EP4248504A1 - Cathode active material, and lithium ion battery comprising said cathode active material - Google Patents
Cathode active material, and lithium ion battery comprising said cathode active materialInfo
- Publication number
- EP4248504A1 EP4248504A1 EP21806705.6A EP21806705A EP4248504A1 EP 4248504 A1 EP4248504 A1 EP 4248504A1 EP 21806705 A EP21806705 A EP 21806705A EP 4248504 A1 EP4248504 A1 EP 4248504A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- active material
- cathode active
- lithium
- particles
- ion battery
- 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
- 239000006182 cathode active material Substances 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 50
- 239000010450 olivine Substances 0.000 claims abstract description 9
- 229910052609 olivine Inorganic materials 0.000 claims abstract description 9
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- 239000011572 manganese Substances 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000006183 anode active material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000011883 electrode binding agent Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910010689 LiFePC Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-O Piperidinium(1+) Chemical compound C1CC[NH2+]CC1 NQRYJNQNLNOLGT-UHFFFAOYSA-O 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 1
- 229920001872 Spider silk Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- HSLXOARVFIWOQF-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-1-methylpyrrolidin-1-ium Chemical compound CCCC[N+]1(C)CCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSLXOARVFIWOQF-UHFFFAOYSA-N 0.000 description 1
- IEFUHGXOQSVRDQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-1-propylpiperidin-1-ium Chemical compound CCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F IEFUHGXOQSVRDQ-UHFFFAOYSA-N 0.000 description 1
- WUFQNPMBKMKEHN-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;diethyl-(2-methoxyethyl)-methylazanium Chemical compound CC[N+](C)(CC)CCOC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F WUFQNPMBKMKEHN-UHFFFAOYSA-N 0.000 description 1
- BLODSRKENWXTLO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;triethylsulfanium Chemical compound CC[S+](CC)CC.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F BLODSRKENWXTLO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000005500 uronium group Chemical group 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- 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
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
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- 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
Definitions
- the invention relates to a cathode active material for a lithium ion battery and a lithium ion battery with such a cathode active material.
- lithium ion battery is used synonymously for all terms commonly used in the prior art for lithium-containing galvanic elements and cells, such as lithium battery cell, lithium battery, lithium cell, lithium ion cell, lithium Polymer cell, lithium polymer battery and lithium ion accumulator.
- rechargeable batteries secondary batteries
- the lithium-ion battery can also be a solid-state battery, for example a ceramic or polymer-based solid-state battery.
- a lithium ion battery has at least two distinct electrodes, a positive electrode (cathode) and a negative electrode (anode). Each of these electrodes includes at least one active material, optionally together with additives such as electrode binders and electrical conductivity additives.
- cathode active material In lithium-ion batteries, both the cathode active material and the anode active material must be able to reversibly absorb or release lithium ions.
- Suitable cathode active materials are known, for example, from EP 0 017 400 B1 and DE 3319939 A1.
- lithium-nickel-manganese-cobalt layered oxide (NMC for short) is often used as the cathode active material, since NMC is characterized in particular by its high energy density.
- the nickel content can be increased to increase the energy density of NMC, for example compositions such as Li(Nio,6Mno,2Coo,2)C>2 (short: NMC622) or Li(Nio,8Mno,iCoo,i)02 (short NMC811) can be used.
- the high energy density of these materials is also associated with high costs, increased reactivity and high safety requirements for the design of the battery cell.
- a problem to be solved according to one aspect of the invention is to provide an improved cathode active material for a lithium ion battery characterized in particular by the highest possible energy density with reduced costs and/or improved safety at the same time. Furthermore, a lithium-ion battery with such a cathode active material is to be specified.
- the cathode active material comprises a multiplicity of first particles which have or consist of a cobalt-free layered lithium oxide.
- the cobalt-free layered lithium oxide is preferably a lithium nickel manganese oxide.
- the cathode active material comprises a multiplicity of second particles which have or consist of a phospho-olivine.
- the phospho-olivine is in particular lithium iron phosphate (LFP) or lithium iron manganese phosphate (LFMP).
- LFP lithium iron phosphate
- LFMP lithium iron manganese phosphate
- the cathode active material proposed here which has both the first particles and the second particles, is characterized by lower costs and increased intrinsic safety compared to pure NMC.
- the admixture of the second particles from the phosho-olivine makes it possible to dispense with the element cobalt in the layered oxide without significantly impairing the stability of the cathode active material.
