CN114256456B - High-voltage positive electrode material and battery containing same - Google Patents
High-voltage positive electrode material and battery containing same Download PDFInfo
- Publication number
- CN114256456B CN114256456B CN202111585946.5A CN202111585946A CN114256456B CN 114256456 B CN114256456 B CN 114256456B CN 202111585946 A CN202111585946 A CN 202111585946A CN 114256456 B CN114256456 B CN 114256456B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- lithium
- doped
- doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 86
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 44
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 30
- 229910052714 tellurium Inorganic materials 0.000 claims description 26
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 25
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 25
- -1 oxygen ions Chemical class 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 8
- 229910003870 O—Li Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 description 68
- 229910052782 aluminium Inorganic materials 0.000 description 49
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 38
- 229910052808 lithium carbonate Inorganic materials 0.000 description 38
- 238000002156 mixing Methods 0.000 description 31
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 26
- 238000007873 sieving Methods 0.000 description 26
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 24
- 238000000498 ball milling Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 229910000428 cobalt oxide Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 239000004327 boric acid Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910018134 Al-Mg Inorganic materials 0.000 description 2
- 229910018467 Al—Mg Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 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
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/50—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-voltage positive electrode material and a battery containing the positive electrode material, wherein the chemical formula of the positive electrode material is Li 1+ x Co 1‑y1‑y2‑z Me y M z B n O 2 Wherein x is more than or equal to-0.05 and less than or equal to 0.1; me includes one or more of metal elements In, Y, mg, sr, ti, zr, ni, mn, W, and y1 and y2 are not 0 and satisfy 0<y1+y2 is less than or equal to 0.03; m comprises one or more of the elements Si, ge, se, sb, te, as, 0<z is less than or equal to 0.01; b is elemental boron, 0<n<0.03. The positive electrode material provided by the invention plays the advantages of different doping elements by regulating the types of the doping elements, the doping amounts of the doping elements and the positions of the doping elements, so that the comprehensive performance of the positive electrode material is greatly improved, wherein the metal elements Al, me and M are used for maintaining the structural stability of the positive electrode material and improving the capacity of the positive electrode material through the cobalt position doped in lithium cobaltate; the element B is used for improving the cycle stability and the first coulombic efficiency of the positive electrode material through surface modification and/or doping at different positions in the lithium cobaltate.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-voltage positive electrode material, a preparation method thereof and a battery containing the positive electrode material.
Background
With the rapid development of science and technology, in order to preempt market, the updating iteration of the 3C electronic product is more and more frequent and faster. In this update iteration, requirements for higher energy density and better cycle performance are also put on the important components of the 3C electronic product, namely the battery.
Lithium cobaltate (LiCoO) is a material for positive electrode of battery such as lithium manganate, lithium nickelate, lithium nickel cobalt manganate and lithium iron phosphate 2 ) Has the highest theoretical density value (5.1 g/cm 3 ) Therefore, the advantages of tap density and compaction density which are shown in practical application are very large. Although the charging voltage can be increased with the increase of the energy density, when the charging voltage is increased to a certain degree (4.5V or more), the positive electrode material LiCoO 2 The irreversible capacity of the battery is increased and the cycle performance is reduced due to the problems of phase change of the surface layer and the inner part of the structure and the like caused by high lithium removal.
Therefore, it is imperative to develop a positive electrode material having a high specific capacity and excellent cycle performance at a high voltage, and capable of alleviating problems of surface layer and internal phase transition of the material structure in a high delithiation state.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-voltage positive electrode material, a preparation method thereof and a battery containing the positive electrode material, wherein the high-voltage positive electrode material has high specific capacity under the working voltage of 3.0-4.50V and excellent cycle stability under the working voltage of 3.0-4.55V, and the positive electrode material can solve the problems of specific capacity and cycle performance degradation and the like caused by the problems of material structure surface layer and internal phase change and the like of the existing lithium cobaltate positive electrode material under the high voltage due to high lithium removal.
The invention aims at realizing the following technical scheme:
the invention provides a positive electrode material, which is characterized in that the chemical formula of the positive electrode material is shown as a formula (1):
Li 1+x Co 1-y1-y2-z Al y1 Me y2 M z B n O 2 (1)
Wherein x is more than or equal to-0.05 and less than or equal to 0.1; me comprises one or more of metal elements In, Y, mg, sr, ti, zr, ni, mn, W, and y1 and y2 are not 0 and satisfy 0< y1+y2.ltoreq.0.03; m comprises one or more of elements Si, ge, se, sb, te, as, 0<z is less than or equal to 0.01; b is elemental boron, 0< n <0.03.
According to the invention, the positive electrode material is a doped positive electrode material containing surface modification, namely the positive electrode material is a lithium cobalt oxide positive electrode material doped with metal element Al, metal element Me and element M modified by element B.
According to the invention, the metal elements Al, me and M replace cobalt ions in the framework layer consisting of oxygen ions and cobalt ions in the lithium cobaltate crystal lattice.
According to the invention, said element B is present in at least one of the following ways:
1) Forming a modification layer on the surface of lithium cobaltate;
2) Substituting cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in a lithium cobalt oxide lattice;
3) Substituting lithium ions in the lithium ion layers at two sides of the framework layer consisting of oxygen ions and cobalt ions in the lithium cobalt oxide crystal lattice;
4) Filling gaps between O-Li and forming a tetrahedral structure with three oxygen ions;
5) Filling in the gaps of O-Co and forming a tetrahedral structure with three cobalt ions.
According to the invention, the morphology of the positive electrode material comprises at least one of single crystal, monocrystalline-like and polycrystalline.
According to the invention, the particle diameter D of the positive electrode material 50 Is 10-22 mu m.
According to the invention, the positive electrode material is a grading of a large-particle positive electrode material with a monocrystalline morphology and a small-particle positive electrode material with a monocrystalline morphology or a polycrystalline morphology.
According to the invention, the mass ratio of the positive electrode material with the single crystal morphology to the positive electrode material with the single crystal morphology or the polycrystal morphology is (2-5): 1.
According to the invention, the grain diameter D of the positive electrode material with single crystal morphology 50 Is 10-20 μm.
According to the invention, the particle diameter D of the positive electrode material with the similar single crystal morphology or the polycrystalline morphology 50 Is 2-8 μm。
The invention provides a positive plate, which comprises the positive material.
The invention provides a battery, which comprises the positive electrode material or the positive electrode plate.
