano hollow tube cathode material, sodium ion battery and preparation method and application thereof |
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 |