CN114566633A - Novel cobalt-free cathode material and preparation method thereof - Google Patents
Novel cobalt-free cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN114566633A CN114566633A CN202210212960.9A CN202210212960A CN114566633A CN 114566633 A CN114566633 A CN 114566633A CN 202210212960 A CN202210212960 A CN 202210212960A CN 114566633 A CN114566633 A CN 114566633A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- positive electrode
- ltoreq
- free
- equal
- 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.)
- Pending
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 15
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000012298 atmosphere Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 25
- 238000000498 ball milling Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000004277 Ferrous carbonate Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 3
- 229960004652 ferrous carbonate Drugs 0.000 claims description 3
- 235000019268 ferrous carbonate Nutrition 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 229940032296 ferric chloride Drugs 0.000 claims description 2
- 229960001781 ferrous sulfate Drugs 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 43
- 238000005245 sintering Methods 0.000 description 24
- 239000011230 binding agent Substances 0.000 description 20
- 239000006258 conductive agent Substances 0.000 description 20
- 239000002904 solvent Substances 0.000 description 18
- 239000011812 mixed powder Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- 238000011056 performance test Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 229910003002 lithium salt Inorganic materials 0.000 description 13
- 159000000002 lithium salts Chemical class 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 11
- 239000002033 PVDF binder Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 239000010937 tungsten Substances 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 229910001290 LiPF6 Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052810 boron oxide Inorganic materials 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- -1 ferrous compound Chemical class 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000012856 weighed raw material Substances 0.000 description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 230000035807 sensation Effects 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000005678 chain carbonates Chemical class 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 238000011534 incubation Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003660 carbonate based solvent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a novel cobalt-free anode material and a preparation method thereof, wherein the chemical formula of the cobalt-free anode material is LimNixFeyAlzM(1‑x‑y‑z)O2·nB2O3Wherein M is one or more elements selected from W, Ta, Ti, Si, Mg, Ca, Sr, Ba, Ra, Sc, Y, Zr, Nb, Hf, Cr and Mo, M is more than or equal to 0.95 and less than or equal to 2, x is more than or equal to 0.05 and less than or equal to 0.9, Y is more than or equal to 0.05 and less than or equal to 0.9, z is more than or equal to 0.02 and less than or equal to 0.3, and n is more than or equal to 0 and less than or equal to 0.005. The cobalt-free cathode material has the advantages of low raw material cost, simple preparation process, good repeatability, easy mass production and para-ringEnvironment-friendly and the like, and the voltage of the discharge platform is higher than that of the lithium iron phosphate anode material.
Description
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a novel cobalt-free anode material and a preparation method thereof.
Background
With the gradual rise of the new energy vehicle market, the power lithium ion battery becomes a strong growth point in the battery industry, and the trend of releasing the product demand is formed. In the research and development and application of lithium batteries, the positive electrode material is required to have the characteristics of high potential, high specific capacity, high density and the like, and can keep longer service life and better use density.
One key raw material of ternary lithium ion batteries which are currently used on a large scale in the field of passenger vehicles is metallic cobalt. However, the reserves of the global cobalt mineral are limited, the average mass content of cobalt in the crusta is only 0.001%, and the reserves of the global cobalt are mainly distributed in australia and african congo with unstable situation all the year round, and the reserves of the cobalt resource of the two countries account for about 62.86% of the total reserves of the world cobalt. Therefore, the low-cost cobalt-free cathode material becomes one of the mainstream trends of the development of the lithium battery industry in the future.
Disclosure of Invention
The invention discloses a cobalt-free anode material and a preparation method thereof. The cathode material provided by the invention has the advantages of low raw material cost, simple preparation process, good repeatability, easiness in mass production, relative environmental friendliness and the like, and the discharge platform voltage is higher than that of a lithium iron phosphate cathode material.
Specifically, the invention provides a cobalt-free cathode material, wherein the chemical formula of the cobalt-free cathode material is LimNixFeyAlzM(1-x-y-z)O2·nB2O3Wherein M is one or more elements selected from W, Ta, Ti, Si, Mg, Ca, Sr, Ba, Ra, Sc, Y, Zr, Nb, Hf, Cr and Mo, M is more than or equal to 0.95 and less than or equal to 2, x is more than or equal to 0.05 and less than or equal to 0.9, Y is more than or equal to 0.05 and less than or equal to 0.9, z is more than or equal to 0.02 and less than or equal to 0.3, and n is more than or equal to 0 and less than or equal to 0.005.
In one or more embodiments, the M is one or more elements selected from W, Ta, Ti, Mg, Sr, Ba, Y, Zr, Hf, Cr, and Mo.
In one or more embodiments, the mass content of M in the cobalt-free cathode material is 500ppm to 100000ppm, preferably 1000-.
In one or more embodiments, the M comprises one or two selected from the group consisting of a W element and a Ti element.
In one or more embodiments, the M comprises a W element; preferably, the content of the element W in the cobalt-free cathode material is 0.1 to 2 wt%, preferably 0.2 to 1 wt%, more preferably 0.25 to 0.5 wt%.
In one or more embodiments, the M comprises Ti element; preferably, the content of the W element in the cobalt-free cathode material is 0.1-2 wt%, preferably 0.2-1 wt%.
In one or more embodiments, the mass content of the B element in the cobalt-free cathode material is 500-2000 ppm.
In one or more embodiments, the cobalt-free cathode material has one or more of the following characteristics:
1. ltoreq. m.ltoreq.1.5, preferably 1.05. ltoreq. m.ltoreq.1.2;
0.5. ltoreq. x.ltoreq.0.8, preferably 0.6. ltoreq. x.ltoreq.0.7;
0.1. ltoreq. y.ltoreq.0.5, preferably 0.1. ltoreq. y.ltoreq.0.2;
0.05. ltoreq. z.ltoreq.0.2, preferably 0.1. ltoreq. z.ltoreq.0.2.
In one or more embodiments, the cobalt-free positive electrode material is formed by stacking micron-sized single-crystal-like particles, wherein the micron-sized single-crystal-like particles are formed by agglomerating nano-sized spherical-like particles; preferably, the particle size of the nanoscale spheroidal particles is 200-600 nm; preferably, the micron-sized mono-like particles have a particle size of 1 to 10 μm.
In one or more embodiments, the cobalt-free cathode material has a D50 particle size ranging from 1 to 3 μm.
In one or more embodiments, the cobalt-free cathode material has a powder tap density of 1-2 g/cc.
The present invention also provides a method of making a cobalt-free cathode material according to any embodiment herein, the method comprising the steps of:
(1) uniformly mixing a lithium source, a nickel source, an iron source, an aluminum source, a carbon source and an M source;
(2) performing heat preservation treatment on the mixed material obtained in the step (1) at the temperature of 750-;
optionally, the method further comprises:
(3) and (3) uniformly mixing the cobalt-free anode material obtained in the step (2) with a boron source, and then carrying out heat preservation treatment in an inert gas atmosphere at the temperature of 250-350 ℃ to obtain the boron-element-containing cobalt-free anode material.
In one or more embodiments, the lithium source is selected from one or both of lithium carbonate and lithium hydroxide.
In one or more embodiments, the nickel source is selected from one or more of nickel hydroxide, nickel carbonate, and nickel sulfate, preferably spherical nickel hydroxide.