The invention has the beneficial effects that:
1. the positive electrode material provided by the invention plays the advantages of different doping elements by regulating the types of the doping elements, the doping amounts of the doping elements and the positions of the doping elements, so that the comprehensive performance of the positive electrode material is greatly improved, wherein the metal elements Al and Me and the element M are used for maintaining the structural stability of the positive electrode material and improving the capacity of the positive electrode material through the cobalt position doped in lithium cobaltate; the element B is used for improving the cycle stability and the first coulombic efficiency of the positive electrode material through surface modification and/or doping at different positions in the lithium cobaltate;
2. according to the doping amount of the doping elements, the doping and mixing are carried out by different methods, wherein the metal elements Al and Me with large doping amount are doped when preparing the cobaltosic oxide, so that the problems of difficult doping of crystal lattice, uneven doping and the like in the doping process of dry sintering are avoided; the element M with small doping amount is easier to be doped into crystal lattices, so that the element M can be doped in a dry sintering mode, and the problem of complex wet preparation is avoided;
3. according to the preparation method, the precursor size is adjusted, the sintering temperature and the sintering time are controlled, the lithium cobalt oxide with large granularity and single crystal or polycrystal morphology and the lithium cobalt oxide with small granularity are prepared, and the lithium cobalt oxide with different morphology is subjected to secondary sintering by grading and size matching in a directional manner, so that the positive electrode material with compaction, capacity, circulation and first coulomb efficiency is prepared;
4. the invention fully exerts the characteristics of small ionic radius of B, strong bonding energy with O and the like by doping the element B, can be doped on the bulk phase and the surface of lithium cobaltate, stabilizes the oxygen skeleton and the surface stability, can effectively improve the discharge characteristic of the material on one hand, improves the first coulomb efficiency, and improves the cycle performance of the positive electrode material under high voltage on the other hand;
5. the preparation method of the positive electrode material provided by the invention has the advantages of simple process, strong operability and easiness in large-scale production.
Drawings
FIG. 1 is a cycle retention curve (button cell) of the positive electrode materials of example 1, example 2, example 6 and comparative example 1 of the present invention at a voltage of 3.0 to 4.55V;
fig. 2 is an SEM image of the positive electrode material of example 1 of the present invention.
Detailed Description
[ Positive electrode Material ]
As described above, the present invention provides a positive electrode material having a chemical formula shown in formula (1):
Li 1+x Co 1-y1-y2-z Al y1 Me y2 M z B n O 2 (1)
Wherein x is more than or equal to-0.05 and less than or equal to 0.1; me comprises one or more of metal elements In, Y, mg, sr, ti, zr, ni, mn, W, and y1 and y2 are not 0 and satisfy 0< y1+y2.ltoreq.0.03; m comprises one or more of elements Si, ge, se, sb, te, as, 0<z is less than or equal to 0.01; b is elemental boron, 0< n <0.03.
According to embodiments of the invention, x may be-0.05, -0.04, -0.03, -0.02, -0.01, 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, or 0.1.
According to an embodiment of the present invention, y1+y2 is 0 to 0.03, more preferably 0.01 to 0.03, and may be 0.012, 0.015, 0.017, 0.02, 0.022, 0.025, 0.027, or 0.03.
According to an embodiment of the present invention, y1 is 0.001 to 0.03, more preferably 0.01 to 0.03, and may be 0.012, 0.015, 0.017, 0.02, 0.022, 0.025, 0.027 or 0.029.
According to embodiments of the invention, z may be 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, or 0.01.
According to an embodiment of the present invention, n may be 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.012, 0.015, 0.018, 0.02, 0.022, 0.025, 0.028 or 0.03.
According to the embodiment of the invention, the positive electrode material is a doped positive electrode material containing surface modification, namely the positive electrode material is a lithium cobalt oxide positive electrode material doped with metal elements Al, me and M modified by elements B.
According to the invention, the variety of the doping element, the doping amount of the doping element and the doping position of the doping element in the positive electrode material are regulated, so that the comprehensive performance of the positive electrode material is improved, and the application under a high-voltage system is realized.
According to an embodiment of the present invention, the metal element Al, the metal element Me, and the element M replace cobalt ions in the framework layer composed of oxygen ions and cobalt ions in the lithium cobaltate lattice.
According to an embodiment of the invention, said element B is present in at least one of the following ways:
1) Forming a modification layer (i.e., a coating layer) on the surface of lithium cobaltate;
2) Substituting cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in a lithium cobalt oxide lattice;
3) Substituting lithium ions in the lithium ion layers at two sides of the framework layer consisting of oxygen ions and cobalt ions in the lithium cobalt oxide crystal lattice;
4) Filling gaps between O-Li and forming a tetrahedral structure with three oxygen ions;
5) Filling in the gaps of O-Co and forming a tetrahedral structure with three cobalt ions.
With respect to the above disclosed cathode materials, it should be noted that the doping elements (Al, me, M, and B) are all in a lithium cobaltate lattice including a framework layer composed of oxygen ions and cobalt ions and lithium ion layers distributed on both sides of the framework. Specifically, the metal element Al, the metal element Me and the element M replace cobalt ions in a framework layer composed of oxygen ions and cobalt ions in a lithium cobaltate crystal lattice. The element B forms a modification layer on the surface of the lithium cobaltate; and/or, substituting cobalt ions in the framework layer consisting of oxygen ions and cobalt ions in the lithium cobaltate crystal lattice; and/or, substituting lithium ions in the lithium ion layers at two sides of the framework layer formed by oxygen ions and cobalt ions in the lithium cobalt oxide crystal lattice; and/or filling gaps of O-Li and forming a tetrahedral structure with three oxygen ions; and/or filling gaps of O-Co and forming a tetrahedral structure with three cobalt ions. The metal element Al and the metal element Me are used for maintaining the structural stability of the positive electrode material and improving a voltage platform; element M is used to increase the capacity of the positive electrode material; the element B can be stably doped to the bulk phase and the surface of lithium cobaltate due to the small ionic radius, and can stabilize the oxygen skeleton and the surface stability due to the strong bonding energy characteristic between the element B and oxygen, so that the cycle stability and the primary charging efficiency of the positive electrode material can be improved.
According to an embodiment of the invention, the morphology of the positive electrode material comprises at least one of monocrystalline, monocrystalline-like and polycrystalline. Preferably, the morphology of the positive electrode material includes single crystal, mono-like crystal and polycrystalline.
