CN114256456A - High-voltage positive electrode material and battery containing same - Google Patents
High-voltage positive electrode material and battery containing same Download PDFInfo
- Publication number
- CN114256456A CN114256456A CN202111585946.5A CN202111585946A CN114256456A CN 114256456 A CN114256456 A CN 114256456A CN 202111585946 A CN202111585946 A CN 202111585946A CN 114256456 A CN114256456 A CN 114256456A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- cathode material
- morphology
- lithium
- 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.)
- Granted
Links
- 239000007774 positive electrode material Substances 0.000 title claims description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000010406 cathode material Substances 0.000 claims abstract description 40
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 11
- 229910052726 zirconium 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
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 5
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 99
- 239000013078 crystal Substances 0.000 claims description 36
- 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 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [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
- 239000010405 anode material Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 9
- 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
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 3
- 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 74
- 238000005245 sintering Methods 0.000 description 66
- 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 34
- 229910052808 lithium carbonate Inorganic materials 0.000 description 34
- 238000002156 mixing Methods 0.000 description 28
- 238000007873 sieving Methods 0.000 description 26
- 239000012298 atmosphere Substances 0.000 description 25
- 238000000498 ball milling Methods 0.000 description 21
- 238000005303 weighing Methods 0.000 description 21
- 239000010410 layer Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 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
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000011163 secondary particle Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019580 granularity Nutrition 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
- 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
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012462 polypropylene substrate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 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
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- 229910032387 LiCoO2 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
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 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
- 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
- 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
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 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
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001155 polypropylene 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
- 238000000926 separation method Methods 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
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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 anode material and a battery containing the same, wherein the chemical formula of the anode material is Li1+ xCo1‑y1‑y2‑zMeyMzBnO2Wherein 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 and 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 anode material of the invention adjusts and controls the doping elementThe method has the advantages that the method exerts the advantages of different doping elements through the types of elements, the doping amount of the doping elements and the positions of the doping elements, so that the comprehensive performance of the anode material is greatly improved, wherein the metal element Al, the metal element Me and the element M are doped in the cobalt position of lithium cobaltate and are used for maintaining the structural stability of the anode material and improving the capacity of the anode material; the element B is used for improving the cycle stability and the first coulombic efficiency of the cathode material by surface modification and/or doping in 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 first, the update iteration of the 3C electronic product is more and more frequent and faster. In this update iteration, requirements of higher energy density and better cycle performance are also placed on the battery, which is an important component of the 3C electronic product.
Lithium cobaltate (LiCoO) is used as a positive electrode material for batteries such as lithium manganate, lithium nickelate, lithium nickel cobalt manganate, and lithium iron phosphate2) Having the highest theoretical density value (5.1 g/cm)3) Therefore, the advantages of tap density and compacted density 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 LiCoO2The problems of phase change of the structural surface layer and the internal part and the like are caused by high lithium removal amount, so that the irreversible capacity of the battery is increased and the cycle performance is reduced.
Therefore, it is imperative to develop a cathode material having high specific capacity and excellent cycling performance at high voltage, and capable of alleviating the problems of phase transformation of the surface layer and the interior 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 cycling stability under the working voltage of 3.0-4.55V.
The purpose of the invention is realized by 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):
Li1+xCo1-y1-y2-zAly1Mey2MzBnO2formula (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 and W, Y1 and Y2 are not 0 and satisfy 0< Y1+ Y2 ≤ 0.03; m comprises one or more of elements Si, Ge, Se, Sb, Te and As, and z is more than 0 and less than or equal to 0.01; b is boron element, 0< n < 0.03.
According to the invention, the positive electrode material is a surface-modified doped positive electrode material, namely the positive electrode material is a lithium cobaltate positive electrode material doped with a metal element Al, a metal element Me and an element M modified by an element B.
According to the invention, the metallic element Al, the metallic element Me and the element M replace cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in the crystal lattice of lithium cobaltate.
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) replacing cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in the lithium cobaltate crystal lattice;
3) replacing lithium ions in lithium ion layers at two sides of a framework layer consisting of oxygen ions and cobalt ions in lithium cobaltate crystal lattices;
4) filling the gaps of O-Li and forming a tetrahedral structure with three oxygen ions;
5) filling the gaps of O-Co and forming a tetrahedral structure with three cobalt ions.
According to the invention, the morphology structure of the cathode material comprises at least one of single crystal, quasi-single crystal and polycrystal.
According to the invention, the particle diameter D of the positive electrode material50Is 10-22 μm.
According to the invention, the cathode material is a graded product of a large-particle cathode material with a single crystal morphology and a small-particle cathode material with a single-crystal-like morphology or a polycrystalline morphology.
According to the invention, the mass ratio of the single-crystal positive electrode material to the single-crystal-like or polycrystalline positive electrode material is (2-5): 1.
According to the invention, the particle diameter D of the cathode material with single crystal morphology50Is 10-20 μm.
According to the invention, the particle diameter D of the cathode material with the single-crystal-like morphology or the polycrystalline morphology502-8 μm.
The invention provides a positive plate which comprises the positive electrode material.
The invention provides a battery, which comprises the positive electrode material or the positive electrode sheet.