In one or more embodiments, the iron source is selected from one or more of ferrous acetate dihydrate, ferrous sulfate, ferrous carbonate, ferrous chloride, and ferric chloride.
In one or more embodiments, the aluminum source is selected from the group consisting of aluminum oxide and aluminum hydroxide, preferably one or both of lamellar aluminum oxide and lamellar aluminum hydroxide.
In one or more embodiments, the carbon source is selected from one or more of glucose, sucrose, and graphene.
In one or more embodiments, the carbon source is used in an amount of 2-10% of the total mass of all raw materials.
In one or more embodiments, the M source comprises one or both selected from tungsten trioxide and titanium dioxide; the tungsten trioxide is preferably nanoscale tungsten trioxide, and the titanium dioxide is preferably nanoscale titanium dioxide.
In one or more embodiments, in step (1), the materials are mixed using a planetary ball mill, the rotation speed of the ball mill is preferably 150-.
In one or more embodiments, in step (2), the holding is performed using a tube-type atmosphere furnace.
In one or more embodiments, in step (2), the incubation temperature is raised at a ramp rate of 1-3 deg.C/min.
In one or more embodiments, in step (2), the incubation time is from 10 to 18 hours.
In one or more embodiments, in step (2), the temperature is reduced to below 100 ℃ after the heat preservation, and the temperature reduction rate is preferably 2-5 ℃/min.
In one or more embodiments, step (2) further comprises milling and sieving the resulting cobalt-free cathode material.
In one or more embodiments, in step (3), the boron source is boric acid.
In one or more embodiments, in step (3), mixing is performed using a high speed mixer, preferably at a speed of 1000-.
In one or more embodiments, in step (3), the holding is performed using a tube-type atmosphere furnace.
In one or more embodiments, in step (3), the incubation temperature is raised at a ramp rate of 1-3 deg.C/min.
In one or more embodiments, in step (3), the incubation time is from 2 to 6 hours.
In one or more embodiments, in step (3), the temperature is reduced to below 100 ℃ after heat preservation, and the temperature reduction is preferably natural temperature reduction.
The invention also provides a cobalt-free cathode material prepared by the method according to any one of the embodiments.
The invention also provides a positive pole piece, which comprises the cobalt-free positive pole material in any embodiment of the invention.
The invention also provides a lithium ion battery, which comprises the positive pole piece in any embodiment of the invention.
The invention also provides a lithium ion battery cell comprising the positive electrode plate according to any of the embodiments herein.
Drawings
Fig. 1 is a scanning electron micrograph (5k times) of the positive electrode material of example 1.
Fig. 2 is a scanning electron micrograph (20k times) of the positive electrode material of example 1.
Fig. 3 is a scanning electron micrograph (2k times) of the positive electrode material of example 2.
Fig. 4 is a scanning electron micrograph (20k times) of the positive electrode material of example 2.
Fig. 5 is a scanning electron micrograph (2k times) of the positive electrode material of example 3.
Fig. 6 is a scanning electron micrograph (20k times) of the positive electrode material of example 3.
Fig. 7 is a scanning electron micrograph (2k times) of the positive electrode material of example 4.
Fig. 8 is a scanning electron micrograph (20k times) of the positive electrode material of example 4.
Fig. 9 is a first round charge-discharge curve diagram of the positive electrode material of example 1.
FIG. 10 is a 50-cycle capacity retention rate graph of the positive electrode material 1CC/1DC of example 1.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
The terms "comprising," including, "" containing, "and the like, herein, encompass the meanings of" consisting essentially of … … "and" consisting of … …, "e.g., when" A comprises B and C, "A consists essentially of B and C" and "A consists of B and C" are disclosed herein, and are to be considered as having been disclosed herein.
All features defined herein as numerical ranges or percentage ranges, such as numbers, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, percentages refer to mass percentages and ratios to mass ratios.
Herein, when embodiments or examples are described, it is to be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
Cobalt-free cathode material
The positive electrode material of the present invention is Li which is obtained by modifying Ni, Fe and Al as main elements with certain specific kinds of elements M (such as W, Ta, Ti, Si, Mg, Ca, Sr, Ba, Ra, Sc, Y, Zr, Nb, Hf, Cr, Mo, etc.)mNixFeyAlzM(1-x-y-z)O2The cobalt-free anode material is characterized in that m is more than or equal to 0.95 and less than or equal to 2, x is more than or equal to 0.05 and less than or equal to 0.90, y is more than or equal to 0.05 and less than or equal to 0.90, and z is more than or equal to 0.02 and less than or equal to 0.30. M is preferably W, Ta, Ti, Mg, Sr, Ba, Y, Zr, Hf, Cr, Mo or the like. M may be present in either doped or clad form. In the positive electrode material, the mass content of M is between 500ppm and 100000ppm, preferably between 1000 and 50000 ppm. Under the content, the positive electrode material has the advantages of good uniformity of particle morphology, moderate granularity, higher gram volume, high cycle stability and the like. In the positive electrode material of the invention, Ni and Fe are valence-variable elements, and Ni is charged with the progress of charging2+To higher valence state Ni3+And Ni4+Transformation, Fe2+To Fe3+Transformation, Ni and Fe as capacity-contributing elements, while Al and modifying element M do not participate in valence stateThe change mainly plays roles in stabilizing the structure, improving the multiplying power and improving the thermal stability.
The invention discovers that the addition of the modified element M, such as tungsten element and titanium element, in the cathode material disclosed by the invention can improve the first charge-discharge performance of the battery, including the first charge specific capacity, the first discharge specific capacity and the first efficiency, improve the voltage of a discharge platform and the retention rate of the circulating capacity, and improve the rate capability, wherein the effect of using the tungsten modification is better than that of using the titanium modification, and the tungsten modification can also improve the low-temperature performance.
In the positive electrode material of the present invention, the modifying element M is contained in an amount of 500ppm to 100000ppm by mass, for example, 1000ppm, 2000ppm, 5000ppm, 10000ppm, 20000ppm, 50000 ppm.
In embodiments where the modifying element M comprises tungsten, the amount of tungsten may be from 0.1 to 2 wt%, preferably from 0.2 to 1 wt%, e.g., 0.25 wt%, 0.3 wt%, 0.33 wt%, 0.35 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 0.9 wt%, 0.95 wt%, 0.98 wt%. In order to maintain good first charge and discharge properties and low temperature properties, the content of tungsten element is preferably 0.25-0.5 wt%.
In the embodiment where the modifying element M comprises titanium, the content of titanium may be 0.1 to 2 wt%, preferably 0.2 to 1 wt%, for example 0.25 wt%, 0.3 wt%, 0.33 wt%, 0.35 wt%, 0.4 wt%, 0.5 wt%, 0.8 wt%, 0.9 wt%, 0.95 wt%, 0.98 wt%.