It is pointed out that the positive electrode material with single crystal morphology has large particle size and small specific surface area, so that the side reaction with electrolyte is less, and the improvement of the battery cycle performance is facilitated, but the initial coulombic efficiency is reduced and the multiplying power performance is also reduced because the particles of the material are larger; the positive electrode material with the similar monocrystalline morphology or polycrystalline morphology is a secondary particle composed of primary particles, and the primary particles have higher first coulombic efficiency and multiplying power performance because of smaller particle size, but side reaction with electrolyte is increased because of larger specific surface area, and in addition, the secondary particle composed of small particles is easy to crack, so that the cycle performance is reduced. The invention plays the advantages of single crystal and polycrystal through the size and granularity collocation.
According to an embodiment of the present invention, the polycrystalline morphology refers to the morphology of spheroidal secondary particle particles formed by agglomeration of a plurality of primary particles; single crystal morphology refers to the morphology of a particle consisting of a single primary particle; the single-crystal-like morphology refers to the morphology of secondary particle particles formed by agglomerating a small amount of primary particles.
According to an embodiment of the present invention, the particle diameter D of the positive electrode material 50 From 10 μm to 22. Mu.m, preferably from 13 μm to 19. Mu.m, such as 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm or 19. Mu.m.
Preferably, the positive electrode material is prepared by grading a positive electrode material with large particle monocrystalline morphology and a positive electrode material with small particle monocrystalline morphology or polycrystalline morphology.
Preferably, the mass ratio of the positive electrode material with single crystal morphology to the positive electrode material with single crystal morphology or polycrystal morphology is (2-5): 1, for example, 2:1, 3:1, 4:1 or 5:1.
Preferably, the particle diameter D of the positive electrode material with single crystal morphology 50 The grain diameter D of the positive electrode material with the similar single crystal morphology or the polycrystal morphology is 10-20 mu m 50 Is 2-8 μm.
[ preparation of cathode Material ]
The invention also provides a preparation method of the positive electrode material, which comprises the following steps:
1) Selecting doped metal element Al and metal element Me and grain diameter D 50 Mixing cobalt oxide with the diameter of 10-20 mu M with lithium source and compound containing element M, sintering, crushing, sieving and grading to obtain grain diameter D with single crystal morphology 50 Lithium cobaltate A1 with the diameter of 10 μm to 20 μm;
2) Selecting doped metal element Al and metal element Me and grain diameter D 50 Mixing cobalt oxide with the size of 2-8 mu M with lithium source and compound containing element M, sintering, crushing, sieving and grading to obtain grain size D similar to that of monocrystal and polycrystal 50 Lithium cobaltate A2 with the diameter of 2-8 μm;
3) Mixing the lithium cobaltate A1 and the lithium cobaltate A2, adding a compound containing B element, mixing, sintering, crushing, sieving and grading to obtain the positive electrode material.
According to an embodiment of the invention, in step 1) and step 2), the metal element Me comprises one or more of In, Y, mg, sr, ti, zr, ni, mn, W.
According to an embodiment of the present invention, in the step 1) and the step 2), in the cobaltosic oxide doped with the metal element Al and the metal element Me, a doping amount of the metal element Al and the metal element Me is 20000ppm or less.
Illustratively, in the cobaltosic oxide doped with the metal element Al and the metal element Me, the doping amount of the metal element Al is 4000ppm to 8000ppm, and the doping amount of the metal element Me is 500ppm to 2000ppm (i.e. the doping amount of each metal element Me is 500ppm to 2000 ppm).
According to an embodiment of the invention, in step 1) and step 2), the element M comprises one or more of Si, ge, se, sb, te, as.
In the step 1) and the step 2), lithium cobaltates with different morphologies can be obtained by controlling the sintering temperature and the sintering time: when the sintering temperature is higher than 1040 ℃ and the sintering time is higher than 12 hours, lithium cobalt oxide with single crystal morphology can be obtained, and the particle size is larger; when the sintering temperature is less than 960 ℃ and the sintering time is less than 8 hours, the lithium cobaltate with a similar monocrystal morphology and a polycrystal morphology can be obtained, and the particle size is smaller.
Illustratively, the sintering temperature in step 1) is 1000 ℃ to 1100 ℃, the sintering time is 12h to 24h, more preferably, the sintering temperature is 1040 ℃ to 1085 ℃, and the sintering time is 12h to 16h.
Illustratively, the sintering temperature in step 2) is 900-1040 ℃, the sintering time is 6-12 hours, more preferably, the sintering temperature is 930-1000 ℃, and the sintering time is 8-10 hours.
Wherein the sintering atmosphere is air atmosphere or oxygen atmosphere, and naturally cooling to room temperature after sintering;
wherein in the step 1) and the step 2), the molar ratio of Li to Co to M in the lithium source, the cobaltosic oxide doped with the metal element Al and the metal element Me and the compound containing the element M is (0.95-1.10) 1 (0-0.01), more preferably the molar ratio of Li to Co to M is (1.02-1.05) 1 (0-0.01), and the molar number of M is not 0.
In the step 1) and the step 2), it is required to explain that the mixing can be performed by a high-speed mixer and ball milling, and the mixing time is 0.5 h-4 h, and more preferably, the mixing time is 0.5 h-2 h.
In the step 1) and the step 2), the requirements for crushing, sieving and grading are that the materials with the target particle size range are obtained by firstly performing preliminary crushing on a roller machine, then passing through a 300-mesh screen and then performing particle size grading on the materials by a jet classifier.
Wherein, in the step 1) and the step 2), the lithium source is at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium acetate, lithium citrate and lithium oxide.
Wherein, in the step 3), the addition amount of the compound containing B element is 0.1 to 5wt%, more preferably 0.1 to 3wt% of the total weight of the lithium cobaltate A1 and the lithium cobaltate A2.
Wherein in the step 3), the compound containing B element is selected from at least one of boron oxide and boric acid.
In the step 3), the mass ratio of the lithium cobaltate A1 to the lithium cobaltate A2 is (2-5): 1.
