CN115092973A - Positive electrode precursor, continuous preparation method thereof, positive electrode material and secondary battery - Google Patents
Positive electrode precursor, continuous preparation method thereof, positive electrode material and secondary battery Download PDFInfo
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- CN115092973A CN115092973A CN202210655152.XA CN202210655152A CN115092973A CN 115092973 A CN115092973 A CN 115092973A CN 202210655152 A CN202210655152 A CN 202210655152A CN 115092973 A CN115092973 A CN 115092973A
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- positive electrode
- precursor material
- nickel
- electrode precursor
- manganese
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- 239000002243 precursor Substances 0.000 title claims abstract description 142
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 137
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 239000002245 particle Substances 0.000 claims abstract description 62
- 239000003513 alkali Substances 0.000 claims abstract description 48
- 239000012266 salt solution Substances 0.000 claims abstract description 48
- 239000002002 slurry Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 27
- 239000008139 complexing agent Substances 0.000 claims abstract description 24
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 238000012544 monitoring process Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 41
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 30
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- 239000002585 base Substances 0.000 claims description 21
- 239000002562 thickening agent Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000010924 continuous production Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000002572 peristaltic effect Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 230000012010 growth Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000011437 continuous method Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
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- 230000000536 complexating effect Effects 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 230000009647 facial growth Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- 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
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application belongs to the technical field of battery materials, and particularly relates to a positive electrode precursor and a continuous preparation method thereof, a positive electrode material and a secondary battery. The continuous preparation method of the positive electrode precursor material comprises the following steps: preparing a mixed salt solution of nickel salt, cobalt salt and manganese salt; adding the mixed salt solution, alkali liquor and complexing agent into a reaction kettle for reaction, and monitoring the particle size of materials in the reaction kettle in real time; when the granularity D50 of the material in the reaction kettle reaches 75-85% of the target granularity D50, starting a concentration circulating system to control the solid content of the slurry; and when the granularity D50 of the materials in the reaction kettle reaches the target granularity D50, collecting qualified materials, and purifying to obtain the anode precursor material. The continuous preparation method of the anode precursor material simplifies the process and equipment, reduces the production cost, and is particularly suitable for the continuous reaction process for improving the tap density of the hydroxide precursor.
Description
Technical Field
The application belongs to the technical field of battery materials, and particularly relates to a positive electrode precursor and a continuous preparation method thereof, a positive electrode material and a secondary battery.
Background
With the rapid development of the electric automobile market, the power lithium ion battery is highly concerned by the industry as one of the core components. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like, wherein the positive electrode material is the most core component of the lithium battery, the performance of the positive electrode material directly influences the performance of the lithium ion battery, and the cost directly determines the cost of the battery. At present, the anode material is mainly lithium cobaltate, lithium manganate, lithium iron phosphate and ternary system anode materials. Ternary materials are preferred for lithium batteries because of their low cost, stable performance, high energy density, and the like.
The preparation process of the precursor of the ternary material is mainly a chemical coprecipitation method at present. In the process, the crystal face growth is controlled mainly by adjusting pH, temperature and ammonia concentration, adding a surfactant and the like. The prior mature process for preparing the precursor by the coprecipitation method comprises a continuous method and a batch method. The tap density of the ternary precursor produced by the batch method is not high; although the tap density of the ternary precursor produced by the continuous method is improved compared with that of a product produced by a batch method, the problems of poor sphericity of small particles and micro powder on the surface of a sphere exist, so that the problems of poor cycle performance, easy self-discharge, low capacity and the like of the cathode material are easily caused. Moreover, as the requirements of the terminal on energy density are continuously increased, higher requirements on the tap density and the compaction density of the material and the precursor are required. Therefore, how to produce the positive electrode precursor with higher tap density, no micro powder and good small particle sphericity has great significance.
Disclosure of Invention
The application aims to provide a positive electrode precursor, a continuous preparation method thereof, a positive electrode material and a secondary battery, and aims to solve the problems of low tap density, micro powder, poor sphericity of small particles and complicated synthesis process of the positive electrode precursor produced by the conventional continuous method to a certain extent.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for continuously preparing a positive electrode precursor material, comprising the steps of:
preparing a mixed salt solution of nickel salt, cobalt salt and manganese salt;
adding the mixed salt solution, alkali liquor and complexing agent into a reaction kettle for reaction, and monitoring the particle size of materials in the reaction kettle in real time;
when the granularity D50 of the material in the reaction kettle reaches 75-85% of the target granularity D50, starting a concentration circulating system to control the solid content of the slurry;
and when the granularity D50 of the materials in the reaction kettle reaches the target granularity D50, collecting qualified materials, and purifying to obtain the anode precursor material.
Further, the step of adding the mixed salt solution, the alkali liquor and the complexing agent into the reaction kettle for reaction comprises the following steps: adding a base solution accounting for 70-80% of the volume of the reaction kettle into the reaction kettle, adding the alkali liquor and the complexing agent under a protective atmosphere with the rotating speed of 100-600 rpm and the temperature of 50-70 ℃, adjusting the pH value of the base solution to 11-12 and the ammonia value to 3-15 g/L, and then feeding at a rate ratio of 2: (4-6) adding the alkali liquor and the mixed salt solution for reaction, and opening unqualified overflow when the slurry in the reaction kettle reaches an overflow port.