In some embodiments, the positive electrode material of the present invention has the formula LimNixFeyAlzM(1-x-y-z)O2·nB2O3Of these, 1. ltoreq. m.ltoreq.1.5, preferably 1.05. ltoreq. m.ltoreq.1.2, for example m may be 1.08, 1.1, 1.12, 1.15; 0.5. ltoreq. x.ltoreq.0.8, preferably 0.6. ltoreq. x.ltoreq.0.7, for example x can be 0.65, 2/3, 0.68; 0.1. ltoreq. y.ltoreq.0.5, preferably 0.1. ltoreq. y.ltoreq.0.2, for example y can be 0.15, 1/6, 0.18; 0.05. ltoreq. z.ltoreq.0.2, preferably 0.1. ltoreq. z.ltoreq.0.2, for example z may be 0.15, 0.1617, 0.165, 0.18. This is advantageous for improving the performance of the battery. In the invention, x + y + z is less than 1.
The positive electrode material has moderate D50 size (about 1-3 mu m) and high powder tap density (1-2g/cc), which is beneficial to improving the battery performance. For example, the particle diameter of D50 in the positive electrode material of the present invention may be 1 μm, 1.3 μm, 1.5 μm, 1.8 μm, 2 μm, 2.5 μm, or 3 μm. The positive electrode material of the present invention may have a powder tap density of 1g/cc, 1.2g/cc, 1.4g/cc, 1.6g/cc, 1.8g/cc, or 2 g/cc. In the invention, the testing method of the tap density of the powder comprises the following steps: a 20g sample of the positive electrode material was placed in a measuring cylinder and tested using a tap density instrument, where it was vibrated 3000 times at a frequency of 250 times/min.
In the present invention, the method for testing the particle size D50 is as follows: a small amount of anode material powder sample is put into a 100mL beaker, 40mL of water is added, 240W external ultrasonic waves are carried out for 15s, the mixture is completely poured into a laser particle analyzer sample introduction system for full dispersion, the light shielding degree is 8-15%, internal ultrasonic waves (about 20W) are always turned on, and the refractive index is 2.90, so that the anode material powder sample D50 test is carried out.
The anode material is formed by stacking micron-sized single-crystal-like particles, wherein the micron-sized single-crystal-like particles are formed by agglomerating nano-sized spherical-like particles. The particle size of the nanoscale spheroidal particles is preferably 200-600nm, for example 300nm, 400nm, 500 nm. The particle size of the micron-sized single-crystal-like particles is preferably 1 to 10 μm, for example, 2 μm, 4 μm, 6 μm, 8 μm, 9 μm. This is advantageous for improving the battery performance.
The cathode material of the present invention may optionally or preferably further contain boron modification, for example, Li in the above chemical formulamNixFeyAlzM(1-x-y-z)O2The cathode material is doped or coated with boron oxide to obtain a chemical formula of LimNixFeyAlzM(1-x-y-z)O2·nB2O3The cathode material can further improve the gram capacity of the cathode active material, and improve the first charge-discharge performance, the cycle performance, the rate performance and the low-temperature performance. In some properties, M and B also have synergistic effects, for example, Ti and B have synergistic effects on improving rate charge capacity retention rate.
The boron modified cathode material Li of the inventionmNixFeyAlzM(1-x-y-z)O2·nB2O3In which m, x, y, z are as defined above, 0. ltoreq. n.ltoreq.0.005, for example n may be 0.001, 0.002, 0.003, 0.004. This is advantageous for improving the performance of the battery. In a preferred embodiment, the mass content of the B element in the positive electrode material is 500-2000ppm, such as 800ppm, 1000ppm, 1200ppm, 1500 ppm.
The cathode material does not contain cobalt element, and is prepared by uniformly mixing a lithium source, a nickel source, an iron source, an aluminum source, a carbon source and an M source and then performing heat preservation treatment (sintering) in an inert gas atmosphere.
In the raw material of the positive electrode material of the present invention, the lithium source may be lithium carbonate (Li)2CO3) Lithium hydroxide (LiOH. H)2O), and the like. In some embodiments, the lithium source is lithium carbonate.
In the raw material of the positive electrode material of the present invention, the nickel source may be nickel hydroxide (Ni (OH))2) Nickel carbonate (NiCO)3) Nickel sulfate (NiSO)4) And the like. The nickel source is preferably spherical. In some embodiments, the nickel source is spherical nickel hydroxide.
In the raw material of the positive electrode material of the present invention, the iron source may be a ferrous compound, a ferric compound or a mixture thereof, and for example, the iron source may be ferrous acetate dihydrate (C)4H6FeO4·2H2O), ferrous sulfate (FeSO)4) Ferrous carbonate (FeCO)3) Ferrous chloride (FeCl)2) Iron chloride (FeCl)3) And the like. In some embodiments, the iron source is ferrous acetate dihydrate.
In the raw materials of the anode material, an aluminum source can be aluminum oxide, aluminum hydroxide and the like. The aluminium source is preferably in the form of a sheet. In some embodiments, the aluminum source is lamellar aluminum oxide.
In the raw material of the cathode material of the present invention, the carbon source may be glucose, sucrose, graphene, or the like. In some embodiments, the carbon source is glucose.
In the present invention, the M source may be an oxide, a hydroxide, a carbonate, or the like of the M element. The M source is preferably nanoscale. In some embodiments, M is one or both selected from the group consisting of elemental tungsten and elemental titanium. In the raw material of the positive electrode material of the present invention, the tungsten source may be tungsten trioxide, and is preferably nano tungsten trioxide. In the raw material of the positive electrode material of the present invention, the titanium source may be titanium dioxide, preferably, nano titanium dioxide.
The raw materials are mixed according to the target element composition of the anode material, and are sintered after being uniformly mixed. Preferably, the raw materials are ball-milled before sintering until the mixed powder material is uniform in color and free from granular sensation during grinding by visual inspection. The rotation speed of the ball mill is preferably 150-250r/min, such as 200r/min, and the ball milling time is preferably 30-60min, which is beneficial to sintering and improving the material performance. Sintering may be carried out in a tube furnace. Inert gas such as nitrogen is used for protection during sintering. The sintering temperature may be 750-850 deg.C, such as 780 deg.C, 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, 840 deg.C. The performance of the cathode material can be adjusted by regulating and controlling the sintering temperature. At higher sintering temperature, the first effect, the cycle performance and the low-temperature performance of the battery are better, so the sintering is preferably carried out at 800-850 ℃, lithium salt is fully melted at the temperature and has more full solid-phase sintering reaction with raw materials, the shape of the generated anode material is more rounded, and the bonding force between a matrix and a coating agent in the coating and secondary sintering is better. The sintering temperature can be raised using a ramp rate of 1-3 deg.C/min, e.g., 1.5 deg.C/min, 2 deg.C/min, 2.5 deg.C/min. The sintering time may be 10-18h, e.g. 12h, 14h, 16 h. After sintering, the temperature is reduced to below 100 ℃, and the cooling rate is preferably 2-5 ℃/min, such as 3 ℃/min and 4 ℃/min. Post-processing of the positive electrode material may be performed. The post-treatment may be selected from grinding, sieving, drying.