Wherein in the step 1), the metal element Al and the metal element Me are doped, and the particle size D 50 The cobaltosic oxide with the diameter of 10 μm to 20 μm can be prepared by a method comprising the following steps:
(1) Dissolving a soluble cobalt source in water to prepare a solution, adding a soluble compound containing an Al element and a soluble compound containing a Me element, and stirring to obtain a mixed solution;
(2) Sequentially adding a complex and a precipitator into the solution prepared in the step (1), uniformly stirring, and carrying out complex precipitation reaction; in the reaction process, the stirring rotation speed is controlled to be in the range of 140 rpm-850 rpm, the pH is controlled to be in the range of 6.5-8.5, and the temperature is controlled to be in the range of 25-80 ℃; stopping stirring after the feeding is finished, standing, layering solid and liquid, pumping supernatant, and continuing the feeding to enable crystals to continuously grow;
(3) Repeating the above-mentioned cyclic processes of charging, standing for solid-liquid layering, drawing supernatant liquor and continuously charging for 6-12 times, controlling crystal grain size to grow to D 50 The feeding is finished when the particle size is 10-20 mu m;
(4) Washing, drying and calcining the reacted slurry to obtain the particle diameter D doped with metal element Al and metal element Me 50 Tricobalt tetraoxide of 10-20 μm.
Wherein, and in the step 2), the metal element Al and the metal element Me are doped, and the particle size D 50 Tricobalt tetraoxide of 2 μm to 8 μm can be obtained by including the followingThe preparation method comprises the following steps:
(1') mixing a soluble cobalt source, a soluble compound containing Al element and a soluble compound containing Me element to prepare a solution, adding a sodium hydroxide solution and a hydrogen peroxide solution, uniformly stirring to obtain a mixed solution, adding the mixed solution into a reaction kettle, controlling the pH in the reaction kettle to be 8.0-8.5 in the reaction process, and controlling the temperature to be 70-75 ℃ and the reaction time to be 22-24 hours;
(2') washing, drying and calcining the mixture once after the reaction is finished to obtain the metal element Al and the metal element Me doped and the particle size D 50 Tricobalt tetraoxide of 2-8 μm.
For the above-mentioned cobaltosic oxide doped with the metal element Al and the metal element Me, it is necessary to further explain that:
wherein the soluble cobalt source is at least one of cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt hydroxide, cobalt acetate and cobalt oxalate; the soluble compound containing Al element is at least one of sulfate, nitrate, oxalate, acetate, fluoride, chloride, oxide and hydroxide containing Al element; the soluble compound containing the Me element is at least one of sulfate, nitrate, oxalate, acetate, fluoride, chloride, oxide and hydroxide containing the Me element; the concentration of the prepared solution is 100-120 g/L.
Wherein the complex is ammonia water or amino hydroxy acid salt solution, and can be diluted ammonia water with concentration of 20-25% diluted by 10 times; the precipitant is a water-soluble base, carbonate or oxalate having a concentration of 0.4 to 3.6mol/L, and may be at least one of sodium carbonate, sodium bicarbonate and ammonia carbonate having a concentration of 0.4 to 3.6 mol/L.
Wherein, the particle diameter D of the doped metal element Al and the doped metal element Me 50 The calcination conditions of the cobaltosic oxide of 10-20 μm are divided into two sections: the first stage is pre-heating decomposition at 250-450 deg.c for 2-6 hr; the second stage is pyrolysis at 550-850 deg.c for 2-6 hr.
Wherein, the metal element Al and the metal element Me are doped and the grain diameter is equal to that of the metal elementD 50 The calcination temperature of the cobaltosic oxide is 800-900 ℃ and the calcination time is 1-3 h.
[ Positive electrode sheet and Battery ]
The invention also provides a positive plate, which comprises the positive material.
According to an embodiment of the present invention, the positive electrode sheet includes a conductive agent and a binder.
According to the embodiment of the invention, the positive plate comprises the following components in percentage by mass: 70-98 wt% of positive electrode material, 1-15 wt% of conductive agent and 1-15 wt% of binder.
Preferably, the positive plate comprises the following components in percentage by mass: 80-98 wt% of positive electrode material, 1-10 wt% of conductive agent and 1-10 wt% of binder.
The invention also provides a battery, which comprises the positive plate.
According to an embodiment of the invention, the battery is a lithium ion battery.
According to an embodiment of the present invention, the battery further includes a negative electrode sheet, a separator, and an electrolyte.
According to an embodiment of the present invention, the negative electrode sheet includes a negative electrode material, a conductive agent, and a binder.
According to the embodiment of the invention, the negative plate comprises the following components in percentage by mass: 70-98 wt% of negative electrode material, 1-15 wt% of conductive agent and 1-15 wt% of binder.
Preferably, the negative plate comprises the following components in percentage by mass: 80-98 wt% of negative electrode material, 1-10 wt% of conductive agent and 1-10 wt% of binder.
According to an embodiment of the present invention, the negative electrode material may be at least one of artificial graphite, natural graphite, hard carbon, silicon carbon, mesophase carbon microspheres, and lithium titanate.
According to an embodiment of the present invention, the conductive agent is at least one of Super P, ketjen black, acetylene black, carbon nanotubes, and carbon fibers.
According to an embodiment of the present invention, the binder is at least one of polyvinylidene fluoride, polytetrafluoroethylene, and lithium polyacrylate.
According to an embodiment of the present invention, the electrolyte includes an organic solvent and a conductive lithium salt, and the organic solvent may be at least one of a cyclic carbonate, a linear carbonate, and a linear hydroxy acid ester; the conductive lithium salt may be at least one of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, and lithium bis (trifluoromethanesulfonyl) imide.
In practice, the organic solvent may comprise 20 to 40vol% cyclic carbonate and 60 to 80vol% linear carbonate and/or linear carboxylate (based on 100vol% total volume).
According to an embodiment of the present invention, the separator may be a polypropylene-based separator, for example, a rubberized polypropylene separator coated with ceramic on one or both sides of a polypropylene-based material.
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
(1) Taking lithium carbonate, and containing Al and Mg doped particle diameter D 50 Cobalt oxide with the doping amount of 14-16 mu M, wherein the doping amount of Al element is 70000 ppm, the doping amount of Mg element is 1000ppm, the mol ratio of Li/Co is 1.05:1, the doping amount of M element is Te, the doping amount of M element is 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with 18 μm Al, mg, te;
(2) Taking lithium carbonate, and containing Al and Mg doped particle diameter D 50 Cobalt oxide with the doping amount of Al element being 70000 ppm, the doping amount of Mg element being 1000ppm, the mole ratio of Li/Co being 1.05:1, the doping amount of M being Te, the doping amount being 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 980 ℃ for 10h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Al, mg, te co-doped lithium cobaltate of 4.5 μm;
(3) The particle diameter D 50 The Al, mg and Te co-doped lithium cobaltate powder with the particle size of 18 mu m and 4.5 mu m is weighed according to the mass ratio of 4:1, 2000ppm boric acid is added, ball milling and mixing are carried out for 1h, sintering is carried out in a muffle furnace in an air atmosphere, the sintering temperature is 950 ℃ and the sintering time is 12h, and the particle size D is obtained through crushing, sieving and grading 50 The SEM image of the 16.8 μm product, i.e., high voltage co-doped lithium cobalt oxide with elemental B modified Al, mg and Te, is shown in FIG. 1.