The invention has the beneficial effects that:
1. the anode material disclosed by the invention has the advantages of different doping elements by regulating and controlling the types of the doping elements, the doping amount of the doping elements and the positions of the doping elements, so that the comprehensive performance of the anode material is greatly improved, wherein metal elements Al and Me and an element M are doped in a cobalt position in lithium cobaltate and are used for maintaining the structural stability of the anode material and improving the capacity of the anode material; the element B is used for improving the cycle stability and the first coulombic efficiency of the cathode material by surface modification and/or doping at different positions in the lithium cobaltate;
2. according to the invention, doping and mixing are carried out by different methods according to the doping amount of the doping element, wherein metal elements Al and Me with large doping amount are doped when cobaltosic oxide is prepared, so that the problems of difficult doping of crystal lattices, uneven doping and the like in the dry sintering process are avoided; the element M with small doping amount can be doped in a form of dry sintering because the element M is easier to be doped in crystal lattices, so that the problem of complex preparation by a wet method is avoided;
3. according to the invention, lithium cobaltate with a large-grain monocrystal morphology and lithium cobaltate with a small-grain monocrystal or polycrystal morphology are prepared by adjusting the size of a precursor and controlling the sintering temperature and time, and the advantages of lithium cobaltates with different morphologies are fully exerted by directionally grading, matching of the size and the grain and secondary sintering, so that the anode material which gives consideration to compaction, capacity, circulation and first coulombic efficiency is prepared;
4. according to the invention, by doping the element B, the characteristics of small ionic radius of B, strong binding energy between B and O and the like are fully exerted, the material can be doped in the phase and surface of lithium cobaltate, the stability of an oxygen skeleton and the surface is stabilized, on one hand, the discharge characteristic of the material can be effectively improved, the first coulombic efficiency is improved, and on the other hand, the cycle performance of the anode material under high voltage is also improved;
5. the preparation method of the anode material provided by the invention is simple in process, strong in operability and easy for large-scale production.
Drawings
FIG. 1 is a cycle retention ratio 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 3.0-4.55V;
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, wherein the chemical formula of the positive electrode material is represented by formula (1):
Li1+xCo1-y1-y2-zAly1Mey2MzBnO2formula (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 and W, Y1 and Y2 are not 0 and satisfy 0< Y1+ Y2 ≤ 0.03; m comprises one or more of elements Si, Ge, Se, Sb, Te and As, and z is more than 0 and less than or equal to 0.01; b is boron element, 0< n < 0.03.
According to an embodiment 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 the embodiment of the 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 present 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 cathode material is a doped cathode material containing surface modification, namely the cathode material is a lithium cobaltate cathode material doped with a metal element Al, a metal element Me and an element M modified by an element B.
According to the invention, by regulating and controlling the types of the doping elements, the doping amount of the doping elements and the doping positions of the doping elements in the anode material, the comprehensive performance of the anode 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 skeleton layer composed of oxygen ions and cobalt ions in the lithium cobaltate crystal 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 (namely a coating layer) on the surface of the lithium cobaltate;
2) replacing cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in the lithium cobaltate crystal lattice;
3) replacing lithium ions in lithium ion layers at two sides of a framework layer consisting of oxygen ions and cobalt ions in lithium cobaltate crystal lattices;
4) filling the gaps of O-Li and forming a tetrahedral structure with three oxygen ions;
5) filling the gaps of O-Co and forming a tetrahedral structure with three cobalt ions.
With respect to the above disclosed positive electrode material, it is noted that the doping elements (Al, Me, M, and B) are all in a lithium cobaltate crystal lattice including a skeleton layer composed of oxygen ions and cobalt ions and lithium ion layers distributed on both sides of the skeleton. Specifically, the metal element Al, the metal element Me, and the element M substitute for cobalt ions in a skeleton layer composed of oxygen ions and cobalt ions in a crystal lattice of lithium cobaltate. The element B forms a modification layer on the surface of the lithium cobaltate; and/or, cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in the lithium cobaltate crystal lattice are replaced; and/or, replacing lithium ions in lithium ion layers at two sides of a framework layer consisting of oxygen ions and cobalt ions in lithium cobaltate crystal lattices; and/or, filling in the gap 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. Wherein, the metal element Al and the metal element Me are used for maintaining the structural stability of the anode material and improving a voltage platform; the element M is used for improving the capacity of the anode material; the element B can be stably doped into the phase and the surface of lithium cobaltate due to the small ionic radius, and the strong binding energy characteristic between the element B and oxygen can stabilize the stability of an oxygen skeleton and the surface, so that the cycle stability and the first charging efficiency of the anode material can be improved.
According to an embodiment of the present invention, the morphology structure of the cathode material includes at least one of single crystal, mono-like and polycrystalline. Preferably, the morphology structure of the cathode material includes single crystal, quasi-single crystal and polycrystal.
The positive electrode material in the single crystal morphology has a large particle size and a small specific surface area, so that the side reaction with the electrolyte is less, and the improvement of the cycle performance of the battery is facilitated; the positive electrode material with the single-crystal-like morphology or the polycrystalline morphology is secondary particles composed of primary particles, and the primary particles are small in particle size, so that the positive electrode material has high first coulombic efficiency and rate capability, but side reactions with electrolyte are increased due to large specific surface area, and in addition, the secondary particles composed of small particles are easy to crack, so that the cycle performance is reduced. The invention exerts the advantages of single crystal and polycrystal through the matching of the sizes and the granularities.