When preparing the boron oxide modified cathode material, the cathode material obtained by sintering is further uniformly mixed with a boron source and then subjected to heat preservation treatment (sintering) in inert gas. The boron source may be boric acid. The cathode material and the boron source can be mixed using a high speed mixer. The rotational speed of the high-speed mixer is preferably 1000-. The mixing time is preferably 10-30min, for example 15 min. In this sintering step, the sintering may be carried out in a tube furnace. Inert gas such as nitrogen is used for protection during sintering. The sintering temperature may be 250-350 deg.C, such as 280 deg.C, 290 deg.C, 300 deg.C, 310 deg.C, 320 deg.C. The sintering temperature can be raised using a ramp rate of 1-3 deg.C/min, e.g., 1.5 deg.C/min, 2 deg.C/min, 2.5 deg.C/min. The sintering time may be 2-6h, e.g. 3h, 4h, 5 h. And cooling to below 100 ℃ after sintering, wherein the temperature can be naturally cooled. The boron oxide-modified positive electrode material may be subjected to post-treatment, such as drying.
Positive pole piece and lithium ion battery
The invention provides a positive pole piece containing the positive pole material, a lithium ion battery cell containing the positive pole piece and a lithium ion battery containing the positive pole piece.
The lithium ion battery cell comprises a positive pole piece, a negative pole piece and a diaphragm. And (3) laminating the positive pole piece, the negative pole piece and the diaphragm according to the design requirement (such as zigzag lamination or winding lamination) to prepare the cell of the lithium ion battery.
The positive pole piece comprises a positive pole current collector and a positive pole material layer formed on the surface of the positive pole current collector. The positive electrode material layer includes a positive electrode material, a conductive agent, and a binder. The positive electrode material layer is generally obtained by coating a positive electrode slurry containing a positive electrode material, a conductive agent, a binder and a solvent on a positive electrode current collector, and then rolling, die cutting and baking the positive electrode slurry. The solvent of the positive electrode slurry may be N-methylpyrrolidone (NMP). The positive electrode current collector may be a copper foil, an aluminum foil, a titanium foil, a nickel foil, an iron foil, a zinc foil, or the like. The anode material can be selected from lithium iron phosphate, binary anode materials, ternary anode materials, quaternary anode materials and the like. Preferably, the positive electrode material is a cobalt-free positive electrode material as described in any embodiment herein. The conductive agent of the positive electrode may be one or more selected from conductive carbon black (SP), Carbon Fiber (CF), acetylene black, conductive graphite, graphene, carbon nanotube, and carbon microsphere. Examples of the conductive carbon black include super-carbon black (super-c 65). The binder of the positive electrode may be one or more selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene, polyvinyl alcohol, polyolefin, styrene-butadiene rubber, fluorinated rubber, polyurethane, and sodium alginate. In some embodiments, the conductive agent in the positive electrode material layer is SP and the binder is PVDF. The content ratio of each component in the positive electrode material layer may be conventional, for example, the mass fraction of the positive electrode active material may be 80% to 98%, for example, 84%, 88%, 92%, 96%, the mass fraction of the conductive agent may be 1% to 10%, for example, 2%, 4%, 6%, 8%, and the mass fraction of the binder may be 1% to 10%, for example, 2%, 4%, 6%, 8%.
The negative pole piece comprises a negative pole current collector and a negative pole material layer arranged on the surface of the negative pole current collector. The negative electrode current collector may be a copper foil. The negative electrode material layer includes a negative electrode material, a conductive agent, and a binder. The negative electrode material layer is obtained by coating negative electrode slurry containing a negative electrode material on a positive electrode current collector, and then rolling, die cutting and baking. The solvent of the anode slurry may be water. The negative electrode material may be selected from graphite, lithium metal, lithium alloy, and the like. In some embodiments, the negative electrode material is graphite.
The membrane may be a polymer membrane, a ceramic membrane or a polymer/ceramic composite membrane. The polymer separator includes a single-layer polymer separator and a multi-layer polymer separator. In some embodiments, the separator is a polypropylene (PP) separator.
After obtaining the battery core, packaging the battery core in a shell, and drying, injecting liquid (injecting electrolyte), packaging, standing, forming and shaping to obtain the lithium ion battery.
The lithium ion battery electrolyte contains an organic solvent and a lithium salt. Organic solvents commonly used in electrolytes are carbonate solvents. Suitable carbonate-based solvents include, but are not limited to, one or more, preferably two or more, selected from the group consisting of Ethylene Carbonate (EC), Propylene Carbonate (PC), butylene carbonate, γ -butyrolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC). Preferably, the carbonate-based solvent comprises at least one cyclic carbonate and at least one chain carbonate. Examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and γ -butyrolactone. Examples of the chain carbonate include dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The mass ratio of the cyclic carbonate to the chain carbonate may be 1:4 to 1: 1. For example 1:3, 3:7, 1: 2. In some embodiments, the organic solvent includes cyclic carbonate EC and chain carbonate EMC. The lithium salt in the electrolyte of the present invention may beTo be a lithium salt commonly used in the art, including, but not limited to, lithium hexafluorophosphate (LiPF)6) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiODFB), lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium perchlorate (LiClO)4) Lithium fluoride (LiF), lithium trifluoromethanesulfonate (LiCF)3SO3) And the like. In some embodiments, the lithium salt is LiPF6. The concentration of the lithium salt in the electrolyte may be 0.5 to 2mol/L, for example, 0.8mol/L, 1mol/L, 1.2 mol/L.
The invention has the following beneficial effects:
the cathode material has the advantages of low raw material cost, simple preparation process, good repeatability, easiness in mass production, relative environmental friendliness and the like, the voltage of a discharge platform (about 3.57V) is higher than that of a lithium iron phosphate cathode material, and the voltage of the lithium iron phosphate discharge platform is generally 3.2V. The positive electrode material has moderate D50 size (about 1-3 mu m) and high powder tap density (1-2 g/cc). The cathode material can endow the battery with improved first charge and discharge performance, cycle capacity retention rate and rate capability. In some preferred embodiments, the cathode material of the present invention can impart superior low-temperature performance to a battery. The invention also provides a preparation method for preparing the cathode material by adopting a solid-phase sintering method. Compared with other materials, the cathode material has the advantages of simple synthesis process and low cost of process conditions required by mass production.
The present invention will be illustrated below by way of specific examples. It should be understood that these examples are illustrative only and are not intended to limit the scope of the present invention. The methods, reagents and materials used in the examples are, unless otherwise indicated, conventional in the art. The starting compounds in the examples are all commercially available.