- the cathode active material thus enables the cathode to be manufactured in a comparatively environmentally friendly and sustainable manner.
- the energy density of the mixed cathode active material is increased compared to a pure phospho-olivine.
- the first particles have Li y (Nii.xMn x )O 2 with 0 ⁇ x ⁇ 1, in particular with 0.1 ⁇ x ⁇ 0.9 and 0.9 ⁇ y ⁇ 1.3.
- the cobalt-free lithium layer oxide is a lithium nickel oxide, a lithium nickel manganese oxide or a lithium manganese oxide.
- the layered oxide is a lithium-rich layered oxide (OLO, over lithiated layered oxide).
- the manganese content is x>0.5.
- the layered lithium oxide is a manganese-rich lithium layered oxide.
- the layered lithium oxide contains more manganese than nickel. Due to the high proportion of manganese, the layered oxide can be produced particularly cost-effectively.
- the second particles have LiFePC or LiFei. y Mn y PO4 and 0 ⁇ y ⁇ 1, ie the phospho-olivine is lithium iron phosphate or a lithium iron manganese phosphate.
- the second particles particularly preferably have LiFei. y Mn y PO4 with 0.5 ⁇ y ⁇ 0.9.
- Such a manganese-rich lithium-iron-manganese phosphate is characterized by a high energy density compared to lithium-iron phosphate.
- the proportion of the first particles in the total of the first and second particles is between 10% by weight and 90% by weight inclusive, preferably between 20% by weight and 80% by weight inclusive.
- the proportion of the first particles in the total of the first and second particles is at least 70% by weight, in particular between 70% by weight and 90% by weight inclusive, particularly preferably at least 80% by weight, in particular between 80% by weight and 90% by weight inclusive.
- the proportion of the first particles can be 85% by weight and the proportion of the second particles can be 15% by weight.
- the proportion of the first particles in the total of the first and second particles is no more than 50% by weight, in particular between 10% by weight and 50% by weight inclusive, particularly preferably no more than 40% by weight %, in particular between 10% by weight and 40% by weight inclusive.
- the proportion of the first particles can be 30% by weight and the proportion of the second particles can be 70% by weight.
- the energy density is higher than that of a lithium-ion battery that has a pure phospho-olivine such as LFP as the cathode active material.
- the improved thermal stability of the cathode active material in this configuration makes it possible in particular to produce the lithium ion battery in a so-called “cell-to-pack” approach, i.e. a lithium ion battery cell can be produced with the cathode active material proposed here, which can be placed directly in a battery pack is inserted.
- the lithium-ion battery cells are not first installed in modules that together form a lithium-ion battery, but are directly assembled to form a battery pack.
- the cathode active material can be formed into a cathode (positive electrode) comprising, for example, the cathode active material, an electrode binder and an electrically conductive additive such as e.g. B. includes conductive carbon black processed.
- a cathode positive electrode
- an electrically conductive additive such as e.g. B. includes conductive carbon black processed.
- a lithium-ion battery which has a cathode with the cathode active material described above.
- the cathode can be produced, for example, from a coating composition which contains the cathode active material with the first particles and the second particles, an electrode binder and an electrically conductive additive such as e.g. B. includes conductive carbon black.
- the lithium-ion battery can, for example, only include a single battery cell or alternatively include one or more modules with multiple battery cells, it being possible for the battery cells to be connected in series and/or in parallel.
- the lithium ion battery includes at least one cathode having the cathode active material and an anode having at least one anode active material.
- the lithium-ion battery can have the other components of a lithium-ion battery known per se, in particular current collectors, a separator and an electrolyte.
- the lithium-ion battery according to the invention can be provided in particular in a motor vehicle or in a portable device.
- the portable device can in particular be a smartphone, an electric tool or power tool, a tablet or a wearable.
- the lithium-ion battery can also be used in a stationary energy store.
- FIG. 1 shows the structure of a lithium-ion battery according to an embodiment
- FIG. 2 shows the cathode active material applied to a current collector in the exemplary embodiment.
- the lithium-ion battery 10 shown purely schematically in FIG. 1 has a cathode 2 and an anode 5 .
- the cathode 2 and the anode 5 each have a current collector 1, 6, it being possible for the current collectors to be in the form of metal foils.
- the current collector 1 of the cathode 2 has, for example, aluminum and the current collector 6 of the anode 5 has copper.