(4) Dispersing the high-voltage lithium cobaltate anode material co-doped with the B element modified Al, mg and Te, a conductive agent Super P and a binder polyvinylidene fluoride PVDF in a nitrogen methyl pyrrolidone NMP solvent according to a mass ratio of 97:1.5:1.5, uniformly stirring in a deaerator to obtain anode slurry, uniformly coating the anode slurry on the surface of an aluminum foil, placing the aluminum foil on a vacuum oven at 120 ℃ for baking for 12 hours, and then rolling and cutting to obtain the anode plate.
The positive plate and the negative electrode of the lithium plate are respectively provided with a PP/PE/PP three-layer diaphragm, and 1mol/L LiPF is used 6 And (C+DEC) electrolyte (volume ratio is 1:1) to assemble the button cell. Electrochemical test is carried out under the environment of normal temperature (25 ℃), the first-circle charge-discharge voltage is 3.0-4.50V, and the charge-discharge multiplying power is 0.1C; the charge-discharge voltage of the cycle performance test is 3.0-4.55V, and the charge-discharge multiplying power is 0.5C.
The cycle curve of the battery made of the positive electrode material obtained in example 1 at normal temperature (25 ℃) is shown in fig. 2.
Example 2
(1) Taking lithium carbonate, and doping the lithium carbonate with Al and Ni to obtain the particle diameter D 50 Cobalt oxide with the doping amount of 16-18 mu M, wherein the doping amount of Al element is 70000 ppm, the doping amount of Ni element is 1500ppm, the mol ratio of Li/Co is 1.05:1, the doping amount of M element is Te, the doping amount of M element is 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with 20 μm of Al, ni and Te;
(2) Taking lithium carbonate, and doping the lithium carbonate with Al and Ni to obtain the particle diameter D 50 Cobalt oxide with the doping amount of Al element being 70000 ppm, the doping amount of Ni element being 1500ppm, the mole ratio of Li/Co being 1.05:1, the doping amount of M being Te, the doping amount being 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 980 ℃ for 10h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with Al, ni and Te of 6 μm;
(3) The particle diameter D 50 Weighing Al, ni and Te co-doped lithium cobaltate powder with the mass ratio of 20 mu m to 6 mu m according to the mass ratio of 4:1, adding 2000ppm boric acid, ball milling and mixing for 1h, sintering in a muffle furnace in an air atmosphere at 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D 50 Is a 18.6 μm product, namely, high voltage lithium cobalt oxide co-doped with Al, ni and Te modified by B element.
The cycle curve of the battery made of the positive electrode material obtained in example 2 at normal temperature (25 ℃) is shown in fig. 2.
(4) As in example 1.
Example 3
(1) Taking lithium carbonate, and doping particle diameter D containing Al and Zr 50 15-17 μm of tricobalt tetraoxide, wherein the doping amount of Al element is 70000 ppm, the doping amount of Zr element is 1500ppm, the mole ratio of Li/Co is 1.05:1, the doping element M is Te, the doping amount is 2000ppm, respectively weighing lithium carbonate, tricobalt tetraoxide and telluric acid, and respectively weighing the lithium carbonate, the tricobalt tetraoxide and the telluric acid, and carrying out the processBall milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with 18 μm Al, zr and Te;
(2) Taking lithium carbonate, and doping particle diameter D containing Al and Zr 50 Cobalt oxide with the doping amount of Al element being 70000 ppm, the doping amount of Zr element being 1500ppm, the mole ratio of Li/Co being 1.05:1, the doping amount of M being Te, the doping amount being 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 980 ℃ for 10h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with Al, zr and Te of 4.5 μm;
(3) The particle diameter D 50 The Al, zr and Te co-doped lithium cobaltate powder with the thickness of 18 mu m and 4.5 mu m is weighed according to the mass ratio of 4:1, 2000ppm boric acid is added, ball milling and mixing are carried out for 1h, sintering is carried out in a muffle furnace in an air atmosphere, the sintering temperature is 950 ℃ and the sintering time is 12h, and the particle size D is obtained through crushing, sieving and grading 50 Is a 16.5 μm product, namely, high voltage lithium cobalt oxide co-doped with Al, zr and Te modified by B element.
(4) As in example 1.
Example 4
(1) Taking lithium carbonate, and doping the lithium carbonate with Al and W to obtain particle diameter D 50 Cobalt oxide with the doping amount of 14-16 mu M, wherein the doping amount of Al element is 70000 ppm, the doping amount of W element is 1000ppm, the mol ratio of Li/Co is 1.05:1, the doping amount of M element is Te, the doping amount of M element is 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with 18 μm Al, W and Te;
(2) Taking lithium carbonate, and doping the lithium carbonate with Al and W to obtain particle diameter D 50 Tricobalt tetraoxide of 2-4 μm, wherein Al elementThe doping amount of element is 70000 ppm, the doping amount of element W is 1000ppm, the doping amount of element M is Te, the doping amount is 2000ppm, respectively weighing lithium carbonate, cobaltosic oxide and telluric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 980 ℃ for 10h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with Al, W and Te of 4 μm;
(3) The particle diameter D 50 Weighing Al, W and Te co-doped lithium cobaltate powder with the mass ratio of 18 mu m to 4 mu m according to the mass ratio of 5:1, adding 2000ppm boric acid, ball milling and mixing for 1h, sintering in a muffle furnace in an air atmosphere at 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D 50 Is a 15.6 μm product, namely, high-voltage lithium cobalt oxide co-doped with Al, W and Te modified by B element.
(4) As in example 1.