Further, the total concentration of the mixed salt solution is 2-3 mol/L.
Further, the concentration of the alkali liquor is 10-11 mol/L.
Further, the concentration of the complexing agent is 10-11 mol/L.
Further, the step of starting the concentration circulating system to control the solid content of the slurry comprises the following steps: and starting a thickener and a slurry circulator in the reaction kettle, fixing the clear water flow of the thickener, and controlling the solid content of the slurry to be 100-500 g/L.
Further, the target particle size D50 is 6-15 μm.
Further, the tap density of the positive electrode precursor is 2.4-2.6 g/cm 3 。
Further, the step of purifying comprises: washing, drying, sieving and removing iron.
Further, the nickel salt comprises at least one of nickel chloride, nickel nitrate, nickel oxalate and nickel sulfate.
Further, the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt oxalate and cobalt sulfate.
Further, the manganese salt comprises at least one of manganese chloride, manganese nitrate, manganese oxalate and manganese sulfate.
Further, the complexing agent is ammonia water.
Further, the alkaline substance in the alkali liquor comprises at least one of sodium hydroxide and potassium hydroxide.
In a second aspect, the present application provides a positive electrode precursor material prepared by the above method, wherein the positive electrode precursor material is nickel-cobalt-manganese hydroxide and/or nickel-manganese hydroxide.
Further, the molar ratio of nickel element, cobalt element and manganese element in the positive electrode precursor material is (0.5-0.8): (0-0.3): (0.1-0.3).
In a third aspect, the present application provides a positive electrode material prepared by sintering a mixture including a lithium source and a positive electrode precursor material, wherein the positive electrode precursor material includes the positive electrode precursor material described above.
In a fourth aspect, the present application provides a secondary battery including the positive electrode material described above in a positive electrode thereof.
According to the continuous preparation method of the anode precursor material, after the mixed salt solution of nickel salt, cobalt salt and manganese salt is prepared, the mixed salt solution, alkali liquor and complexing agent are added into a reaction kettle for reaction, and in the reaction process, through the complexing action of the complexing agent and the coprecipitation action of the alkali liquor, the nickel-cobalt-manganese salt is converted into hydroxide to form crystal nuclei, and then the crystal grows continuously through agglomeration. By monitoring the particle size of the materials in the reaction kettle in real time, when the particle size D50 of the materials in the reaction kettle reaches 75% -85% of the target particle size D50, a concentration circulating system is started to control the solid content of the slurry, so that the solid content of the slurry is increased, the friction force between spheres in the slurry is increased, the anode precursor grows into particles with better spherical degree, meanwhile, the surface smoothness of the particles is improved, the specific surface area of the particles is reduced, and the tap density of the anode precursor material is increased. And when the granularity D50 of the materials in the reaction kettle reaches the target granularity D50, collecting qualified materials, and purifying to obtain the anode precursor material with high tap density and basically no micro powder. Compared with the traditional mode that a plurality of reaction kettles are required to be connected in series, the continuous preparation method of the anode precursor material simplifies the process and equipment, reduces the production cost, is easy to control, can be widely applied to the continuous process of the anode precursor material, and is particularly suitable for the continuous reaction process of improving the tap density of the hydroxide precursor.
The positive electrode precursor material provided by the second aspect of the application is prepared by the method, is nickel-cobalt-manganese hydroxide, has the characteristics of good sphericity, smooth surface, small specific surface area, high tap density, no micro powder and the like, and is favorable for improving the electrochemical performance of the prepared positive electrode material.
The positive electrode material provided by the third aspect of the application is obtained by sintering a lithium source and the positive electrode precursor material, and the positive electrode precursor material is nickel-cobalt-manganese hydroxide, and has the characteristics of good sphericity, smooth surface, small specific surface area, high tap density, no micro powder and the like. Therefore, the anode material obtained by sintering the lithium ion battery and the lithium source has the characteristics of higher gram capacity, cyclic stability, structural stability and the like.
In the secondary battery provided by the fourth aspect of the present application, since the positive electrode includes the positive electrode material, the positive electrode material has characteristics of high gram capacity, high cycle stability, high structural stability, and the like, and thus the energy density, cycle stability, and safety performance of the secondary battery are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a schematic flow chart of a continuous preparation method of a cathode precursor material provided in an embodiment of the present application;
fig. 2 is an SEM image of a positive electrode precursor material provided in example 1 of the present application;
fig. 3 is an SEM image of a positive electrode precursor material provided in example 2 of the present application;
fig. 4 is an SEM image of a positive electrode precursor material provided in example 3 of the present application;
fig. 5 is an SEM image of a positive electrode precursor material provided in comparative example 1 of the present application;
fig. 6 is an SEM image of the cathode precursor material provided in comparative example 2 of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1, a first aspect of embodiments of the present application provides a method for continuously preparing a positive electrode precursor material, including the steps of:
s10, preparing a mixed salt solution of nickel salt, cobalt salt and manganese salt;
s20, adding the mixed salt solution, the alkali liquor and the complexing agent into a reaction kettle for reaction, and monitoring the particle size of materials in the reaction kettle in real time;
s30, when the granularity D50 of the material in the reaction kettle reaches 75% -85% of the target granularity D50, starting a concentration circulating system to control the solid content of the slurry;
s40, when the granularity D50 of the materials in the reaction kettle reaches the target granularity D50, collecting the qualified materials, and purifying to obtain the anode precursor material.