- the cathode 2 and the anode 5 are separated from one another by a separator 4 which is permeable to lithium ions but impermeable to electrons.
- Polymers can be used as separators, in particular a polymer selected from the group consisting of polyesters, in particular polyethylene terephthalate, polyolefins, in particular polyethylene and/or polypropylene, polyacrylonitriles, polyvinylidene fluoride, polyvinylidene hexafluoropropylene, polyetherimide, polyimide, aramid, polyether, polyetherketone, synthetic spider silk or mixtures thereof.
- the separator can optionally also be coated with ceramic material and a binder, for example based on Al2O3.
- the lithium ion battery has an electrolyte 3 which is conductive for lithium ions and which can be a solid electrolyte or a liquid which includes a solvent and at least one lithium conducting salt, for example lithium hexafluorophosphate (LiPFe), dissolved therein.
- the solvent is preferably inert.
- suitable solvents are organic solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate (FEC), sulpholane, 2-methyltetrahydrofuran, acetonitrile and 1,3-dioxolane.
- Ionic liquids can also be used as solvents.
- Such ionic liquids contain only ions.
- Preferred cations which can be alkylated in particular, are imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, Thiuronium, piperidinium, morpholinium, sulfonium, ammonium and phosphonium cations.
- Examples of anions that can be used are halide, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate anions.
- ionic liquids which may be mentioned are: N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide, N-butyl-N-trimethyl -ammonium bis(trifluoromethylsulfonyl)imide, triethylsulfonium bis(trifluoromethylsulfonyl)imide and N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide.
- Preferred conductive salts are lithium salts which have inert anions and which are preferably non-toxic. Suitable lithium salts are, in particular, lithium hexafluorophosphate (LiPFe), lithium tetrafluoroborate (UBF4) and mixtures of these salts.
- the separator 4 can be impregnated or wetted with the lithium salt electrolyte if it is liquid.
- the anode 5 has an anode active material.
- the anode active material may be selected from the group consisting of carbonaceous materials, silicon, silicon suboxide, silicon alloys, aluminum alloys, indium, indium alloys, tin, tin alloys, cobalt alloys, and mixtures thereof.
- the anode active material is preferably selected from the group consisting of synthetic graphite, natural graphite, graphene, mesocarbon, doped carbon, hard carbon, soft carbon, fullerene, silicon-carbon composite, silicon, surface-coated silicon, silicon suboxide, silicon alloys, lithium, aluminum alloys, indium , tin alloys, cobalt alloys and mixtures thereof.
- anode active materials known from the prior art are also suitable, for example niobium pentoxide, titanium dioxide, titanates such as lithium titanate (Li4TisOi2), tin dioxide, lithium, lithium alloys and/or mixtures thereof.
- niobium pentoxide titanium dioxide
- titanates such as lithium titanate (Li4TisOi2)
- tin dioxide lithium, lithium alloys and/or mixtures thereof.
- FIG. 2 shows a schematic representation of the cathode 2 on the current collector 1, which can in particular be an aluminum foil.
- the cathode 2 has a cathode active material.
- the cathode active material has a multiplicity of first particles 11 and second particles 12 .
- the particles 11, 12 can be bound into an electrode binder 13, possibly with an additive that increases the conductivity, such as a conductive carbon black.
- the first particles 11 have a cobalt-free layered oxide, in particular Li(Nii-xMn x )O2 with 0 ⁇ x ⁇ 1.
- x>0.5 preferably applies, particularly preferably x>0.6.
- the second particles 12 have a phospho-olivine, in particular LiFel. y Mn y PO4 with 0 ⁇ y ⁇ 1.
- a particularly good ratio of costs and energy density is achieved when the first particles 11 are a manganese-rich layer oxide, in particular Li( Ni.xMnx )O2 with x >0.5, preferably x>0.6, and the second particles 12 a manganese-rich lithium-iron-manganese phosphate, in particular LiFei. y Mn y PO4 with 0.5 ⁇ y ⁇ 0.9.
- the proportion of the first particles 11 in the totality of the particles 11 , 12 can be between 10% and 90% inclusive, in particular between 20% and 80% inclusive. In an embodiment in which the highest possible energy density is to be achieved at still moderate costs, the proportion of the first particles 11 is between 70% and 90% inclusive, for example approximately 85%. In this case, the proportion of the second particles 12 is between 10% and 30% inclusive, for example approximately 15%.