Example 5
(1) Taking lithium carbonate, and doping the lithium carbonate with Al and Y to obtain the particle diameter D 50 Cobaltosic oxide with the doping amount of the Al element of 7000ppm and the doping amount of the Y element of 2000ppm, wherein the doping amount of the cobaltosic oxide is 18-20 mu m, and the mole ratio of Li/Co is 1.05:1, doping element M is Te, doping amount is 2000ppm, respectively weighing lithium carbonate, cobaltosic oxide and telluric acid, ball-milling and mixing for 1h, placing in a muffle furnace in air atmosphere for sintering at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain particle size D 50 Lithium cobalt oxide co-doped with 22 μm Al, Y and Te;
(2) Taking lithium carbonate, and doping the lithium carbonate with Al and Y to obtain the particle diameter D 50 Tricobalt tetraoxide with the doping amount of the Al element being 7000ppm, the doping amount of the Y element being 2000ppm, and the mole ratio of Li/Co being 1.05:1, doping element M is Te, doping amount is 2000ppm, respectively weighing lithium carbonate, cobaltosic oxide and telluric acid, ball-milling and mixing for 1h, placing in a muffle furnace in air atmosphere for sintering at 980 ℃ for 10h, naturally cooling after sintering, crushing, sieving and grading to obtain particle size D 50 Lithium cobalt oxide co-doped with 8 μm Al, Y and Te;
(3) The particle diameter D 50 The Al, Y and Te co-doped lithium cobaltate powder with the particle size of 22 mu m and 8 mu m is weighed according to the mass ratio of 5:1, 2000ppm boric acid is added, ball milling and mixing are carried out for 1h, sintering is carried out in a muffle furnace in an air atmosphere, the sintering temperature is 950 ℃ and the sintering time is 12h, and the particle size D is obtained through crushing, sieving and grading 50 Is a 20 μm product, namely, high-voltage lithium cobalt oxide co-doped with Al, Y and Te modified by B element.
(4) As in example 1.
Example 6
(1) Same as in example 2;
(2) Same as in example 2;
(3) The particle diameter D 50 Weighing Al, ni and Te co-doped lithium cobaltate powder with the mass ratio of 18 mu m to 6 mu m according to the mass ratio of 1:1, adding 2000ppm boric acid, ball milling and mixing for 1h, sintering in a muffle furnace in an air atmosphere at 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D 50 Is a 18.6 μm product, namely, high voltage lithium cobalt oxide co-doped with Al, ni and Te modified by B element.
The cycle curve of the battery made of the positive electrode material obtained in example 6 at normal temperature (25 ℃) is shown in fig. 2.
The capacity and cycle performance of example 6 were deteriorated, even inferior to those of the battery of comparative example 1, compared to example 2, indicating that a reasonable size particle size collocation was able to improve the specific capacity and cycle performance of high voltage lithium cobaltate.
Comparative example 1
(1) Taking lithium carbonate, and containing Al and Mg doped particle diameter D 50 Cobalt oxide with the doping amount of 14-16 mu M, wherein the doping amount of Al element is 70000 ppm, the doping amount of Mg element is 1000ppm, the mol ratio of Li/Co is 1.05:1, the doping amount of M element is Te, the doping amount of M element is 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with 18 μm of Al, mg and Te;
(2) Taking lithium carbonate, and containing Al and Mg doped particle diameter D 50 Cobalt oxide with the doping amount of Al element being 70000 ppm, the doping amount of Mg element being 1000ppm, the mole ratio of Li/Co being 1.05:1, the doping amount of M being Te, the doping amount being 2000ppm, respectively weighing lithium carbonate, cobalt oxide and telluric acid, ball milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at 980 ℃ for 10h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D 50 Lithium cobalt oxide co-doped with Al, mg and Te of 4.5 μm;
(3) The particle diameter D 50 Weighing Al, mg and Te co-doped lithium cobaltate powder with the mass ratio of 18 mu m to 4.5 mu m according to the mass ratio of 4:1, ball milling and mixing for 1h, sintering in a muffle furnace in an air atmosphere at 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D 50 Is 16.8 mu m product, namely Al, mg and Te co-doped high-voltage lithium cobalt oxide.
(4) As in example 1.
The cycle curve of the battery made of the positive electrode material obtained in comparative example 1 at normal temperature (25 ℃) is shown in fig. 2.
As can be seen from fig. 2, comparative example 1 shows inferior capacity, initial coulombic efficiency and cycle compared to example 1, because the B element as a modifying element can significantly improve electrochemical performance of high-voltage lithium cobaltate.
Comparative example 2
Other operations are the same as in example 1, except that: with particle size D doped with Al 50 Tricobalt tetraoxide of 14 μm to 16 μm (wherein the doping amount of Al element is 7000 ppm) was used in place of the Al-Mg-containing doping particle diameter D of example 1 50 Tricobalt tetraoxide of 14-16 mu m; particle diameter D doped with Al 50 Tricobalt tetraoxide (wherein the doping amount of Al element is 7000 ppm) of 2 μm to 4 μm was used in place of the Al-Mg-containing doping particle diameter D of example 1 50 Tricobalt tetraoxide of 2-4 μm.
Comparative example 3
Other operations are the same as in example 1, except that: by particle size D 50 Tricobalt tetraoxide of 14-16 μm replaces the particle diameter D containing Al and Mg doping in example 1 50 Tricobalt tetraoxide with the diameter of 14-16 μm; by particle size D 50 Tricobalt tetraoxide of 2-4 μm replaces the particle diameter D containing Al and Mg doping in example 1 50 Tricobalt tetraoxide of 2-4 μm.
Comparative example 4
(1) Taking lithium carbonate, and containing Al and Mg doped particle diameter D 50 Cobalt oxide with the doping amount of Al element being 70000 ppm and the doping amount of Mg element being 1000ppm, respectively weighing lithium carbonate and cobalt oxide according to the mole ratio of Li/Co being 1.05:1, ball-milling and mixing the lithium carbonate and the cobalt oxide for 1h, sintering the mixture in a muffle furnace in an air atmosphere at 1080 ℃ for 14h, naturally cooling the mixture after sintering, and obtaining the particle size D through crushing, sieving and grading 50 Lithium cobalt oxide co-doped with 18 μm of Al and Mg;
(2) Taking lithium carbonate, and containing Al and Mg doped particle diameter D 50 Cobalt oxide with the doping amount of Al element being 70000 ppm and the doping amount of Mg element being 1000ppm, respectively weighing lithium carbonate and cobalt oxide according to the mole ratio of Li/Co being 1.05:1, ball-milling and mixing the lithium carbonate and the cobalt oxide for 1h, sintering the mixture in a muffle furnace in an air atmosphere at 980 ℃ for 10h, naturally cooling the mixture after sintering, and obtaining the particle size D through crushing, sieving and grading 50 Al and Mg co-doped lithium cobalt oxide of 4.5 μm;
(3) The particle diameter D 50 Al and Mg co-doped lithium cobaltate powder with the mass ratio of 18 mu m to 4.5 mu m is weighed according to the mass ratio of 4:1, 2000ppm boric acid is added, ball milling and mixing are carried out for 1h, sintering is carried out in a muffle furnace in an air atmosphere, the sintering temperature is 950 ℃ and the sintering time is 12h, and the particle size D is obtained through crushing, sieving and grading 50 Is 16.8 mu m product, namely high-voltage lithium cobalt oxide co-doped with Al and Mg modified by B element.