According to the continuous preparation method of the cathode precursor material provided by the embodiment of the application, after the mixed salt solution of nickel salt, cobalt salt and manganese salt is prepared, the mixed salt solution, alkali liquor and complexing agent are added into the reaction kettle for reaction, and in the reaction process, through the complexing action of the complexing agent and the coprecipitation action of the alkali liquor, the nickel-cobalt-manganese salt is converted into hydroxide to form crystal nuclei, and then the crystals continue to grow through agglomeration. By monitoring the particle size of the materials in the reaction kettle in real time, when the particle size D50 of the materials in the reaction kettle reaches 75% -85% of the target particle size D50, a concentration circulating system is started to control the solid content of the slurry, so that the solid content of the slurry is increased, the friction force between spheres in the slurry is increased, the anode precursor grows into particles with better spherical degree, meanwhile, the surface smoothness of the particles is improved, the specific surface area of the particles is reduced, and the tap density of the anode precursor material is increased. If the particle size is less than 75% of the target particle size D50, the concentrator is started, the crystal growth speed is slowed down along with the rise of solid content, the synthesis time reaching the target D50 is too long, and equipment and raw material resources are wasted; if the particle size is larger than 85% of the target particle size D50, the thickener is started, because the actual D50 is close to the target D50, the overshoot phenomenon easily occurs in the particle size growth, and further the actual D50 fluctuation state is formed, the difficulty of particle size stability control is increased, the time for collecting synthetic slurry is prolonged, the resources are wasted, and the cost is increased. The starting node of the concentration circulating system can be too early or too late to form micro powder, and the tap density of the positive electrode precursor material is influenced. And when the granularity D50 of the materials in the reaction kettle reaches the target granularity D50, collecting qualified materials, and purifying to obtain the anode precursor material with high tap density and basically no micro powder. Compared with the traditional mode that a plurality of reaction kettles are required to be connected in series, the continuous preparation method of the anode precursor material in the embodiment of the application simplifies the process and equipment, reduces the production cost, is easy to control, can be widely applied to the continuous process of the anode precursor material, and is particularly suitable for the continuous reaction process of improving the tap density of the hydroxide anode precursor.
In some embodiments, the step of preparing the mixed salt solution of nickel salt, cobalt salt and manganese salt in the step S10 includes: dissolving nickel salt, cobalt salt and manganese salt in water to prepare a mixed salt solution.
In some embodiments, the total concentration of the mixed salt solution is 2-3 mol/L; if the total concentration of the mixed salt solution is smaller, the yield is reduced, and the finished product is increased; if the total concentration of the mixed salt solution is too high, the growth of precursor crystal nuclei is not facilitated.
In some embodiments, the nickel salt comprises at least one of nickel chloride, nickel nitrate, nickel oxalate, nickel sulfate. In some embodiments, the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt oxalate, cobalt sulfate. In some embodiments, the manganese salt comprises at least one of manganese chloride, manganese nitrate, manganese oxalate, manganese sulfate. The nickel salt, the cobalt salt and the manganese salt adopted in the embodiment of the application have good solubility, and are favorable for reacting with alkali liquor and a complexing agent in a reaction system to generate anode precursor particles, and the nickel-cobalt-manganese hydroxide precursor material is obtained when the anode precursor particles grow to a target particle size D50. The proportion of nickel salt, cobalt salt and manganese salt is not particularly limited in the embodiment of the application, and the mixed salt solution can be prepared according to the actual application requirement and the molar ratio of nickel, cobalt and manganese in the target anode material.