- the proportion of the first particles 11 is between 10% and 50% inclusive, for example approximately 30%.
- the proportion of the second particles 12 is between 50% and 90% inclusive, for example approximately 70%.
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Abstract
Described is a cathode active material for a lithium ion battery (10), comprising a multitude of first particles (11) that contain a cobalt-free lithium layered oxide, and a multitude of second particles (12) that contain a phospho-olivine. Also described is a lithium ion battery (10) comprising a cathode (2) containing said cathode active material.
Description
Kathodenaktivmaterial und Lithiumionen-Batterie mit dem Kathodenaktivmaterial Cathode active material and lithium ion battery having the cathode active material
Die Erfindung betrifft ein Kathodenaktivmaterial für eine Lithiumionen-Batterie und eine Lithiumionen-Batterie mit einem solchen Kathodenaktivmaterial. The invention relates to a cathode active material for a lithium ion battery and a lithium ion battery with such a cathode active material.
Im Folgenden wird der Begriff „Lithiumionen-Batterie“ synonym für alle im Stand der Technik gebräuchlichen Bezeichnungen für Lithium enthaltende galvanische Elemente und Zellen verwendet, wie beispielsweise Lithium-Batterie-Zelle, Lithium-Batterie, Lithium-Zelle, Lithiumionen-Zelle, Lithium-Polymer-Zelle, Lithium-Polymer-Batterie und Lithiumionen- Akkumulator. Insbesondere sind wieder aufladbare Batterien (Sekundärbatterien) inbegriffen. Die Lithiumionen-Batterie kann auch eine Festkörperbatterie sein, beispielsweise eine keramische oder polymerbasierte Festkörperbatterie. In the following, the term "lithium ion battery" is used synonymously for all terms commonly used in the prior art for lithium-containing galvanic elements and cells, such as lithium battery cell, lithium battery, lithium cell, lithium ion cell, lithium Polymer cell, lithium polymer battery and lithium ion accumulator. Specifically, rechargeable batteries (secondary batteries) are included. The lithium-ion battery can also be a solid-state battery, for example a ceramic or polymer-based solid-state battery.
Eine Lithiumionen-Batterie hat mindestens zwei verschiedene Elektroden, eine positive Elektrode (Kathode) und eine negative Elektrode (Anode). Jede dieser Elektroden weist zumindest ein Aktivmaterial auf, wahlweise zusammen mit Zusätzen wie Elektrodenbindern und elektrischen Leitfähigkeitszusätzen. A lithium ion battery has at least two distinct electrodes, a positive electrode (cathode) and a negative electrode (anode). Each of these electrodes includes at least one active material, optionally together with additives such as electrode binders and electrical conductivity additives.
In Lithiumionen-Batterien muss sowohl das Kathodenaktivmaterial als auch das Anodenaktivmaterial in der Lage sein, reversibel Lithiumionen aufzunehmen bzw. abzugeben. Geeignete Kathodenaktivmaterialien sind beispielsweise aus der EP 0 017 400 B1 sowie der DE 3319939 A1 bekannt. In lithium-ion batteries, both the cathode active material and the anode active material must be able to reversibly absorb or release lithium ions. Suitable cathode active materials are known, for example, from EP 0 017 400 B1 and DE 3319939 A1.
In Lithiumionen Batterien für elektrisch angetriebene Fahrzeuge wird häufig Lithium-Nickel- Mangan-Cobalt-Schichtoxid (kurz: NMC) als Kathodenaktivmaterial eingesetzt, da sich NMC insbesondere durch eine hohe Energiedichte auszeichnet. Zur Erhöhung der Energiedichte von NMC kann der Nickel-Anteil erhöht werden, beispielsweise können Zusammensetzungen wie Li(Nio,6Mno,2Coo,2)C>2 (kurz: NMC622) oder Li(Nio,8Mno,iCoo,i)02 (kurz NMC811) eingesetzt werden. Mit der hohen Energiedichte dieser Materialien sind allerdings auch hohe Kosten, eine erhöhte Reaktivität und hohe Sicherheitsanforderungen an die Konstruktion der Batteriezelle verbunden. In lithium-ion batteries for electrically powered vehicles, lithium-nickel-manganese-cobalt layered oxide (NMC for short) is often used as the cathode active material, since NMC is characterized in particular by its high energy density. The nickel content can be increased to increase the energy density of NMC, for example compositions such as Li(Nio,6Mno,2Coo,2)C>2 (short: NMC622) or Li(Nio,8Mno,iCoo,i)02 (short NMC811) can be used. However, the high energy density of these materials is also associated with high costs, increased reactivity and high safety requirements for the design of the battery cell.