According to an embodiment of the present invention, polycrystalline morphology refers to the morphology of spheroidal secondary particle particles formed by agglomeration of a plurality of primary particles; the single crystal morphology refers to the morphology of a particle composed of a single primary particle; the single crystal-like morphology refers to the morphology of secondary particle particles formed by agglomeration of a small number of primary particles.
According to an embodiment of the present invention, the particle diameter D of the positive electrode material50From 10 μm to 22 μm, preferably from 13 μm to 19 μm, such as 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm or 19 μm.
Preferably, the cathode material is obtained by grading a large-particle cathode material with a single-crystal morphology and a small-particle cathode material with a single-crystal-like morphology or a polycrystalline morphology.
Preferably, the mass ratio of the single-crystal-morphology cathode material to the single-crystal-like-morphology or polycrystalline-morphology cathode material is (2-5: 1), for example, 2:1, 3:1, 4:1 or 5:1.
Preferably, the particle size D of the cathode material with single crystal morphology50The grain diameter D of the anode material with the single crystal-like morphology or the polycrystalline morphology is 10-20 mu m502-8 μm.
[ preparation of cathode Material ]
The invention also provides a preparation method of the cathode material, which comprises the following steps:
1) selecting metal element Al and metal element Me which are doped, and the particle diameter D50Mixing cobaltosic oxide with the particle diameter of 10-20 mu M with a lithium source and a compound containing an element M, sintering, crushing, sieving and grading to obtain the particle diameter D of the single crystal morphology50Lithium cobaltate A1 with the particle size of 10-20 mu m;
2) selecting metal element Al and metal element Me which are doped, and the particle diameter D50Cobaltosic oxide with the particle size of 2-8 mu M, a lithium source and a compound containing an element M are mixed, sintered, crushed, sieved and classified to obtain the single crystal-like and polycrystalline shapesParticle diameter D502-8 μm lithium cobaltate A2;
3) and mixing the lithium cobaltate A1 and the lithium cobaltate A2, adding a compound containing the B element, mixing, sintering, crushing, sieving and grading to obtain the cathode material.
According to an embodiment of the invention, the metal elements Me In step 1) and step 2) comprise one or more of In, Y, Mg, Sr, Ti, Zr, Ni, Mn, W.
According to the embodiment of the present invention, in the cobaltosic oxide doped with the metal element Al and the metal element Me in the step 1) and the step 2), the doping amounts of the metal element Al and the metal element Me are 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 (namely, the doping amount of each metal element Me is 500ppm to 2000 ppm).
According to an embodiment of the present invention, in step 1) and step 2), the element M comprises one or more of Si, Ge, Se, Sb, Te, As.
Wherein, in step 1) and step 2), lithium cobaltate with different morphologies can be obtained by controlling the sintering temperature and the sintering time: when the sintering temperature is more than 1040 ℃ and the sintering time is more than 12 hours, the lithium cobaltate with the 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 8h, the lithium cobaltate with the single crystal-like morphology and the polycrystalline morphology can be obtained, and the particle size is smaller.
Illustratively, the sintering temperature in the step 1) is 1000-1100 ℃ and the sintering time is 12-24 h, more preferably, the sintering temperature is 1040-1085 ℃ and the sintering time is 12-16 h.
Illustratively, the sintering temperature in the step 2) is 900-1040 ℃, and the sintering time is 6-12 h, more preferably, the sintering temperature is 930-1000 ℃, and the sintering time is 8-10 h.
Wherein the sintering atmosphere is air atmosphere or oxygen atmosphere, and the sintered product is naturally cooled to room temperature;
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) to 1 (0-0.01), more preferably, the molar ratio of Li to Co to M is (1.02-1.05) to 1 (0-0.01), and the mole number of M is not 0.
In the step 1) and the step 2), for mixing, it is noted that mixing can be performed by a high-speed mixer and ball milling, and the mixing time is 0.5h to 4h, more preferably 0.5h to 2 h.
In the step 1) and the step 2), it is required to be stated that crushing, sieving and grading are performed by firstly performing primary crushing on a roller machine, then sieving the crushed material with a 300-mesh screen, and then performing particle size grading on the crushed material with a jet flow classifier to obtain the material with the target particle size range.
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.
In the step 3), the amount of the compound containing the B element is 0.1 to 5 wt%, more preferably 0.1 to 3 wt%, based on the total weight of the lithium cobaltate a1 and the lithium cobaltate a 2.
Wherein, in the step 3), the compound containing the B element is at least one selected from 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 is50The cobaltosic oxide with the particle size of 10-20 mu m 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 an 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 a complex precipitation reaction; in the reaction process, the stirring speed is controlled within the range of 140 rpm-850 rpm, the pH is controlled within the range of 6.5-8.5, and the temperature is controlled within the range of 25-80 ℃; after the feeding is finished, stopping stirring, standing for solid-liquid separation, pumping away supernatant liquid, and continuously feeding to enable crystals to continuously grow;
(3) repeating the cyclic process of feeding, standing for solid-liquid layering, extracting supernatant and continuing feeding for 6-12 times, and controlling the grain size of the crystal to grow to D50Finishing feeding when the particle size is 10-20 mu m;
(4) washing, drying and calcining the slurry after the reaction to obtain the particle size D of the doped metal element Al and the metal element Me50Cobaltosic oxide with the particle size of 10-20 mu m.