In some embodiments, in the step S20, the step of adding the mixed salt solution, the alkali solution and the complexing agent into the reaction kettle for reaction includes: adding a base solution with the volume of 70-80% of that of the reaction kettle, adding an alkali solution and a complexing agent under a protective atmosphere with the rotating speed of 100-600 rpm and the temperature of 50-70 ℃, adjusting the pH value of the base solution to 11-12 and the ammonia value to 3-15 g/L, and then, feeding the base solution at a rate ratio of 2: (4-6) adding alkali liquor and mixed salt solution for reaction, and opening unqualified overflow when the slurry in the reaction kettle reaches an overflow port. Wherein the reaction temperature of 50-70 ℃ and the pH value of 11-12 are favorable for the forward reaction of the mixed salt ultra nickel cobalt manganese hydroxide positive electrode precursor. The rotating speed of 100-600 rpm is not only beneficial to improving the sphericity of the anode precursor, but also beneficial to maintaining the structural stability of the anode precursor, if the rotating speed is lower, the sphericity of the product is poorer, and if the rotating speed is higher, the product is easy to crack and break. Further preferably, the rotation speed is 300 to 550 rpm. The ammonia value is 3-15 g/L, the ammonia value is preferably 9-10 g/L, the supersaturation degree of precipitates in the solution can be controlled by properly increasing the ammonia value, the growth rate is controlled, and the whiskers are thicker and densely arranged, so that the tap density of the positive electrode precursor material is improved. In addition, the feed rate ratio was 2: (4-6) adding alkali liquor and mixed salt solution for reaction, adjusting the feeding rate of a complexing agent according to the ammonia value range, and under the condition, facilitating the crystallization of nickel-cobalt-manganese metal ions in the reaction kettle into hydroxide precursor particles.
In some embodiments, the complexing agent is ammonia, which is beneficial for regulating and controlling the ammonia value range in the reaction system.
In some embodiments, the alkaline material in the alkaline solution comprises at least one of sodium hydroxide and potassium hydroxide, which is beneficial to adjust the pH value in the reaction system, so that the nickel-cobalt-manganese metal ions are converted into nickel-cobalt-manganese hydroxide precursor particles.
In some embodiments, the concentration of the alkali solution is 10-11 mol/L. If the concentration of the alkali liquor is lower, the use amount of equipment in the alkali liquor storage tank is increased; if the concentration of the alkali liquor is higher, solid is easy to precipitate, the storage is inconvenient, the operation danger and the corrosion to equipment are increased, and the pH accuracy control in the synthesis process is not facilitated.
In some embodiments, the concentration of the complexing agent is 10-11 mol/L. If the concentration of the complexing agent is low, the shape of the precursor is loose and the tap density is low; if the concentration of the complexing agent is too high, the control of the crystal whisker of the product is influenced, so that other physical and chemical indexes are influenced.
In some embodiments, the step of monitoring the particle size of the material in the reaction vessel in real time includes, but is not limited to: the particle size of the precursor was measured by sampling every 2h during the reaction.
In some embodiments, in the step S30, the target particle size D50 is 6-15 μm; the particle size range is beneficial to improving the tap density of the anode precursor material.
In some embodiments, the step of activating the concentration circulation system to control the solids content of the slurry comprises: and starting a thickener and a slurry circulator in the reaction kettle, fixing the clear water flow of the thickener, and controlling the solid content of the slurry to be 100-500 g/L. When the solid content of the slurry is 100-500 g/L, the friction force among products is increased, the sphericity is better, the porosity of the whisker is reduced, and the tap density is increased. When the solid content of the slurry is low, the sphericity of the product is poor, the whiskers on the surface are loose, the tap density is not high enough, and even micro powder is generated. However, if the solid content of the slurry is too high, the friction force between products is too large, and the products are easy to break and crack.
In some embodiments, in step S40, when the particle size D50 of the material in the reaction kettle reaches the target particle size D50, the qualified material is collected into the slurry transit tank, and when a certain amount of the material is collected in the slurry transit tank, the material is sequentially washed to remove the dissolved residue on the particle surface, dried, sieved to further homogenize the particle size, and subjected to iron removal and other purification processes, so as to obtain the positive electrode precursor material.
In some embodiments, the positive electrode precursor has a tap density of 2.4 to 2.6g/cm 3 . According to the continuous preparation method of the cathode precursor material in the embodiment of the application, through the combined action of the operation steps, the prepared cathode precursor material is good in sphericity, smooth in surface, small in specific surface area, high in tap density and free of micro powder. Is beneficial to improving the capacity, the cycling stability and other electrochemical properties of the anode material.
In a second aspect of the embodiments of the present application, a positive electrode precursor material prepared by the above method is a nickel-cobalt-manganese hydroxide and/or a nickel-manganese hydroxide.
The cathode precursor material provided by the second aspect of the embodiment of the application is prepared by the method, and the cathode precursor material is nickel-cobalt-manganese hydroxide and/or nickel-manganese hydroxide, has the characteristics of good sphericity, smooth surface, small specific surface area, high tap density, no micro powder and the like, and is particularly favorable for improving the electrochemical performance of the prepared cathode material.