Eine zu lösende Aufgabe gemäß einem Aspekt der Erfindung besteht darin, ein verbessertes Kathodenaktivmaterial für eine Lithiumionen-Batterie zur Verfügung zu stellen, das sich
insbesondere durch eine möglichst hohe Energiedichte bei gleichzeitig verminderten Kosten und/oder verbesserter Sicherheit auszeichnet. Weiterhin soll eine Lithiumionen-Batterie mit einem solchen Kathodenaktivmaterial angegeben werden. A problem to be solved according to one aspect of the invention is to provide an improved cathode active material for a lithium ion battery characterized in particular by the highest possible energy density with reduced costs and/or improved safety at the same time. Furthermore, a lithium-ion battery with such a cathode active material is to be specified.
Diese Aufgaben werden gelöst durch ein Kathodenaktivmaterial und eine Lithiumionen-Batterie gemäß den unabhängigen Patentansprüchen. Vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung sind Gegenstand der abhängigen Ansprüche. These objects are solved by a cathode active material and a lithium ion battery according to the independent patent claims. Advantageous refinements and developments of the invention are the subject matter of the dependent claims.
Gemäß einer Ausführungsform der Erfindung umfasst das Kathodenaktivmaterial eine Vielzahl erster Partikel, die ein Cobalt-freies Lithium-Schichtoxid aufweisen oder daraus bestehen. Das Cobalt-freie Lithium-Schichtoxid ist vorzugsweise ein Lithium-Nickel-Mangan-Oxid. Weiterhin umfasst das Kathodenaktivmaterial eine Vielzahl zweiter Partikel, die aus ein Phospho-Olivin aufweisen oder daraus bestehen. Das Phopsho-Olivin ist insbesondere Lithium-Eisen-Phosphat (LFP) oder Lithium-Eisen-Mangan-Phosphat (LFMP). Das Kathodenaktivmaterial ist somit ein gemischtes Kathodenaktivmaterial, das erste Partikel und zweite Partikel der verschiedenen Materialien enthält. According to one embodiment of the invention, the cathode active material comprises a multiplicity of first particles which have or consist of a cobalt-free layered lithium oxide. The cobalt-free layered lithium oxide is preferably a lithium nickel manganese oxide. Furthermore, the cathode active material comprises a multiplicity of second particles which have or consist of a phospho-olivine. The phospho-olivine is in particular lithium iron phosphate (LFP) or lithium iron manganese phosphate (LFMP). The cathode active material is thus a mixed cathode active material containing first particles and second particles of the different materials.
Das hier vorgeschlagene Kathodenaktivmaterial, das sowohl die ersten Partikel als auch die zweiten Partikel aufweist, zeichnet sich im Vergleich zu reinem NMC durch geringere Kosten und eine erhöhte intrinsische Sicherheit aus. Insbesondere hat sich herausgestellt, dass die Beimischung der zweiten Partikel aus dem Phosho-Olivin einen Verzicht auf das Element Cobalt in dem Schichtoxid ermöglicht, ohne die Stabilität des Kathodenaktivmaterials wesentlich zu beeinträchtigen. Das Kathodenaktivmaterial ermöglicht so eine vergleichsweise umweltfreundliche und nachhaltige Herstellung der Kathode. Die Energiedichte des gemischten Kathodenaktivmaterials ist hierbei im Vergleich zu einem reinen Phospho-Olivin erhöht. The cathode active material proposed here, which has both the first particles and the second particles, is characterized by lower costs and increased intrinsic safety compared to pure NMC. In particular, it has been found that the admixture of the second particles from the phosho-olivine makes it possible to dispense with the element cobalt in the layered oxide without significantly impairing the stability of the cathode active material. The cathode active material thus enables the cathode to be manufactured in a comparatively environmentally friendly and sustainable manner. The energy density of the mixed cathode active material is increased compared to a pure phospho-olivine.