Wherein, in the step 2), the metal element Al and the metal element Me are doped, and the particle diameter D is50The cobaltosic oxide with the particle size of 2-8 mu m can be prepared by a method comprising the following steps:
(1') mixing a soluble cobalt source, a soluble compound containing an Al element and a soluble compound containing an 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 value in the reaction kettle to be 8.0-8.5, controlling the temperature to be 70-75 ℃ and controlling the reaction time to be 22-24 hours in the reaction process;
(2') after the reaction is finished, washing, drying and calcining are carried out once to obtain the metal element Al and the metal element Me doped with the particle size D50Cobaltosic oxide with the particle size of 2-8 mu m.
For the cobaltosic oxide doped with the sizes and the granularities of the metal element Al and the metal element Me, it needs to be further explained 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 the Al element is at least one of sulfate, nitrate, oxalate, acetate, fluoride, chloride, oxide and hydroxide containing the Al element; the soluble compound containing Me element is at least one of sulfate, nitrate, oxalate, acetate, fluoride, chloride, oxide and hydroxide containing 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 by 10 times with ammonia water with the concentration of 20-25%; the precipitant is water-soluble alkali, carbonate or oxalate with concentration of 0.4-3.6 mol/L, and may be at least one of sodium carbonate, sodium bicarbonate and ammonia carbonate with concentration of 0.4-3.6 mol/L.
Wherein, the grain diameter D of the doped metal element Al and the doped metal element Me50The calcination condition of cobaltosic oxide with the particle size of 10-20 mu m is divided into two sections: the first stage is preheating decomposition at 250-450 deg.c for 2-6 hr; the second stage is high temperature pyrolysis at 550-850 deg.c for 2-6 hr.
Wherein, metal element Al and metal element Me are doped and the grain diameter D is50The calcining temperature of cobaltosic oxide with the particle size of 2-8 mu m is 800-900 ℃, and the time is 1-3 h.
[ Positive electrode sheet and Battery ]
The invention also provides a positive plate which comprises the positive electrode 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 a positive electrode material, 1-10 wt% of a conductive agent and 1-10 wt% of a 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 a negative electrode material, 1-15 wt% of a conductive agent and 1-15 wt% of a binder.
Preferably, the negative electrode sheet comprises the following components in percentage by mass: 80-98 wt% of a negative electrode material, 1-10 wt% of a conductive agent and 1-10 wt% of a 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, mesocarbon microbeads 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 nanotube, and carbon fiber.
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, which may be at least one of cyclic carbonate, linear carbonate, and linear hydroxy acid ester, and a conductive lithium salt; the conductive lithium salt may be at least one of lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide and lithium bis (trifluoromethanesulfonyl) imide.
In specific implementation, the organic solvent may include 20 to 40 vol% of cyclic carbonate and 60 to 80 vol% of linear carbonate and/or linear carboxylate (based on the total volume of 100 vol%).
According to an embodiment of the present invention, the membrane may be a polypropylene substrate membrane, for example, a rubberized polypropylene membrane coated on one or both sides with a ceramic on a polypropylene substrate.
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) Taking lithium carbonate and particle diameter D containing Al and Mg doping50Weighing lithium carbonate, cobaltosic oxide and telluric acid respectively according to the Li/Co molar ratio of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Mg element of 1000ppm, the doping element M of Te and the doping amount of 2000ppm, ball-milling and mixing for 1h, placing in a muffle furnace in an air atmosphere for sintering at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D50Is 18 mu m of Al, Mg and Te co-doped lithium cobaltate;
(2) taking lithium carbonate and particle diameter D containing Al and Mg doping50Respectively weighing lithium carbonate, cobaltosic oxide and telluric acid according to the molar ratio of Li to Co of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Mg element of 1000ppm, the doping element M of Te and the doping amount of 2000ppm, 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 the particle size D50Is Al, Mg and Te co-doped lithium cobaltate with the particle size of 4.5 mu m;
(3) the particle diameter D is50Weighing 18 mu m and 4.5 mu m Al, Mg and Te co-doped lithium cobaltate powder according to the mass ratio of 4:1, adding 2000ppm boric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D50The SEM image of the product of 16.8 μm, namely the B element modified Al, Mg and Te co-doped high voltage lithium cobaltate, is shown in FIG. 1.
(4) Dispersing the Al, Mg and Te co-doped high-voltage lithium cobaltate positive electrode material modified by the B element, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) in a N-methylpyrrolidone (NMP) solvent according to a mass ratio of 97:1.5:1.5, uniformly stirring in a defoaming machine to obtain positive electrode slurry, uniformly coating the positive electrode slurry on the surface of an aluminum foil, baking in a vacuum oven at 120 ℃ for 12 hours, rolling and cutting to obtain a positive electrode sheet.