In some embodiments, the molar ratio of the nickel element, the cobalt element and the manganese element in the nickel-cobalt-manganese hydroxide is (0.5-0.8): (0-0.3): (0.1-0.3). The molar ratio of nickel, cobalt and manganese in the cathode precursor material in the embodiment of the application determines the molar ratio of nickel, cobalt and manganese in the cathode material, and the proportion of nickel, cobalt and manganese affects the capacity, the structural stability and the like of the cathode material. The nickel plays a role in improving the volume energy density of the material, but the cathode material with too high nickel content can also cause the mixed discharge of lithium and nickel, so that the precipitation of lithium is caused; the cobalt has the functions of stabilizing the layered structure of the material and improving the cycle and rate performance of the material, but the actual capacity is reduced due to the excessively high cobalt content; the manganese has the effects of reducing the material cost and improving the material safety and the structural stability, but the excessively high manganese content can damage the layered structure of the material, so that the specific capacity of the material is reduced. In some embodiments, the molar ratio of the nickel element, the cobalt element and the manganese element in the nickel-cobalt-manganese hydroxide is (0.5-0.8): (0.1-0.3): (0.1-0.3). In some embodiments, the molar ratio of nickel, cobalt, and manganese in the nickel, cobalt, and manganese hydroxide includes, but is not limited to 424, 333, or 523, and the like.
In a third aspect of the embodiments of the present application, there is provided a positive electrode material prepared by sintering a mixture including a lithium source and a positive electrode precursor material, where the positive electrode precursor material includes the positive electrode precursor material of the above embodiments.
The positive electrode material provided by the third aspect of the embodiment of the present application is obtained by sintering a lithium source and the positive electrode precursor material, and the positive electrode precursor material is a nickel-cobalt-manganese hydroxide, and has the characteristics of good sphericity, smooth surface, small specific surface area, high tap density, no micro powder, and the like. Therefore, the anode material obtained by sintering the lithium ion battery and the lithium source has the characteristics of higher gram capacity, cyclic stability, structural stability and the like.
In some embodiments, a method for preparing a positive electrode material is provided, which includes the steps of: mixing and sintering the positive electrode precursor material and a lithium source to obtain a positive electrode material; wherein the temperature of the mixed sintering treatment is 300-1000 ℃. And grinding or crushing to obtain the cathode material particles.
In some embodiments, the lithium source is selected from one or more of lithium carbonate, lithium hydroxide monohydrate, lithium acetate, lithium nitrate, lithium oxalate, lithium acetate, lithium hydroxide, lithium oxide, each of which can be sintered at high temperature with the positive electrode precursor material to form the positive electrode material.
In some embodiments, the molar ratio of the positive electrode precursor material to the lithium source is 1: (1-1.1), the proportion is favorable for the positive electrode precursor material to fully react with the lithium salt to generate the positive electrode material. By controlling the molar ratio of the positive electrode precursor material to the lithium source, the obtained positive electrode material is ensured to have higher capacity and cycle performance.
A fourth aspect of the embodiments of the present application provides a secondary battery including the positive electrode material described above in a positive electrode thereof.
In the secondary battery provided by the fourth aspect of the embodiment of the present application, since the positive electrode includes the positive electrode material, the positive electrode material has characteristics of high gram capacity, high cycle stability, high structural stability, and the like, and thus the energy density, the cycle stability, and the safety performance of the secondary battery are improved.
In some embodiments, the positive electrode sheet in the secondary battery includes a current collector and a positive electrode active material layer, which are laminated and attached, and the positive electrode active material layer includes a positive electrode material, a conductive agent, a binder and the like.
In some embodiments, the process of making the positive active material into a positive electrode sheet includes, but is not limited to: mixing a positive electrode material, a conductive agent and a binder to obtain electrode slurry, coating the electrode slurry on a current collector, and drying, rolling, die cutting and the like to obtain the positive electrode plate.
In some embodiments, the binder is present in the positive electrode active paste in an amount of 2 wt% to 4 wt%. In particular embodiments, the binder may be present in an amount of 2 wt%, 3 wt%, 4 wt%, and the like, which are typical and not limiting. In some embodiments, the binder comprises one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene butadiene rubber, hydroxypropyl methylcellulose, carboxymethylcellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives. In some embodiments, the conductive agent is present in the electrode paste in an amount of 3 wt% to 5 wt%. In specific embodiments, the content of the conductive agent may be 3 wt%, 4 wt%, 5 wt%, and the like, which are typical, but not limiting, contents. In some embodiments, the conductive agent comprises one or more of graphite, carbon black, acetylene black, graphene, carbon fibers, C60, and carbon nanotubes.
In some embodiments, the positive electrode current collector includes, but is not limited to, any one of a copper foil, an aluminum foil.
The secondary battery in the embodiment of the present application may be a lithium ion battery or a lithium metal battery or the like.
The negative electrode sheet, the electrolyte, the diaphragm and the like in the secondary battery of the embodiment are not particularly limited, and can be applied to any battery system.
In order to make the details and operations of the above-mentioned embodiments of the present application clearly understood by those skilled in the art, and to make the performance of the positive electrode precursor material and its continuous preparation method and application remarkably better apparent, the above-mentioned technical solutions are illustrated below by a plurality of examples.