Example 1
The embodiment provides a novel cathode material, and the preparation, characterization and performance test methods are as follows:
(1) according to the elements of nickel, iron, aluminum and tungstenIn a molar ratio of 400:100:99:1, spherical nickel hydroxide (Ni (OH))2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H2O)34.974g, lamellar alumina (Al)2O3)8.412g, nanometer tungsten trioxide (WO)3)0.3864g (W accounts for 3300ppm of the final positive electrode material) and lithium carbonate (Li)2CO3)40.635 g; 7.695g of glucose with a mass fraction of 5% (based on the sum of all raw materials) was weighed;
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, visually observing the uniform color of the mixed powder material, grinding without granular sensation, and stopping ball milling and mixing;
(3) transferring the mixed powder material into a sagger, uniformly spreading, placing in a tubular atmosphere furnace, and performing reaction in a N atmosphere furnace2Heating to 820 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the positive electrode material cooled to room temperature;
(5) in order to further improve gram capacity, cycle and low-temperature performance of the positive active material, the obtained positive material and 1000ppm (calculated according to the mass of boron element) of boric acid are mechanically stirred and mixed, then the mixture is placed in a high-speed mixer 2000r/min for mixing and stirring 15min, then the mixture is placed in a tubular atmosphere furnace, and in a N atmosphere furnace2Raising the temperature to 300 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 4h, then naturally cooling to 100 ℃, and taking out to finally obtain the boron oxide modified Li1.1Ni2/3Fe1/ 6Al0.165W0.00167O2A positive electrode material; drying the prepared anode material in a vacuum drying oven at 100 ℃ for 4h, taking out, weighing a proper amount of powder, adhering the powder to a sample table, placing the sample table in a sample cavity of an instrument, and carrying out surface micro-topography test under different magnifications under a high vacuum condition; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(6) will be provided withHomogenizing the prepared positive electrode material, conductive agent super carbon black (super-c65), binder (PVDF glue solution with solid content of 6.25%) and NMP solvent, and coating to prepare a positive electrode plate, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the conductive agent super carbon black (super-c65) and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC and EMC with the mass ratio of 3:7, and the 2Ah soft package battery is assembled;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(8) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Example 2
The embodiment provides a novel cathode material, and the preparation, characterization and performance test methods are as follows:
(1) spherical nickel hydroxide (Ni (OH)) was weighed so that the molar ratio of nickel, iron, aluminum, and tungsten was 400:100:99:1, respectively2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H2O)34.974g, lamellar alumina (Al)2O3)8.412g, nanometer tungsten trioxide (WO)3)0.3864g (W accounts for 3300ppm of the final positive electrode material) and lithium carbonate (Li)2CO3)40.635 g; 7.695g of glucose with a mass fraction of 5% (based on the sum of all raw materials) was weighed;
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, visually observing the uniform color of the mixed powder material, grinding without granular sensation, and stopping ball milling and mixing;
(3) the mixed powder material is transferred into a sagger, evenly spread and placed in a tubular atmosphere furnaceN2Heating to 780 ℃ at the speed of 2 ℃/min in the atmosphere, preserving heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the positive electrode material cooled to room temperature;
(5) in order to further improve gram capacity, cycle and low-temperature performance of the positive active material, the obtained positive material and 1000ppm (calculated according to the mass of boron element) of boric acid are mechanically stirred and mixed, then the mixture is placed in a high-speed mixer 2000r/min for mixing and stirring 15min, then the mixture is placed in a tubular atmosphere furnace, and in a N atmosphere furnace2Raising the temperature to 300 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 4h, naturally cooling to 100 ℃, and taking out to finally obtain the boron oxide modified Li1.1Ni2/3Fe1/ 6Al0.165W0.00167O2A cobalt-free positive electrode material; drying the prepared anode material in a vacuum drying oven at 100 ℃ for 4h, taking out, weighing a proper amount of powder, adhering the powder to a sample table, placing the sample table in a sample cavity of an instrument, and carrying out surface micro-topography test under different magnifications under a high vacuum condition; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(6) homogenizing the prepared positive electrode material, super-c65 as a conductive agent, a binder (PVDF glue solution with solid content of 6.25%) and an NMP solvent, and coating to prepare a positive electrode plate, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the super-c65 as the conductive agent and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC and EMC in a mass ratio of 3:7, and the battery is assembled into a 2Ah soft package battery;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(8) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Example 3
The embodiment provides a novel cathode material, and the preparation, characterization and performance test methods are as follows:
(1) according to the molar ratio of nickel, iron, aluminum and tungsten elements of 400:100: 97: 3, weighing spherical nickel hydroxide (Ni (OH))2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H2O)34.974g, lamellar alumina (Al)2O3)8.242g, nanometer tungsten trioxide (WO)3)1.159g (W accounts for 9800ppm of the mass fraction of the final cathode material) and lithium carbonate (Li)2CO3)40.635 g; 7.727g of glucose with a mass fraction of 5% (based on the sum of all raw materials) was weighed;
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, visually observing the uniform color of the mixed powder material, grinding without granular sensation, and stopping ball milling and mixing;
(3) transferring the mixed powder material into a sagger, uniformly spreading, placing in a tubular atmosphere furnace, and performing reaction in a N atmosphere furnace2Heating to 820 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the positive electrode material cooled to room temperature;
(5) in order to further improve gram capacity, cycle and low-temperature performance of the positive electrode active material, the obtained positive electrode material and 1000ppm (calculated according to the mass of boron element) of boric acid are mechanically stirred and mixed, then the mixture is placed in a high-speed mixer 2000r/min for mixing and stirring 15min, then the mixture is placed in a tubular atmosphere furnace, the temperature is increased to 300 ℃ at the speed of 2 ℃/min under the atmosphere of N2, the temperature is kept for 4h, then the temperature is naturally reduced to 100 ℃ and then the mixture is taken out, and finally the boron oxide modified Li is obtained1.1Ni2/3Fe1/ 6Al0.1617W0.005O2A cobalt-free positive electrode material; will be preparedPlacing the anode material in a vacuum drying oven at 100 ℃ for drying for 4h, taking out, weighing a proper amount of powder, adhering the powder on a sample table, placing the sample table in a sample cavity of an instrument, and carrying out surface micro-topography test under different magnifications under a high vacuum condition; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(6) homogenizing the prepared positive electrode material, super-c65 serving as a conductive agent, a binder (PVDF glue solution with solid content of 6.25%) and an NMP solvent, and coating to prepare a positive electrode piece, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the super-c65 serving as the conductive agent and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC and EMC with the mass ratio of 3:7, and the 2Ah soft package battery is assembled;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(8) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Example 4
The embodiment provides a novel cathode material, and the preparation, characterization and performance test methods are as follows:
(1) spherical nickel hydroxide (Ni (OH)) was weighed so that the molar ratio of nickel, iron, aluminum, and titanium was 400:100:99:1, respectively2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H234.974g of O), lamellar alumina (Al)2O3)8.412g of nanoscale titanium dioxide (TiO)2)0.133g (900 ppm of Ti based on the final positive electrode material) and lithium carbonate (Li)2CO3)40.635 g; weighing 5% glucose by mass7.682g (based on the sum of all raw materials);
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, visually observing the uniform color of the mixed powder material, grinding without granular sensation, and stopping ball milling and mixing;
(3) transferring the mixed powder material into a sagger, uniformly spreading, placing in a tubular atmosphere furnace, and performing reaction in a N atmosphere furnace2Heating to 820 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the positive electrode material cooled to room temperature;