The positive plate and the negative plate of the lithium plate are provided with a PP/PE/PP three-layer diaphragm, and 1mol/L LiPF is used6And (EC + DEC) electrolyte (volume ratio is 1:1), and assembling the button cell. Performing electrochemical test at normal temperature (25 ℃), wherein the charge-discharge voltage of the first circle 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 at normal temperature (25 ℃) of the battery made of the positive electrode material obtained in example 1 is shown in fig. 2.
Example 2
(1) Taking lithium carbonate and Al and Ni doped particle size D50Weighing lithium carbonate, cobaltosic oxide and telluric acid respectively according to the Li/Co molar ratio of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Ni element of 1500ppm, the doping element M of Te and the doping amount of 2000ppm, ball-milling and mixing for 1h, placing in a muffle furnace in an air atmosphere for sintering at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D50Lithium cobalt oxide co-doped with Al, Ni and Te of 20 μm;
(2) taking lithium carbonate and Al and Ni doped particle size D50Respectively weighing lithium carbonate, cobaltosic oxide and telluric acid according to the molar ratio of Li to Co of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Ni element of 1500ppm, the doping amount of doping element M of Te of 2000ppm, 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 the particle size D50Is 6 μm of Al, Ni and Te co-doped lithium cobaltate;
(3) the particle diameter D is50Weighing Al, Ni and Te co-doped lithium cobaltate powder with the particle size of 20 mu m and 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 the sintering temperatureSintering at 950 deg.C for 12h, crushing, sieving and grading to obtain particle diameter D50The product is 18.6 mu m, namely Al, Ni and Te co-doped high-voltage lithium cobaltate modified by B element.
The cycle curve at normal temperature (25 ℃) of the battery made of the positive electrode material obtained in example 2 is shown in fig. 2.
(4) The same as in example 1.
Example 3
(1) Taking lithium carbonate and grain diameter D containing Al and Zr doping50Weighing lithium carbonate, cobaltosic oxide and telluric acid respectively according to the Li/Co molar ratio of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Zr element of 1500ppm, the doping amount of doping element M of Te of 2000ppm and the Li/Co molar ratio of 1.05:1, placing the mixture in a muffle furnace in an air atmosphere for sintering at 1080 ℃ for 14h, naturally cooling the mixture after sintering, crushing, sieving and grading the mixture to obtain the particle size D5018 μm of lithium cobalt oxide co-doped with Al, Zr and Te;
(2) taking lithium carbonate and grain diameter D containing Al and Zr doping50Respectively weighing lithium carbonate, cobaltosic oxide and telluric acid according to the molar ratio of Li to Co of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Zr element of 1500ppm, the doping amount of doping element M of Te of 2000ppm, ball-milling and mixing the lithium carbonate, the cobaltosic oxide and the telluric acid for 1h, sintering the mixture in a muffle furnace in air atmosphere at the sintering temperature of 980 ℃ for 10h, naturally cooling the mixture after sintering, crushing, sieving and grading the mixture to obtain the particle size D50Al, Zr and Te co-doped lithium cobaltate with the particle size of 4.5 mu m;
(3) the particle diameter D is50Weighing 18 mu m and 4.5 mu m Al, Zr and Te co-doped lithium cobaltate powder according to the mass ratio of 4:1, adding 2000ppm boric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D50The product is 16.5 mu m, namely the Al, Zr and Te co-doped high-voltage lithium cobaltate modified by the B element.
(4) The same as in example 1.
Example 4
(1) Taking lithium carbonate and particle diameter D containing Al and W doping50Respectively weighing lithium carbonate, cobaltosic oxide and telluric acid according to the Li/Co molar ratio of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of W element of 1000ppm, the doping amount of doping element M of Te of 2000ppm, ball-milling and mixing the lithium carbonate, the cobaltosic oxide and the telluric acid for 1h, sintering the mixture in a muffle furnace in an air atmosphere at the sintering temperature of 1080 ℃ for 14h, naturally cooling the sintered mixture, crushing, sieving and grading the sintered mixture to obtain the particle size D5018 μm of Al, W and Te co-doped lithium cobaltate;
(2) taking lithium carbonate and particle diameter D containing Al and W doping50Respectively weighing lithium carbonate, cobaltosic oxide and telluric acid according to the molar ratio of Li to Co of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of W element of 1000ppm, the doping amount of doping element M of Te of 2000ppm, ball-milling and mixing the lithium carbonate, the cobaltosic oxide and the telluric acid for 1h, sintering the mixture in a muffle furnace in air atmosphere at the sintering temperature of 980 ℃ for 10h, naturally cooling the sintered mixture, crushing, sieving and grading the sintered mixture to obtain the particle size D50Is 4 μm of Al, W and Te co-doped lithium cobaltate;
(3) the particle diameter D is50Weighing 18 mu m and 4 mu m Al, W and Te co-doped lithium cobaltate powder according to the mass ratio of 5:1, adding 2000ppm boric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D50The product is 15.6 mu m, namely the Al, W and Te co-doped high-voltage lithium cobaltate modified by the B element.
(4) The same as in example 1.