Example 1
A positive electrode precursor material has a target particle size D50 of 7.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight percentages of the soluble salts are as follows: co: the Mn molar ratio is 0.7:0:0.3, and pure water is prepared into a mixed salt solution with the total concentration of 2.3 mol/L. And preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80% of that of the kettle is added as base solution before starting the kettle, the stirring is started at 540rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base solution is adjusted to 11.80 +/-0.05/45 ℃, and the ammonia value is 6 g/L. And (3) introducing protective gas for 2-4h, and then simultaneously starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water, wherein the salt solution feeding rate is 16L/h, the ratio of the alkali liquor feeding rate to the salt solution feeding rate is 2:5, and the ammonia water feeding rate is regulated and controlled according to the ammonia value.
And thirdly, sampling every 2h in the reaction process to measure the particle size of the precursor, starting a thickener to feed when the particle size D50 of the precursor reaches 5.3 mu m (75% of a target D50), and reacting for 30-40 h from the start of the thickener to the target D50. The clear flow rate of the thickener is 16-17L/h, and the protective gas is kept introduced in the whole process. The solid content of the system is controlled to be 400 g/L.
And fourthly, starting to collect qualified overflow slurry when the D50 is stabilized at 7 mu m +/-0.5. And after the slurry is collected, washing, drying, sieving and removing iron to obtain the anode precursor material.
Example 2
A positive electrode precursor material has a target particle size D50 of 10.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight ratio of Ni: co: the Mn molar ratio is 0.7:0:0.3, and pure water is prepared into a mixed salt solution with the total concentration of 2.3 mol/L. Preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80 percent of the kettle volume is added as base solution before starting the kettle, the stirring is started to be 450rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base solution is adjusted to 11.90 +/-0.05/45 ℃, and the ammonia value is 8 g/L. And (3) introducing protective gas for 2-4h, and then starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water at the same time, wherein the feeding rate of the salt solution is 16L/h, the ratio of the feeding rate of the alkali liquor to the feeding rate of the salt solution is 2:5, and the feeding rate of the ammonia water is regulated and controlled according to the ammonia value.
And thirdly, sampling every 2h in the reaction process to measure the particle size of the precursor, starting a thickener to feed when the particle size D50 of the precursor reaches 8.0 mu m (80% of a target D50), and reacting for 30-40 h from the start of the thickener to the target D50. The clear flow rate of the thickener is 15.5L/h, and the protective gas is kept introduced in the whole process. The solid content of the system is controlled to be 430 g/L.
And fourthly, when the D50 is stabilized at 10 mu m +/-0.5, starting to collect qualified overflow slurry. And after the slurry is collected, washing, drying, sieving and removing iron to obtain the precursor.
Example 3
A positive electrode precursor material has a target particle size D50 of 13.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight percentages of the soluble salts are as follows: co: the Mn molar ratio is 0.7:0:0.3, and pure water is prepared into a mixed salt solution with the total concentration of 2.3 mol/L. Preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80 percent of the kettle volume is added as base solution before starting the kettle, the stirring is started at 410rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base solution is adjusted to 11.70 +/-0.05/45 ℃, and the ammonia value is 10 g/L. And (3) introducing protective gas for 2-4h, and then simultaneously starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water, wherein the salt solution feeding rate is 16L/h, the ratio of the alkali liquor feeding rate to the salt solution feeding rate is 2:5, and the ammonia water feeding rate is regulated and controlled according to the ammonia value.
And thirdly, sampling every 2 hours in the reaction process to measure the particle size of the precursor, starting a concentrator to feed when the particle size D50 of the precursor reaches 11.0 mu m (85% of a target D50), and reacting for 30-40 hours from the start of the concentrator to the target D50. The clear flow rate of the thickener is 18.5L/h, and the protective gas is kept introduced in the whole process. The solid content of the system is controlled to be 485 g/L.
And fourthly, when the D50 is stable at 13 mu m +/-0.5, the qualified overflow slurry is collected. And after the slurry is collected, washing, drying, sieving and removing iron to obtain the precursor.
Comparative example 1
A positive electrode precursor material has a target particle size D50 of 7.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight ratio of Ni: co: the Mn molar ratio is 0.65:0:0.35, and pure water are prepared into a mixed salt solution with the total concentration of 2.3 mol/L. Preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80 percent of the kettle is added as base solution before starting the kettle, the stirring is started at 540rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base solution is adjusted to 11.35 +/-0.05/45 ℃, and the ammonia value is 6 g/L. And (3) introducing protective gas for 2-4h, and then starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water at the same time, wherein the feeding rate of the salt solution is 16L/h, the ratio of the feeding rate of the alkali liquor to the feeding rate of the salt solution is 2:5, and the feeding rate of the ammonia water is regulated and controlled according to the ammonia value.
Thirdly, protective gas is kept to be introduced, the solid content of the system is controlled to be 145g/L, the particle size of the precursor is sampled and measured every 2h in the reaction process, and qualified overflow slurry is collected when D50 is stabilized at 7 mu m +/-0.5.
And fourthly, after the slurry is collected, washing, drying, sieving and removing iron from the slurry to obtain a precursor.