Gemäß einer Ausgestaltung weisen die ersten Partikel Liy(Nii.xMnx)O2 mit 0 < x < 1 , insbesondere mit 0,1 < x < 0,9 und 0.9 < y < 1.3 auf. Das Cobalt-freie Lithium-Schichtoxid ist in diesem Fall ein Lithium-Nickel-Oxid, ein Lithium-Nickel-Mangan-Oxid oder ein Lithium-Mangan- Oxid. Es ist möglich, dass das Schichtoxid ein Lithium-reiches Schichtoxid (OLO, over lithiated layered oxide) ist. According to one embodiment, the first particles have Li y (Nii.xMn x )O 2 with 0<x<1, in particular with 0.1<x<0.9 and 0.9<y<1.3. In this case, the cobalt-free lithium layer oxide is a lithium nickel oxide, a lithium nickel manganese oxide or a lithium manganese oxide. It is possible that the layered oxide is a lithium-rich layered oxide (OLO, over lithiated layered oxide).
Bei einer vorteilhaften Ausgestaltung ist der Mangan-Anteil x > 0,5. Bevorzugt ist x > 0,6 oder sogar x > 0,7. In diesem Fall ist das Lithium-Schichtoxid ein Mangan-reiches Lithium-
Schichtoxid. Insbesondere enthält das Lithium-Schichtoxid mehr Mangan als Nickel. Durch den hohen Mangananteil ist das Schichtoxid besonders kostengünstig herstellbar. In an advantageous embodiment, the manganese content is x>0.5. Preferably x > 0.6 or even x > 0.7. In this case the layered lithium oxide is a manganese-rich lithium layered oxide. In particular, the layered lithium oxide contains more manganese than nickel. Due to the high proportion of manganese, the layered oxide can be produced particularly cost-effectively.
Gemäß zumindest einer Ausführungsform weisen die zweiten Partikel LiFePC oder LiFei.yMnyPO4 und 0 < y < 1 auf, d.h. der Phospho-Olivin ist Lithium-Eisenphosphat oder ein Lithium-Eisen-Manganphosphat. According to at least one embodiment, the second particles have LiFePC or LiFei. y Mn y PO4 and 0<y<1, ie the phospho-olivine is lithium iron phosphate or a lithium iron manganese phosphate.
Besonders bevorzugt weisen die zweiten Partikel LiFei.yMnyPO4 mit 0,5 < y < 0,9 auf. Ein solches Mangan-reiches Lithium-Eisen-Mangan-Phosphat zeichnet sich durch eine hohe Energiedichte aus, im Vergleich zum Lithium-Eisen-Phosphat. The second particles particularly preferably have LiFei. y Mn y PO4 with 0.5 < y < 0.9. Such a manganese-rich lithium-iron-manganese phosphate is characterized by a high energy density compared to lithium-iron phosphate.
Gemäß zumindest einer Ausführungsform beträgt ein Anteil der ersten Partikel an der Gesamtheit der ersten und zweiten Partikel zwischen einschließlich 10 Gew.-% und einschließlich 90 Gew.-%, vorzugsweise zwischen einschließlich 20 Gew.-% und einschließlich 80 Gew.-%. According to at least one embodiment, the proportion of the first particles in the total of the first and second particles is between 10% by weight and 90% by weight inclusive, preferably between 20% by weight and 80% by weight inclusive.
Bei einer bevorzugten Ausgestaltung beträgt der Anteil der ersten Partikel an der Gesamtheit der ersten und zweiten Partikel mindestens 70 Gew.-%, insbesondere zwischen einschließlich 70 Gew.-% und einschließlich 90 Gew.-%, besonders bevorzugt mindestens 80 Gew.-%, insbesondere zwischen einschließlich 80 Gew.-% und einschließlich 90 Gew.-%. Beispielsweise kann der Anteil der ersten Partikel 85 Gew.-% und der Anteil der zweiten Partikel 15 Gew.-% betragen. Auf diese Weise kann eine Lithiumionen-Batterie realisiert werden, die sich im Vergleich zu einer Lithiumionen-Batterie, die nur ein Schichtoxid wie NMC als Kathodenaktivmaterial aufweist, durch verringerte Kosten, eine verbesserte thermische Stabilität bei nur geringfügig verringerter Energiedichte auszeichnet. In a preferred embodiment, the proportion of the first particles in the total of the first and second particles is at least 70% by weight, in particular between 70% by weight and 90% by weight inclusive, particularly preferably at least 80% by weight, in particular between 80% by weight and 90% by weight inclusive. For example, the proportion of the first particles can be 85% by weight and the proportion of the second particles can be 15% by weight. In this way, a lithium-ion battery can be realized which, compared to a lithium-ion battery that only has a layer oxide such as NMC as cathode active material, is characterized by reduced costs and improved thermal stability with only slightly reduced energy density.