Example 5
(1) Taking lithium carbonate and particle diameter D containing Al and Y doping50Cobaltosic oxide with the thickness of 18-20 mu m, wherein the doping amount of Al element is 7000ppm, the doping amount of Y element is 2000ppm, and the ratio of Li/Co is 1.05:1, doping element M into Te with the doping amount of 2000ppm, respectively weighing lithium carbonate, cobaltosic oxide and telluric acid, ball-milling and mixing for 1h, and placing in the airSintering in a muffle furnace in an atmosphere at 1080 ℃ for 14h, naturally cooling after sintering, and crushing, sieving and grading to obtain the particle size D5022 μm of lithium cobalt oxide co-doped with Al, Y and Te;
(2) taking lithium carbonate and particle diameter D containing Al and Y doping50Tricobalt tetraoxide with 4-6 μm, wherein the doping amount of Al element is 7000ppm, the doping amount of Y element is 2000ppm, and the ratio of Li/Co is 1.05:1, doping element M into Te, wherein the doping amount is 2000ppm, respectively weighing lithium carbonate, cobaltosic oxide and telluric acid, ball-milling and mixing the lithium carbonate, the cobaltosic oxide and the telluric acid for 1h, placing the mixture into a muffle furnace in an air atmosphere for sintering at 980 ℃ for 10h, naturally cooling the mixture after sintering, and crushing, sieving and grading the mixture to obtain particle size D50Lithium cobalt oxide co-doped with Al, Y and Te of 8 μm;
(3) the particle diameter D is50Weighing 22-micron and 8-micron Al, Y and Te co-doped lithium cobaltate powder 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 the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D50The product is 20 mu m, namely Al, Y and Te co-doped high-voltage lithium cobaltate modified by B element.
(4) The same as in example 1.
Example 6
(1) The same as example 2;
(2) the same as example 2;
(3) the particle diameter D is50Weighing 18 mu m and 6 mu m Al, Ni and Te co-doped lithium cobaltate powder according to the mass ratio of 1:1, adding 2000ppm boric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle diameter D50The product is 18.6 mu m, namely Al, Ni and Te co-doped high-voltage lithium cobaltate modified by B element.
The cycle curve at normal temperature (25 ℃) of the battery made of the positive electrode material obtained in example 6 is shown in fig. 2.
The capacity and cycling performance of example 6 was inferior to that of the battery of comparative example 1, compared to example 2, indicating that a reasonable size particle size match can improve the specific capacity and cycling performance of the high voltage lithium cobaltate.
Comparative example 1
(1) Taking lithium carbonate and particle diameter D containing Al and Mg doping50Weighing lithium carbonate, cobaltosic oxide and telluric acid respectively according to the Li/Co molar ratio of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Mg element of 1000ppm, the doping element M of Te and the doping amount of 2000ppm, ball-milling and mixing for 1h, placing in a muffle furnace in an air atmosphere for sintering at 1080 ℃ for 14h, naturally cooling after sintering, crushing, sieving and grading to obtain the particle size D5018 μm of lithium cobalt oxide co-doped with Al, Mg and Te;
(2) taking lithium carbonate and particle diameter D containing Al and Mg doping50Respectively weighing lithium carbonate, cobaltosic oxide and telluric acid according to the molar ratio of Li to Co of 1.05:1, the doping amount of Al element of 7000ppm and the doping amount of Mg element of 1000ppm, the doping element M of Te and the doping amount of 2000ppm, 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 the particle size D50Lithium cobalt oxide co-doped with Al, Mg and Te of 4.5 μm;
(3) the particle diameter D is50Weighing 18 mu m and 4.5 mu m Al, Mg and Te co-doped lithium cobaltate powder according to the mass ratio of 4:1, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle size D50The product was 16.8 μm, i.e., Al, Mg, Te co-doped high voltage lithium cobaltate.
(4) The same as in example 1.
The cycle curve at normal temperature (25 ℃) of the battery made of the positive electrode material obtained in comparative example 1 is shown in fig. 2.
As can be seen from fig. 2, comparative example 1 exhibited less excellent capacity, first coulombic efficiency and cycle performance than example 1, because the B element as a modifier can significantly improve the electrochemical performance of the high voltage lithium cobaltate.
Comparative example 2
The other operations are the same as example 1, except that: particle size D doped with Al50Cobaltosic oxide with the grain diameter D of 14-16 mu m (wherein the doping amount of Al element is 7000ppm) is substituted for the grain diameter D containing Al and Mg doping in the embodiment 150Cobaltosic oxide with the particle size of 14-16 mu m; and particle diameter D doped with Al50Cobaltosic oxide (wherein the doping amount of Al element is 7000ppm) with 2-4 μm is substituted for the particle diameter D containing Al and Mg doping in example 150Cobaltosic oxide with the particle size of 2-4 mu m.
Comparative example 3
The other operations are the same as example 1, except that: by particle diameter D50The particle diameter D of doped cobaltosic oxide containing Al and Mg in the alternative embodiment 1 is 14-16 mu m50Cobaltosic oxide with the particle size of 14-16 mu m; and by the particle diameter D50The particle diameter D of doped cobaltosic oxide containing Al and Mg in the embodiment 1 is replaced by cobaltosic oxide with the particle diameter of 2-4 mu m50Cobaltosic oxide with the particle size of 2-4 mu m.