(5) in order to further improve gram capacity, cycle and low-temperature performance of the positive active material, the obtained positive material and 1000ppm (calculated according to the mass of boron element) of boric acid are mechanically stirred and mixed, then the mixture is placed in a high-speed mixer 2000r/min for mixing and stirring 15min, then the mixture is placed in a tubular atmosphere furnace, and in a N atmosphere furnace2Raising the temperature to 300 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 4h, naturally cooling to 100 ℃, and taking out to finally obtain the boron oxide modified Li1.1Ni2/3Fe1/ 6Al0.165Ti0.00167O2A cobalt-free positive electrode material; drying the prepared anode material in a vacuum drying oven at 100 ℃ for 4h, taking out, weighing a proper amount of powder, adhering the powder to a sample table, placing the sample table in a sample cavity of an instrument, and carrying out surface micro-topography test under different magnifications under a high vacuum condition; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(6) homogenizing the prepared positive electrode material, super-c65 as a conductive agent, a binder (PVDF glue solution with solid content of 6.25%) and an NMP solvent, and coating to prepare a positive electrode plate, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the super-c65 as the conductive agent and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC and EMC with the mass ratio of 3:7, and the 2Ah soft package is assembledA pool;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(8) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Example 5
The embodiment provides a novel cathode material, and the preparation, characterization and performance test methods are as follows:
(1) spherical nickel hydroxide (Ni (OH)) was weighed in a molar ratio of nickel, iron, aluminum and titanium of 400:100:99:1, respectively2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H2O)34.974g, lamellar alumina (Al)2O3)8.412g of nanoscale titanium dioxide (TiO)2)0.133g (900 ppm of Ti based on the final positive electrode material) and lithium carbonate (Li)2CO3)40.635 g; 7.682g of glucose with the mass fraction of 5 percent is weighed (taking the sum of all raw materials as a reference);
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, visually observing the uniform color of the mixed powder material, grinding without granular sensation, and stopping ball milling and mixing;
(3) transferring the mixed powder material into a sagger, uniformly spreading, placing in a tubular atmosphere furnace, and performing reaction in a N atmosphere furnace2Heating to 820 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the anode material cooled to room temperature to finally obtain Li1.1Ni2/3Fe1/ 6Al0.165Ti0.00167O2A cobalt-free positive electrode material; drying the prepared anode material at 100 ℃ in vacuumDrying for 4h in a drying box, taking out, weighing a proper amount of powder, adhering the powder on a sample table, placing the powder in a sample cavity of an instrument, and carrying out surface micro-topography test under different magnifications under a high vacuum condition; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(5) homogenizing the prepared positive electrode material, super-c65 serving as a conductive agent, a binder (PVDF glue solution with solid content of 6.25%) and an NMP solvent, and coating to prepare a positive electrode piece, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the super-c65 serving as the conductive agent and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC and EMC with the mass ratio of 3:7, and the 2Ah soft package battery is assembled;
(6) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Comparative example 1
The comparative example provides a positive electrode material, and the preparation, characterization and performance test methods are as follows:
(1) according to the molar ratio of nickel, iron and aluminum of 4: 1:1, weighing spherical nickel hydroxide (Ni (OH))2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H2O)34.974g, lamellar alumina (Al)2O3)8.497g and lithium carbonate (Li)2CO3)40.635 g; 7.679g of glucose with a mass fraction of 5% (based on the sum of all raw materials) was weighed;
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, and stopping ball milling and mixing until the color of the mixed powder material is uniform and the mixed powder material is not ground into a granular feeling by visual inspection
(3) Transferring the mixed powder material into a sagger, uniformly spreading, placing in a tubular atmosphere furnace, and performing reaction in a N atmosphere furnace2Heating to 820 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the positive electrode material cooled to room temperature;
(5) in order to further improve gram capacity, cycle and low-temperature performance of the positive active material, the obtained positive material and 1000ppm (calculated according to the mass of boron element) of boric acid are mechanically stirred and mixed, then the mixture is placed in a high-speed mixer 2000r/min for mixing and stirring 15min, then the mixture is placed in a tubular atmosphere furnace, and in a N atmosphere furnace2Raising the temperature to 300 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 4h, naturally cooling to 100 ℃, and taking out to finally obtain the boron oxide modified Li1.1Ni2/3Fe1/6Al1/ 6O2A cobalt-free positive electrode material; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(6) homogenizing the prepared positive electrode material, super-c65 as a conductive agent, a binder (PVDF glue solution with solid content of 6.25%) and an NMP solvent, and coating to prepare a positive electrode plate, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the super-c65 as the conductive agent and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC + EMC with the mass ratio of 3:7, and the 2Ah soft package battery is assembled;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(8) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Comparative example 2
The comparative example provides a positive electrode material, and the preparation, characterization and performance test methods are as follows:
(1) according to the molar ratio of nickel, iron and aluminum of 4: 1:1, weighing spherical nickel hydroxide (Ni (OH))2)61.795g, ferrous acetate dihydrate (C)4H6FeO4·2H2O)34.974g, lamellar alumina (Al)2O3)8.497g and lithium carbonate (Li)2CO3)40.635 g; 7.679g of glucose with a mass fraction of 5% (based on the sum of all raw materials) was weighed;
(2) placing the weighed raw materials into a ball milling tank, ball milling and stirring for 30-60min by using a planetary ball mill at 200r/min, visually observing that the mixed powder material has uniform color and no grain sense during grinding, and stopping ball milling and mixing
(3) Transferring the mixed powder material into a sagger, uniformly spreading, placing in a tubular atmosphere furnace, and performing reaction in a N atmosphere furnace2Heating to 820 ℃ at the speed of 2 ℃/min in the atmosphere, preserving the heat for 14h, cooling to 100 ℃ at the speed of 4 ℃/min, and taking out;
(4) carrying out ultracentrifugal grinding and screening on the anode material cooled to room temperature to finally obtain Li1.1Ni2/3Fe1/ 6Al1/6O2A cobalt-free positive electrode material; weighing 20.00g of prepared positive electrode material sample, placing the positive electrode material sample in a measuring cylinder, and testing tap density by using a tap density instrument, wherein the tap density is vibrated for 3000 times and the frequency is 250 times/min;
(5) homogenizing the prepared positive electrode material, super-c65 as a conductive agent, a binder (PVDF glue solution with solid content of 6.25%) and an NMP solvent, and coating to prepare a positive electrode plate, wherein the mass fraction of the positive electrode material is 92%, and the mass fractions of the super-c65 as the conductive agent and the binder are respectively 4%; graphite is used as a negative electrode, a PP diaphragm is used, and lithium salt of the electrolyte is 1mol/L LiPF6The solvent is EC and EMC with the mass ratio of 3:7, and the mixture is assembled into a 2Ah soft packageA battery;
(6) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the first charge-discharge test is carried out under the charge of 0.1C and the discharge of 0.1C, after two weeks of circulation, the charge-discharge cycle is changed into the charge-discharge cycle under the charge of 1C and the discharge of 1C for 50 weeks, and after the charge-discharge cycle under the charge of 0.1C and the discharge of 0.1C for two weeks, the data are shown in a table 2;
(7) a blue battery test system is adopted, the voltage range is 2.75-4.25V, the 0.33C/0.5C/1C/2C rate charging and the 0.33C/0.5C/1C/2C/3C rate discharging tests are carried out, the high and low temperature performance tests are carried out at 25 ℃/55 ℃/10 ℃/0 ℃/10 ℃/20 ℃, and the data are shown in table 3.
Fig. 1 and 2 are scanning electron micrographs of the positive electrode material of example 1, from which: the anode material is formed by stacking 200-600nm nano-scale spheroidal particle aggregates and 1-10 mu m micro-scale single crystal particles, the D50 particle size is about 1.5 mu m, and more island-shaped coatings exist on the particle surface, so that the coating is relatively compact and uniform, the side reaction is favorably reduced, and the material performance is improved.