Performance test:
charging 0.1C to 4.5V, and stopping current at 0.025C to obtain the first charge capacity of the positive electrode active material, standing for 15min, and discharging 0.1C to 3V to obtain the first discharge capacity of the positive electrode active material; dividing the first charge capacity by the mass of the positive electrode active material to obtain a first charge specific capacity of the positive electrode active material, and dividing the first discharge capacity by the mass of the positive electrode active material to obtain a first discharge specific capacity of the positive electrode active material; the first coulombic efficiency of the positive electrode active material is remembered by dividing the first discharge specific capacity of the positive electrode material by its first charge specific capacity.
At normal temperature (25 ℃) the battery was charged to 4.55V at 0.5C, the off-current was 0.05C, left for 15min, then discharged to 3V at a constant current of 0.5C, the initial capacity Q0 was recorded, the capacity after each cycle was recorded, the previous discharge capacity was taken as the capacity Q2 of the battery, and the capacity retention (%) (the calculation formula used therein was as follows: cyclic capacity retention = Q2/q0×100%).
Table 1 results of performance test of batteries of examples and comparative examples
The specific test results of examples and comparative examples are shown in table 1, and it can be seen from the results in table 1 that the battery samples employing the embodiments of the present invention exhibit excellent properties in terms of specific capacity, initial coulombic efficiency and battery cycle performance, while the comparative examples are inferior to the electrochemical properties of the examples. The cathode material in the embodiment of the invention is modified by the B element and is co-doped with different elements, so that the surface layer and internal phase change of the lithium cobaltate in a high lithium removal state are relieved, the structure of the cathode material is stabilized, the specific capacity and the cycle performance of the cathode material are improved, and further, the overall reaction dynamics and the electrochemical performance of the cathode material are improved through the matching of large and small particles.
In particular, in comparative example 2 doped with Al element, te element and B element, the doping of Al element can improve the stability of the positive electrode material, but the higher the doping amount, the lower the capacity; the comparative example 3 was not doped with Al and the metal element Me, resulting in deterioration of the overall performance of the positive electrode material, especially the battery performance at high voltage was significantly deteriorated; the absence of the doping element M in comparative example 4 also leads to deterioration of the overall electrochemical performance of the battery.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The positive electrode material is characterized in that the chemical formula of the positive electrode material is shown as a formula (1):
Li 1+x Co 1-y1-y2-z Al y1 Me y2 M z B n O 2 (1)
Wherein x is more than or equal to-0.05 and less than or equal to 0.1; me comprises one or more of metal elements Y, mg, zr, ni, W, and y1 and y2 are not 0 and satisfy 0.01-y 1 +y2-0.03; m comprises one or more of Se and Te, and z is more than or equal to 0.001 and less than or equal to 0.003; n is more than or equal to 0.01 and less than or equal to 0.03;
the positive electrode material is a grading material of a large-particle positive electrode material with a monocrystal appearance and a small-particle positive electrode material with a monocrystal-like appearance or a polycrystal appearance;
particle diameter D of the positive electrode material with single crystal morphology 50 Is 10-20 mu m;
particle diameter D of the positive electrode material similar to single crystal morphology or polycrystalline morphology 50 Is 2-8 mu m;
the mass ratio of the monocrystal appearance positive electrode material to the monocrystal appearance or polycrystal appearance positive electrode material is (2-5) 1.
2. The positive electrode material according to claim 1, wherein the positive electrode material is a surface-modified doped positive electrode material, i.e. the positive electrode material is a lithium cobalt oxide positive electrode material doped with a metal element Al, a metal element Me and an element M modified with an element B.
3. The positive electrode material according to claim 1, wherein the metal element Al, the metal element Me, and the element M replace cobalt ions in a framework layer composed of oxygen ions and cobalt ions in a lithium cobaltate lattice.
4. The positive electrode material according to claim 1, wherein the element B is present in at least one of the following ways:
1) Forming a modification layer on the surface of lithium cobaltate;
2) Substituting cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in a lithium cobalt oxide lattice;
3) Substituting lithium ions in the lithium ion layers at two sides of the framework layer consisting of oxygen ions and cobalt ions in the lithium cobalt oxide crystal lattice;
4) Filling gaps between O-Li and forming a tetrahedral structure with three oxygen ions;
5) Filling in the gaps of O-Co and forming a tetrahedral structure with three cobalt ions.
5. The positive electrode material according to any one of claims 1 to 4, wherein the positive electrode material has a particle diameter D 50 Is 10 μm to 19 μm.
6. A positive electrode sheet, characterized in that the positive electrode sheet comprises the positive electrode material according to any one of claims 1 to 5.