Comparative example 4
(1) Taking lithium carbonate and particle diameter D containing Al and Mg doping50The preparation method comprises the steps of weighing lithium carbonate and cobaltosic oxide according to the Li/Co molar ratio of 1.05:1, ball-milling and mixing the lithium carbonate and the cobaltosic oxide for 1h, sintering the mixture in a muffle furnace in an air atmosphere at the sintering temperature of 1080 ℃ for 14h, naturally cooling the sintered product, crushing, sieving and grading to obtain the particle size D5018 μm of lithium cobalt oxide co-doped with Al and Mg;
(2) taking lithium carbonate and particle diameter D containing Al and Mg doping50The doping amount of Al element is 7000ppm, the doping amount of Mg element is 1000ppm, lithium carbonate and cobaltosic oxide are respectively weighed according to the Li/Co molar ratio of 1.05:1, and are sintered in a muffle furnace in air atmosphere after being ball-milled and mixed for 1h, the sintering temperature is 980 ℃, and the sintering temperature is highSetting time is 10h, sintering, naturally cooling, crushing, sieving and grading to obtain particle diameter D504.5 μm of lithium cobalt oxide co-doped with Al and Mg;
(3) the particle diameter D is50Weighing 18 mu m and 4.5 mu m Al-Mg co-doped lithium cobaltate powder according to the mass ratio of 4:1, adding 2000ppm boric acid, ball-milling and mixing for 1h, sintering in a muffle furnace in air atmosphere at the sintering temperature of 950 ℃ for 12h, crushing, sieving and grading to obtain the particle diameter D50The product is 16.8 mu m, namely Al and Mg co-doped high-voltage lithium cobaltate modified by B element.
And (3) performance testing:
charging to 4.5V at 0.1C, cutting off current to 0.025C to obtain the first charge capacity of the positive active material, standing for 15min, and discharging to 3V at constant current at 0.1C to obtain the first discharge capacity of the positive active material; dividing the first charge capacity by the mass of the positive active material to obtain the first charge specific capacity of the positive active material, and dividing the first discharge capacity by the mass of the positive active material to obtain the first discharge specific capacity of the positive active material; and (3) dividing the first discharge specific capacity of the positive electrode material by the first charge specific capacity of the positive electrode material to obtain the first coulombic efficiency of the positive electrode active material.
At normal temperature (25 ℃), the battery was charged to 4.55V at 0.5C, the current was cut off at 0.05C, left for 15min, and then discharged to 3V at a constant current of 0.5C, and the initial capacity Q0 was recorded, and the capacity after each cycle was recorded, and the previous discharge capacity was taken as the capacity Q2 of the battery, and the capacity retention (%) was calculated (where the following calculation formula was used: cycle capacity retention ═ Q2/Q0 × 100%).
Table 1 results of performance test of batteries of examples and comparative examples
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 using the embodiment of the present invention exhibited excellent performance in specific capacity, first coulombic efficiency and battery cycle performance, while the performance of the comparative example was inferior to the electrochemical performance of the examples. The positive electrode material is modified by the B element and co-doped with different elements, so that the surface layer and internal phase change of lithium cobaltate in a high-delithiation state is relieved, the structure of the positive electrode material is stabilized, the specific capacity and the cycle performance of the positive electrode material are improved, and the overall reaction kinetics and the electrochemical performance of the positive electrode material are improved by matching the large particles and the small particles.
In particular, comparative example 2 is doped with Al element, Te element, and B element, and the doping of Al element can improve the stability of the positive electrode material, but the higher the doping amount is, the lower the capacity is; comparative example 3 does not dope Al and the metal element Me, resulting in deterioration of the overall performance of the positive electrode material, particularly, significant deterioration of the battery performance at high voltage; the absence of doping element M in comparative example 4 also results in a deterioration of the overall electrochemical performance of the cell.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present 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, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A positive electrode material is characterized in that the chemical formula of the positive electrode material is shown as formula (1):
Li1+xCo1-y1-y2-zAly1Mey2MzBnO2formula (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 and W, Y1 and Y2 are not 0 and satisfy 0< Y1+ Y2 ≤ 0.03; m comprises one or more of elements Si, Ge, Se, Sb, Te and As, and z is more than 0 and less than or equal to 0.01; 0< n < 0.03.
2. The cathode material according to claim 1, wherein the cathode material is a doped cathode material with surface modification, that is, the cathode material is a lithium cobaltate cathode material doped with a metal element Al, a metal element Me and an element M modified by 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 substitute cobalt ions in a skeleton layer composed of oxygen ions and cobalt ions in a lithium cobaltate crystal 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) replacing cobalt ions in a framework layer consisting of oxygen ions and cobalt ions in the lithium cobaltate crystal lattice;
3) replacing lithium ions in lithium ion layers at two sides of a framework layer consisting of oxygen ions and cobalt ions in lithium cobaltate crystal lattices;
4) filling the gaps of O-Li and forming a tetrahedral structure with three oxygen ions;
5) filling the gaps of O-Co and forming a tetrahedral structure with three cobalt ions.