Comparative example 2
A positive electrode precursor material has a target particle size D50 of 10.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight ratio of Ni: co: the Mn molar ratio is 0.65:0:0.35, and pure water is prepared into a mixed salt solution with the total concentration of 2.3 mol/L. Preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80 percent of the kettle is added as base liquid before starting the kettle, the stirring is started to be 450rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base liquid is adjusted to 11.00 +/-0.05/45 ℃, and the ammonia value is 6 g/L. And (3) introducing protective gas for 2-4h, and then starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water at the same time, wherein the feeding rate of the salt solution is 16L/h, the ratio of the feeding rate of the alkali liquor to the feeding rate of the salt solution is 2:5, and the feeding rate of the ammonia water is regulated and controlled according to the ammonia value.
Thirdly, protective gas is kept to be introduced, the solid content of the system is controlled to be 145g/L, the particle size of the precursor is sampled and measured every 2h in the reaction process, and qualified overflow slurry is collected when D50 is stabilized at 10.0 mu m +/-0.5.
And fourthly, after the slurry is collected, washing, drying, sieving and removing iron to obtain the precursor.
Comparative example 3
A positive electrode precursor material has a target particle size D50 of 7.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight ratio of Ni: co: the Mn molar ratio is 0.7:0:0.3, and pure water is prepared into a mixed salt solution with the total concentration of 2.3 mol/L. And preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80% of that of the kettle is added as base solution before starting the kettle, the stirring is started at 540rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base solution is adjusted to 11.80 +/-0.05/45 ℃, and the ammonia value is 6 g/L. And (3) introducing protective gas for 2-4h, and then starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water at the same time, wherein the feeding rate of the salt solution is 16L/h, the ratio of the feeding rate of the alkali liquor to the feeding rate of the salt solution is 2:5, and the feeding rate of the ammonia water is regulated and controlled according to the ammonia value.
And thirdly, sampling every 2h in the reaction process to measure the particle size of the precursor, starting a thickener to feed when the particle size D50 of the precursor reaches 4.90 mu m (70% of the target D50), and reacting for 40-50 h from the start of the thickener to the achievement of the target D50. After the thickener is started, the growth speed is slowed down along with the rise of solid content, the synthesis time reaching the target D50 is prolonged, and equipment and raw material resources are wasted. The clear flow rate of the thickener is 16-17L/h, and the protective gas is kept introduced in the whole process. The solid content of the system is controlled to be 400 g/L.
And fourthly, starting to collect qualified overflow slurry when the D50 is stabilized at 7 mu m +/-0.5. And after the slurry is collected, washing, drying, sieving and removing iron to obtain the anode precursor material.
Comparative example 4
A positive electrode precursor material has a target particle size D50 of 13.0 μm. The continuous preparation method of the anode precursor material comprises the following steps:
soluble salts of nickel, cobalt and manganese are selected as raw materials, and the weight ratio of Ni: co: the Mn molar ratio is 0.7:0:0.3, and pure water is prepared into a mixed salt solution with the total concentration of 2.3 mol/L. Preparing a sodium hydroxide solution with the concentration of 10.5mol/L and an ammonia water solution with the concentration of 10.5 mol/L.
Secondly, a titanium reaction kettle with the temperature of 200L and the rotation speed controllable is adopted, pure water with the volume of 80 percent of the kettle volume is added as base solution before starting the kettle, the stirring is started at 410rpm, the temperature is increased to 59.7-60.3 ℃, ammonia water and alkali liquor with the concentration are added, the pH value of the base solution is adjusted to 11.70 +/-0.05/45 ℃, and the ammonia value is 10 g/L. And (3) introducing protective gas for 2-4h, and then simultaneously starting a peristaltic pump for feeding the metal liquid, the alkali liquor and the ammonia water, wherein the salt solution feeding rate is 16L/h, the ratio of the alkali liquor feeding rate to the salt solution feeding rate is 2:5, and the ammonia water feeding rate is regulated and controlled according to the ammonia value.
And thirdly, sampling and measuring the particle size of the precursor every 2h in the reaction process, starting the thickener to feed when the particle size D50 of the precursor reaches 12.0 mu m (92% of the target D50), wherein overshoot phenomenon easily occurs in growth from the start of the thickener to the reaching of the target D50, so that the difficulty of controlling the stability of the particle size is increased, the actual D50 is in a state of fluctuating greatly from top to bottom around the target D50, the time for collecting qualified slurry is prolonged, resources are wasted, and the cost is increased. The clear flow rate of the thickener is 18.5L/h, and the protective gas is kept introduced in the whole process. The solid content of the system is controlled to be 485 g/L.
And fourthly, when the D50 is stabilized at 13 mu m +/-0.5, starting to collect qualified overflow slurry. And after the slurry is collected, washing, drying, sieving and removing iron to obtain the precursor.