Fig. 3 and 4 are scanning electron micrographs of the positive electrode material of example 2, from which: the anode material is formed by stacking 200-500nm nano-scale spheroidal particle aggregates and 1-8 mu m micron-scale single-crystal-like particles, and the D50 particle size is about 1.3 mu m.
Fig. 5 and 6 are scanning electron micrographs of the positive electrode material of example 3, from which: the anode material is formed by stacking 300-500 nano-scale spheroidal particle aggregates and 1-9 mu m micro-scale mono-crystalline particles, the hard aggregates of the whole particles are more, and the D50 particle size is about 1.5 mu m.
Fig. 7 and 8 are scanning electron micrographs of the positive electrode material of example 4, from which: the anode material is formed by stacking 200-600nm nano-scale spheroidal particle aggregates and 1-10 mu m micron-scale single-crystal-like particles, and the D50 particle size is about 2 mu m.
Fig. 9 is a first round charge and discharge curve of the positive electrode material of example 1, in which the first charge capacity, the first discharge capacity, and the first efficiency are 189.21mAh/g, 98.41mAh/g, and 52.01%, respectively.
FIG. 10 is a graph showing the 50-cycle capacity retention rate of the positive electrode material 1CC/1DC of example 1, wherein the discharge capacity of the material 1CC/1DC in cycles is 74.31mAh/g, and the 50-cycle capacity retention rate is 48.99%.
Table 1 shows the Li/Me ratio (ratio of the number of moles of Li to the total number of moles of all metal elements except Li), the mole fraction of each metal element except Li to all metal elements except Li, the doping element and the mass fraction thereof in the positive electrode material, which correspond to example 1, example 2, example 3, example 4, example 5, and comparative example 1, comparative example 2.
Table 1: compositions and tap densities of cathode materials of examples 1 to 5 and comparative examples 1 to 2
Table 2 shows the initial charge specific capacity, initial discharge specific capacity, initial efficiency, plateau voltage, and 50-cycle capacity retention ratio for examples 1 to 5 and comparative examples 1 to 2.
Table 2: specific first Charge Capacity, specific first discharge Capacity, first efficiency, plateau Voltage, 50-cycle Capacity holding ratio of examples 1 to 5 and comparative examples 1 to 2
Table 3 shows cell rate charge, rate discharge and low temperature performance data for examples 1, 2, 3, 4, 5 and comparative examples 1 and 2.
Table 3: rate Charge, Rate discharge, and Low temperature Performance data for examples 1-5 and comparative examples 1-2
Claims (10)
1. A cobalt-free cathode material, whichCharacterized in that the chemical formula of the cobalt-free cathode material is LimNixFeyAlzM(1-x-y-z)O2·nB2O3Wherein M is one or more elements selected from W, Ta, Ti, Si, Mg, Ca, Sr, Ba, Ra, Sc, Y, Zr, Nb, Hf, Cr and Mo, M is more than or equal to 0.95 and less than or equal to 2, x is more than or equal to 0.05 and less than or equal to 0.9, Y is more than or equal to 0.05 and less than or equal to 0.9, z is more than or equal to 0.02 and less than or equal to 0.3, and n is more than or equal to 0 and less than or equal to 0.005.
2. The cobalt-free positive electrode material according to claim 1,
m is one or more elements selected from W, Ta, Ti, Mg, Sr, Ba, Y, Zr, Hf, Cr and Mo; and/or
In the cobalt-free cathode material, the mass content of M is 500ppm-100000ppm, preferably 1000-50000 ppm.
3. The cobalt-free positive electrode material according to claim 1, wherein the M contains one or two selected from a W element and a Ti element;
preferably, said M comprises a W element; preferably, in the cobalt-free cathode material, the content of the W element is 0.1-2 wt%, preferably 0.2-1 wt%, and more preferably 0.25-0.5 wt%;
preferably, said M comprises Ti element; preferably, the content of the W element in the cobalt-free cathode material is 0.1-2 wt%, preferably 0.2-1 wt%.
4. The cobalt-free cathode material as claimed in claim 1, wherein the mass content of the element B in the cobalt-free cathode material is 500-2000 ppm.
5. The cobalt-free positive electrode material of claim 1, wherein the cobalt-free positive electrode material has one or more of the following characteristics:
1. ltoreq. m.ltoreq.1.5, preferably 1.05. ltoreq. m.ltoreq.1.2;
0.5. ltoreq. x.ltoreq.0.8, preferably 0.6. ltoreq. x.ltoreq.0.7;
0.1. ltoreq. y.ltoreq.0.5, preferably 0.1. ltoreq. y.ltoreq.0.2;
0.05. ltoreq. z.ltoreq.0.2, preferably 0.1. ltoreq. z.ltoreq.0.2.
6. The cobalt-free positive electrode material of claim 1, wherein the cobalt-free positive electrode material has one or more of the following characteristics:
the cobalt-free anode material is formed by stacking micron-sized single-crystal-like particles, and the micron-sized single-crystal-like particles are formed by agglomerating nano-sized spherical-like particles; preferably, the particle size of the nanoscale spheroidal particles is 200-600 nm; preferably, the micron-sized mono-like particles have a particle size of 1 to 10 μm;
the particle size of D50 of the cobalt-free cathode material is 1-3 μm;
the tap density of the powder of the cobalt-free cathode material is 1-2 g/cc.
7. A method of preparing the cobalt-free positive electrode material of any one of claims 1-6, comprising the steps of:
(1) uniformly mixing a lithium source, a nickel source, an iron source, an aluminum source, a carbon source and an M source;
(2) performing heat preservation treatment on the mixed material obtained in the step (1) at the temperature of 750-;
optionally, the method further comprises:
(3) and (3) uniformly mixing the cobalt-free anode material obtained in the step (2) with a boron source, and then carrying out heat preservation treatment in an inert gas atmosphere at the temperature of 250-350 ℃ to obtain the boron-element-containing cobalt-free anode material.
8. The method of claim 7, wherein the method has one or more of the following features:
the lithium source is selected from one or two of lithium carbonate and lithium hydroxide;
the nickel source is selected from one or more of nickel hydroxide, nickel carbonate and nickel sulfate, and is preferably spherical nickel hydroxide;
the iron source is selected from one or more of ferrous acetate dihydrate, ferrous sulfate, ferrous carbonate, ferrous chloride and ferric chloride;
the aluminum source is selected from one or two of aluminum oxide and aluminum hydroxide, preferably one or two of lamellar aluminum oxide and lamellar aluminum hydroxide;
the carbon source is selected from one or more of glucose, sucrose and graphene;
the using amount of the carbon source is 2-10% of the total mass of all the raw materials;
the M source comprises one or two selected from tungsten trioxide and titanium dioxide; the tungsten trioxide is preferably nano-scale tungsten trioxide, and the titanium dioxide is preferably nano-scale titanium dioxide;
in the step (1), a planetary ball mill is used for mixing materials, the rotating speed of the ball mill is preferably 150-250r/min, and the ball milling time is preferably 30-60 min;
in the step (2), a tubular atmosphere furnace is used for heat preservation;
in the step (2), the temperature is increased to the heat preservation temperature at the heating rate of 1-3 ℃/min;
in the step (2), the heat preservation time is 10-18 h;
in the step (2), after heat preservation, the temperature is reduced to be below 100 ℃, and the temperature reduction rate is preferably 2-5 ℃/min;
the step (2) also comprises grinding and screening the obtained cobalt-free anode material;
in the step (3), the boron source is boric acid;
in the step (3), a high-speed mixer is used for mixing, wherein the rotating speed of the high-speed mixer is preferably 1000-3000r/min, and the mixing time is preferably 10-30 min;
in the step (3), a tubular atmosphere furnace is used for heat preservation;
in the step (3), the temperature is increased to the heat preservation temperature at the heating rate of 1-3 ℃/min;
in the step (3), the heat preservation time is 2-6 h;
in the step (3), the temperature is reduced to be below 100 ℃ after heat preservation, and natural temperature reduction is preferable.