7. A battery comprising the positive electrode material according to any one of claims 1 to 5, or the positive electrode sheet according to claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111585946.5A CN114256456B (en) | 2021-12-20 | 2021-12-20 | High-voltage positive electrode material and battery containing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111585946.5A CN114256456B (en) | 2021-12-20 | 2021-12-20 | High-voltage positive electrode material and battery containing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114256456A CN114256456A (en) | 2022-03-29 |
| CN114256456B true CN114256456B (en) | 2024-01-16 |
Family
ID=80797006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111585946.5A Active CN114256456B (en) | 2021-12-20 | 2021-12-20 | High-voltage positive electrode material and battery containing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114256456B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116092615B (en) * | 2023-04-06 | 2023-08-29 | 宁德时代新能源科技股份有限公司 | Method and device for determining distribution trend of doping element |
| CN117239111B (en) * | 2023-11-13 | 2024-02-02 | 北京中科海钠科技有限责任公司 | Nickel-free layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application |
| CN117276532B (en) * | 2023-11-21 | 2024-03-29 | 宜宾锂宝新材料有限公司 | High-tap-density positive electrode material, preparation method thereof and lithium battery |
| CN117542961A (en) * | 2024-01-10 | 2024-02-09 | 宁德时代新能源科技股份有限公司 | Battery monomer, battery and power consumption device |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281964A (en) * | 2007-04-04 | 2008-10-08 | 三星Sdi株式会社 | Positive electrode and rechargeable lithium battery including same |
| CN104134791A (en) * | 2014-07-10 | 2014-11-05 | 宁波金和新材料股份有限公司 | High-voltage mono-crystal lithium nickel cobalt manganese oxide anode material and preparation method thereof |
| CN104205439A (en) * | 2012-03-23 | 2014-12-10 | 法拉典有限公司 | Metallate electrodes |
| CN105680009A (en) * | 2016-01-18 | 2016-06-15 | 湖南杉杉能源科技股份有限公司 | M-contained multifunctional metal oxide modified high-voltage lithium cobalt oxide positive electrode powder material and preparation method therefor |
| JP2018037372A (en) * | 2016-09-02 | 2018-03-08 | 株式会社豊田自動織機 | Lithium ion secondary battery |
| CN108767255A (en) * | 2018-05-28 | 2018-11-06 | 格林美（无锡）能源材料有限公司 | A kind of high voltage high capacity type lithium cobaltate cathode material and preparation method thereof |
| CN110350188A (en) * | 2019-07-29 | 2019-10-18 | 昆山宝创新能源科技有限公司 | Anode material of lithium battery and preparation method thereof and lithium battery |
| JP2019185920A (en) * | 2018-04-04 | 2019-10-24 | 株式会社豊田自動織機 | Lithium ion secondary battery |
| CN110649232A (en) * | 2018-06-27 | 2020-01-03 | 株式会社村田制作所 | Positive electrode active material for lithium ion secondary battery |
| CN113675383A (en) * | 2021-07-09 | 2021-11-19 | 惠州锂威新能源科技有限公司 | Modified positive electrode material and preparation method thereof, positive plate and lithium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11757096B2 (en) * | 2019-08-21 | 2023-09-12 | Apple Inc. | Aluminum-doped lithium cobalt manganese oxide batteries |
-
2021
- 2021-12-20 CN CN202111585946.5A patent/CN114256456B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101281964A (en) * | 2007-04-04 | 2008-10-08 | 三星Sdi株式会社 | Positive electrode and rechargeable lithium battery including same |
| CN104205439A (en) * | 2012-03-23 | 2014-12-10 | 法拉典有限公司 | Metallate electrodes |
| CN104134791A (en) * | 2014-07-10 | 2014-11-05 | 宁波金和新材料股份有限公司 | High-voltage mono-crystal lithium nickel cobalt manganese oxide anode material and preparation method thereof |
| CN105680009A (en) * | 2016-01-18 | 2016-06-15 | 湖南杉杉能源科技股份有限公司 | M-contained multifunctional metal oxide modified high-voltage lithium cobalt oxide positive electrode powder material and preparation method therefor |
| JP2018037372A (en) * | 2016-09-02 | 2018-03-08 | 株式会社豊田自動織機 | Lithium ion secondary battery |
| JP2019185920A (en) * | 2018-04-04 | 2019-10-24 | 株式会社豊田自動織機 | Lithium ion secondary battery |
| CN108767255A (en) * | 2018-05-28 | 2018-11-06 | 格林美（无锡）能源材料有限公司 | A kind of high voltage high capacity type lithium cobaltate cathode material and preparation method thereof |
| CN110649232A (en) * | 2018-06-27 | 2020-01-03 | 株式会社村田制作所 | Positive electrode active material for lithium ion secondary battery |
| CN110350188A (en) * | 2019-07-29 | 2019-10-18 | 昆山宝创新能源科技有限公司 | Anode material of lithium battery and preparation method thereof and lithium battery |
| CN113675383A (en) * | 2021-07-09 | 2021-11-19 | 惠州锂威新能源科技有限公司 | Modified positive electrode material and preparation method thereof, positive plate and lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114256456A (en) | 2022-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114256456B (en) | High-voltage positive electrode material and battery containing same | |
| CN108390022B (en) | Carbon-metal oxide composite coated lithium battery ternary positive electrode material, preparation method thereof and lithium battery | |
| WO2021088168A1 (en) | Lithium supplement material and positive electrode comprising same | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| CN110817972B (en) | Fluorine modified high-voltage lithium cobaltate, preparation method thereof and battery | |
| CN112542589B (en) | Preparation method, product and application of positive electrode prelithiation material | |
| CN112768687A (en) | Lithium-site-doped modified high-nickel low-cobalt ternary cathode material for lithium ion battery and preparation method thereof | |
| WO2016176928A1 (en) | Negative electrode material, preparation method therefor, and lithium-ion secondary battery using the negative electrode material | |
| JPH0922693A (en) | Nonaqueous electrolyte battery, positive active material thereof, and manufacture of positive plate | |
| CN110311121B (en) | Lithium-containing silicon oxide negative electrode material for lithium ion battery and preparation method thereof | |
| CN112928246B (en) | Composite material, preparation method and application thereof | |
| US20220013773A1 (en) | Lithium compound, nickel-based cathode active material, method for preparing lithium oxide, method for preparing nickel-based cathode active material, and secondary battery using same | |
| CN115810743B (en) | Single crystal layered oxide positive electrode material, preparation method and application thereof in sodium ion battery | |
| JP2024533903A (en) | Nano-sized sulfide solid electrolyte material and preparation method thereof | |
| CN113044891A (en) | Preparation method of surface grafting type high-voltage lithium cobaltate, surface grafting type high-voltage lithium cobaltate and application thereof | |
| CN116750810B (en) | Single-crystal type high-nickel ternary positive electrode material for high-voltage lithium ion battery and preparation method thereof | |
| CN115995531A (en) | Positive electrode active material, positive electrode plate, lithium ion battery and application of positive electrode active material and positive electrode plate | |
| CN114824267A (en) | Layered lithium nickel manganese oxide positive electrode material and preparation method and application thereof | |
| TWI651272B (en) | Process for producing lr-lnmo composite materials and use the same | |
| CN116093271A (en) | Positive electrode material, positive electrode plate comprising positive electrode material and battery | |
| CN116014104A (en) | Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery | |
| Guo et al. | A novel SnxSbNi composite as anode materials for Li rechargeable batteries | |
| CN114938686B (en) | Lithium cobalt oxide layered anode material and preparation method and application thereof | |
| CN115650313A (en) | High-voltage high-specific-capacity lithium cobalt oxide cathode material and preparation method thereof | |
| CN115566182A (en) | Positive electrode active material, preparation method thereof, battery and power utilization device |
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 |