Further, in order to verify the improvement of the examples of the present application, the tap density TD, the specific surface area, and the like of the positive electrode precursor materials prepared in each example and each comparative example were measured, and the test results are shown in table 1 below:
TABLE 1
From the test results, compared with the anode precursor material prepared by the traditional continuous method in the comparative examples 1-2, the anode precursor material prepared by the continuous method in the embodiments 1-3 of the present application has higher tap density, and the tap density can reach 2.4g/cm 3 As described above, the tap density of example 3 reached 2.54g/cm 3 . By comparing example 1 with comparative exampleIn example 1, example 2 and comparative example 2, it can be seen that the positive electrode precursor material having the same particle size prepared by the method of the example of the present application has a smaller specific surface area. In addition, if the time node for starting the concentration process is too early (comparative example 3 starts at 70% of the target D50), or if the time node for starting the concentration process is too late (comparative example 4 starts at 92% of the target D50), the tap density of the prepared cathode precursor material is affected, and the optimization of the specific surface area of the cathode precursor material is also not facilitated.
In addition, the appearances of the positive electrode precursor materials prepared in the embodiments 1 to 3 and the comparative examples 1 to 2 are observed through a scanning electron microscope, and the test results are shown in the attached drawings 2 to 6, wherein the attached drawings 2 to 4 are SEM images of the positive electrode precursor materials prepared in the embodiments 1 to 3 in sequence, so that the positive electrode precursor materials are high in spherical integrity, relatively low in surface roughness, high in distribution density and free of micro powder. And the attached figures 5-6 are SEM images of the anode precursor materials prepared in comparative examples 1-2 in sequence, and it can be seen that the anode precursor materials are irregular in shape, low in spherical integrity, low in distribution density and large in surface roughness.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A continuous preparation method of a positive electrode precursor material is characterized by comprising the following steps:
preparing a mixed salt solution of nickel salt, cobalt salt and manganese salt;
adding the mixed salt solution, alkali liquor and complexing agent into a reaction kettle for reaction, and monitoring the particle size of materials in the reaction kettle in real time;
when the granularity D50 of the material in the reaction kettle reaches 75-85% of the target granularity D50, starting a concentration circulating system to control the solid content of the slurry;
and when the granularity D50 of the materials in the reaction kettle reaches the target granularity D50, collecting qualified materials, and purifying to obtain the anode precursor material.
2. The method for continuously preparing a positive electrode precursor material according to claim 1, wherein the step of adding the mixed salt solution, the alkali solution, and the complexing agent to a reaction vessel for reaction comprises: adding a base solution accounting for 70-80% of the volume of the reaction kettle into the reaction kettle, adding the alkali liquor and the complexing agent under a protective atmosphere with the rotating speed of 100-600 rpm and the temperature of 50-70 ℃, adjusting the pH value of the base solution to 11-12 and the ammonia value to 3-15 g/L, and then feeding at a rate ratio of 2: and (4-6) adding the alkali liquor and the mixed salt solution for reaction, and opening unqualified overflow when the slurry in the reaction kettle reaches an overflow port.
3. The continuous preparation method of a positive electrode precursor material according to claim 2, wherein the total concentration of the mixed salt solution is 2 to 3 mol/L;
and/or the concentration of the alkali liquor is 10-11 mol/L;
and/or the concentration of the complexing agent is 10-11 mol/L.
4. A continuous production method of a positive electrode precursor material according to any one of claims 1 to 3, wherein the step of starting the concentration circulation system to control the solid content of the slurry comprises: and starting a thickener and a slurry circulator in the reaction kettle, fixing the clear water flow of the thickener, and controlling the solid content of the slurry to be 100-500 g/L.
5. The continuous production method of a positive electrode precursor material according to claim 4, wherein the target particle size D50 is 6 to 15 μm;
and/or the tap density of the positive electrode precursor is 2.4-2.6 g/cm 3 。
6. The continuous production method of a positive electrode precursor material according to any one of claims 1 to 3 or 5, wherein the purification step comprises: washing, drying, sieving and removing iron;
and/or the nickel salt comprises at least one of nickel chloride, nickel nitrate, nickel oxalate and nickel sulfate;
and/or the cobalt salt comprises at least one of cobalt chloride, cobalt nitrate, cobalt oxalate and cobalt sulfate;
and/or the manganese salt comprises at least one of manganese chloride, manganese nitrate, manganese oxalate and manganese sulfate;
and/or the complexing agent is ammonia water;
and/or the alkaline substance in the alkali liquor comprises at least one of sodium hydroxide and potassium hydroxide.
7. A positive electrode precursor material prepared by the method according to any one of claims 1 to 6, wherein the positive electrode precursor material is nickel-cobalt-manganese hydroxide and/or nickel-manganese hydroxide.
8. The continuous production method of a positive electrode precursor material according to claim 7, wherein the molar ratio of nickel element, cobalt element, and manganese element in the positive electrode precursor material is (0.5 to 0.8): (0-0.3): (0.1-0.3).
9. A positive electrode material prepared by sintering a mixture including a lithium source and a positive electrode precursor material, wherein the positive electrode precursor material includes the positive electrode precursor material according to any one of claims 7 to 8.
10. A secondary battery characterized in that a positive electrode material according to claim 9 is contained in a positive electrode of the secondary battery.
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