9. A positive electrode sheet comprising the cobalt-free positive electrode material according to any one of claims 1 to 6.
10. A lithium ion battery or a lithium ion battery cell, characterized in that the lithium ion battery or the lithium ion battery cell comprises the positive electrode sheet of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210212960.9A CN114566633A (en) | 2022-03-04 | 2022-03-04 | Novel cobalt-free cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210212960.9A CN114566633A (en) | 2022-03-04 | 2022-03-04 | Novel cobalt-free cathode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114566633A true CN114566633A (en) | 2022-05-31 |
Family
ID=81718350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210212960.9A Pending CN114566633A (en) | 2022-03-04 | 2022-03-04 | Novel cobalt-free cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114566633A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101635349A (en) * | 2009-08-21 | 2010-01-27 | 广州市云通磁电有限公司 | Method for preparing metal-silver-doped carbon-covering lithium iron phosphate of lithium-ion battery cathode material |
| CN101740768A (en) * | 2008-11-27 | 2010-06-16 | 比亚迪股份有限公司 | Hydrogen storage alloy and preparation method thereof and cathode and battery using same |
| WO2012060084A1 (en) * | 2010-11-05 | 2012-05-10 | 株式会社豊田自動織機 | Lithium borate compound and method for producing same |
| CN103703593A (en) * | 2011-07-13 | 2014-04-02 | 日本电气株式会社 | Active material for secondary batteries |
| WO2016110123A1 (en) * | 2015-01-05 | 2016-07-14 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte and lithium ion secondary battery |
| WO2019050282A1 (en) * | 2017-09-08 | 2019-03-14 | 주식회사 엘지화학 | Lithium secondary battery cathode active material, preparation method therefor, lithium secondary battery cathode comprising same, and lithium secondary battery |
| WO2020043153A1 (en) * | 2018-08-31 | 2020-03-05 | 宁德时代新能源科技股份有限公司 | Secondary lithium ion battery |
| CN111933930A (en) * | 2020-08-13 | 2020-11-13 | 松山湖材料实验室 | Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery |
| CN111943283A (en) * | 2020-08-13 | 2020-11-17 | 松山湖材料实验室 | Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery |
-
2022
- 2022-03-04 CN CN202210212960.9A patent/CN114566633A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740768A (en) * | 2008-11-27 | 2010-06-16 | 比亚迪股份有限公司 | Hydrogen storage alloy and preparation method thereof and cathode and battery using same |
| CN101635349A (en) * | 2009-08-21 | 2010-01-27 | 广州市云通磁电有限公司 | Method for preparing metal-silver-doped carbon-covering lithium iron phosphate of lithium-ion battery cathode material |
| WO2012060084A1 (en) * | 2010-11-05 | 2012-05-10 | 株式会社豊田自動織機 | Lithium borate compound and method for producing same |
| CN103703593A (en) * | 2011-07-13 | 2014-04-02 | 日本电气株式会社 | Active material for secondary batteries |
| WO2016110123A1 (en) * | 2015-01-05 | 2016-07-14 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte and lithium ion secondary battery |
| WO2019050282A1 (en) * | 2017-09-08 | 2019-03-14 | 주식회사 엘지화학 | Lithium secondary battery cathode active material, preparation method therefor, lithium secondary battery cathode comprising same, and lithium secondary battery |
| WO2020043153A1 (en) * | 2018-08-31 | 2020-03-05 | 宁德时代新能源科技股份有限公司 | Secondary lithium ion battery |
| CN111933930A (en) * | 2020-08-13 | 2020-11-13 | 松山湖材料实验室 | Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery |
| CN111943283A (en) * | 2020-08-13 | 2020-11-17 | 松山湖材料实验室 | Positive electrode active material, preparation method thereof, secondary battery positive electrode and lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101771086B1 (en) | Composite positive active material and manufacturing method thereof, positive electrode and lithium battery containing the material | |
| CN103378357B (en) | Negative electrode compositions, negative electrode and lithium rechargeable battery | |
| JP5474880B2 (en) | Positive electrode active material for lithium secondary battery, method for producing the same, and lithium secondary battery including the same | |
| EP3588627B1 (en) | Lithium-ion battery | |
| KR102183996B1 (en) | Positive active material and manufacturing method thereof, positive electrode and lithium battery containing the material | |
| JP5732533B2 (en) | Method for preparing negative electrode active material, negative electrode material, and lithium ion battery | |
| CN105720259B (en) | Negative active material and lithium battery including the same | |
| JP5684915B2 (en) | Anode active material for lithium secondary battery, method for producing the same, and lithium secondary battery including the same | |
| CN113471442B (en) | Negative active material, and negative electrode sheet, electrochemical device, and electronic device using same | |
| CN109671999B (en) | Lithium ion battery in-situ pre-lithiation method and lithium ion battery | |
| WO2020135767A1 (en) | Positive electrode active material, positive electrode plate, electrochemical energy storage apparatus, and apparatus | |
| KR20160134317A (en) | Positive active material and manufacturing method thereof, positive electrode and lithium battery containing the material | |
| KR102152367B1 (en) | Method for manufacturing composite positive active material, composite positive active material obtained thereby, positive electrode and lithium battery containing the material | |
| KR20170080104A (en) | Positive active material, and positive electrode and lithium battery containing the material | |
| EP2916375B1 (en) | Negative active material, negative electrode and lithium battery including the negative active material, and method of manufacturing the negative active material | |
| JP7010545B2 (en) | Negative electrode active material, negative electrode using it, and lithium battery | |
| US8986886B2 (en) | Positive active material, method of preparing the same, and lithium battery including the positive active material | |
| US7556887B2 (en) | Nonaqueous electrolyte secondary battery with negative electrode having a La3Co2Sn7 type crystal structure | |
| JP2021190430A (en) | Composite positive electrode active material, positive electrode including the same, lithium battery, and manufacturing method for the same | |
| US11916229B2 (en) | Positive electrode active material and preparation method therefor, positive electrode plate containing same, secondary battery, and power consuming device | |
| KR20170042115A (en) | Negative active material, and negative electrode and lithium battery including the material | |
| CN114566633A (en) | Novel cobalt-free cathode material and preparation method thereof | |
| US11888154B2 (en) | Positive electrode sheet, secondary battery, battery module, battery pack and electrical apparatus | |
| CN114314689B (en) | Lithium battery anode material and preparation method thereof | |
| KR20110128591A (en) | Rechargeable lithium battery |
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 |