5. The cathode material according to any one of claims 1 to 4, wherein the morphology structure of the cathode material comprises at least one of single crystal, mono-like and polycrystalline.
6. The positive electrode material according to any one of claims 1 to 4, wherein the particle diameter D of the positive electrode material50Is 10-22 μm.
7. The cathode material according to any one of claims 1 to 4, wherein the cathode material is a large-grained single-crystal morphology cathode material and a small-grained single-crystal-like morphology or a polycrystalline morphology cathode material graded.
8. The cathode material according to claim 7, wherein the mass ratio of the cathode material with the single crystal morphology to the cathode material with the single-crystal-like morphology or the polycrystalline morphology is (2-5): 1;
and/or the particle size D of the cathode material with the single crystal morphology5010-20 μm;
and/or the particle size D of the cathode material with the single-crystal-like morphology or the polycrystalline morphology502-8 μm.
9. A positive electrode sheet, characterized in that it comprises the positive electrode material according to any one of claims 1 to 8.
10. A battery comprising the positive electrode material according to any one of claims 1 to 8, or comprising the positive electrode sheet according to claim 9.
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 true CN114256456A (en) | 2022-03-29 |
| CN114256456B 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116092615A (en) * | 2023-04-06 | 2023-05-09 | 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 |
| CN117239111A (en) * | 2023-11-13 | 2023-12-15 | 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 |
| CN117276532A (en) * | 2023-11-21 | 2023-12-22 | 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 (11)
| 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 |
| US20210057745A1 (en) * | 2019-08-21 | 2021-02-25 | Apple Inc. | Aluminum-doped lithium cobalt manganese oxide batteries |
| 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 |
-
2021
- 2021-12-20 CN CN202111585946.5A patent/CN114256456B/en active Active
Patent Citations (11)
| 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 |
| US20210057745A1 (en) * | 2019-08-21 | 2021-02-25 | Apple Inc. | Aluminum-doped lithium cobalt manganese oxide batteries |
| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116092615A (en) * | 2023-04-06 | 2023-05-09 | 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 |
| 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 |
| CN117239111A (en) * | 2023-11-13 | 2023-12-15 | 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 |
| 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 |
| CN117276532A (en) * | 2023-11-21 | 2023-12-22 | 宜宾锂宝新材料有限公司 | High-tap-density positive electrode material, preparation method thereof and lithium battery |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114256456B (en) | 2024-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114256456B (en) | High-voltage positive electrode material and battery containing same | |
| CN110233250B (en) | Preparation method of single crystal particle ternary cathode material | |
| JP3362564B2 (en) | Non-aqueous electrolyte secondary battery, and its positive electrode active material and method for producing positive electrode plate | |
| CN109516509B (en) | High-compaction single crystal ternary positive electrode material and preparation method and application thereof | |
| CN110817972B (en) | Fluorine modified high-voltage lithium cobaltate, preparation method thereof and battery | |
| CN103137960B (en) | Anode material for lithium-ion batteries and preparation method thereof and lithium ion battery | |
| Lou et al. | Mg-doped Li1. 2Mn0. 54Ni0. 13Co0. 13O2 nano flakes with improved electrochemical performance for lithium-ion battery application | |
| CN112018372A (en) | Single-crystal ternary cathode material, preparation method thereof and lithium ion battery | |
| CN103825015A (en) | Preparation method of high compaction density lithium nickel cobalt manganese oxide NCM523 ternary material | |
| CN115995531A (en) | Positive electrode active material, positive electrode plate, lithium ion battery and application of positive electrode active material and positive electrode plate | |
| CN115010108A (en) | Preparation method of high-compaction lithium iron manganese phosphate cathode material for lithium ion battery | |
| CN111204813B (en) | Preparation method of vanadium-doped lithium-rich manganese-based positive electrode material | |
| CN112701276A (en) | Quaternary polycrystalline positive electrode material and preparation method and application thereof | |
| CN111916730A (en) | Preparation method of WO3 modified nickel-rich ternary lithium ion battery positive electrode material | |
| CN116093271A (en) | Positive electrode material, positive electrode plate comprising positive electrode material and battery | |
| CN115084508A (en) | Positive active material, battery and preparation method thereof | |
| CN114368790A (en) | Preparation method of magnesium-aluminum-vanadium co-doped lithium cobaltate cathode material | |
| CN115566182A (en) | Positive electrode active material, preparation method thereof, battery and power utilization device | |
| CN105742617B (en) | A kind of preparation method of anode material for lithium-ion batteries copper acid lithium | |
| CN115995548A (en) | Lithium cobalt oxide positive electrode material and preparation method thereof | |
| CN113161526A (en) | Positive electrode material and preparation method and application thereof | |
| CN117280499A (en) | Lithium cobalt oxide positive electrode material, preparation method and application thereof | |
| CN117239114A (en) | Positive electrode active material, positive electrode plate and lithium ion battery | |
| Wu et al. | Improving Structure and Electrochemical Performance of Single-Crystal Ni-Rich Cathodes by Aluminium Doping | |
| Liu et al. | Effect of Heat Treatment Time on Electrochemical Performance of LiMg0. 04Mn1. 96O4 cathode Materials Synthesized by a Solid-State Combustion Method |
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 |