Bei einer alternativen Ausgestaltung beträgt der Anteil der ersten Partikel an der Gesamtheit der ersten und zweiten Partikel nicht mehr als 50 Gew.-%, insbesondere zwischen einschließlich 10 Gew.-% und einschließlich 50 Gew.-%, besonders bevorzugt nicht mehr als 40 Gew.-%, insbesondere zwischen einschließlich 10 Gew.-% und einschließlich 40 Gew.-%. Beispielsweise kann der Anteil der ersten Partikel 30 Gew-% und der Anteil der zweiten Partikel 70 Gew.-% betragen. Auf diese Weise kann eine Lithiumionen-Batterie realisiert werden, die sich im Vergleich zu einer Lithiumionen-Batterie, die nur ein Schichtoxid wie NMC als Kathodenaktivmaterial aufweist, durch erheblich verringerte Kosten und eine wesentlich
verbesserte thermische Stabilität auszeichnet. Die Energiedichte ist in diesem Fall höher als bei einer Lithiumionen-Batterie, die einen reinen Phospho-Olivin wie LFP als Kathodenaktivmaterial aufweist. Die verbesserte thermische Stabilität des Kathodenaktivmaterials bei dieser Ausgestaltung ermöglicht es insbesondere, die Lithiumionen-Batterie in einem sogenannten „Cell-to-Pack“-Ansatz herzustellen, d.h. mit dem hier vorgeschlagenen Kathodenaktivmaterial kann eine Lithiumionen-Batteriezelle hergestellt werden, die direkt in ein Batteriepack eingefügt wird. Bei dem sogenannten „Cell to Pack“-Ansatz werden die Lithiumionen-Batteriezellen nicht zunächst in Module verbaut, die zusammen eine Lithiumionen-Batterie ausbilden, sondern direkt zu einem Batteriepack zusammengefügt. In an alternative embodiment, the proportion of the first particles in the total of the first and second particles is no more than 50% by weight, in particular between 10% by weight and 50% by weight inclusive, particularly preferably no more than 40% by weight %, in particular between 10% by weight and 40% by weight inclusive. For example, the proportion of the first particles can be 30% by weight and the proportion of the second particles can be 70% by weight. In this way, a lithium ion battery can be realized, which compared to a lithium ion battery, which has only a layer oxide such as NMC as a cathode active material, by significantly reduced cost and a significant improved thermal stability. In this case, the energy density is higher than that of a lithium-ion battery that has a pure phospho-olivine such as LFP as the cathode active material. The improved thermal stability of the cathode active material in this configuration makes it possible in particular to produce the lithium ion battery in a so-called “cell-to-pack” approach, i.e. a lithium ion battery cell can be produced with the cathode active material proposed here, which can be placed directly in a battery pack is inserted. With the so-called "cell to pack" approach, the lithium-ion battery cells are not first installed in modules that together form a lithium-ion battery, but are directly assembled to form a battery pack.
Das Kathodenaktivmaterial kann durch konventionelle Elektroden-Herstellungsprozesse zu einer Kathode (positiven Elektrode), die beispielsweise das Kathodenaktivmaterial, einen Elektroden-Binder und ein elektrisches Leitadditiv wie z. B. Leitruß umfasst, verarbeitet werden. The cathode active material can be formed into a cathode (positive electrode) comprising, for example, the cathode active material, an electrode binder and an electrically conductive additive such as e.g. B. includes conductive carbon black processed.
Es wird weiterhin eine Lithiumionen-Batterie vorgeschlagen, die eine Kathode mit dem zuvor beschriebenen Kathodenaktivmaterial aufweist. Die Kathode kann beispielsweise aus einer Beschichtungsmasse hergestellt werden, die das Kathodenaktivmaterial mit den ersten Partikeln und den zweiten Partikeln, einen Elektroden-Binder und ein elektrisches Leitadditiv wie z. B. Leitruß umfasst. Die Lithiumionen-Batterie kann beispielsweise nur eine einzelne Batteriezelle umfassen oder alternativ ein oder mehrere Module mit mehreren Batteriezellen umfassen, wobei die Batteriezellen in Serie und/oder parallel geschaltet sein können. Die Lithiumionen-Batterie umfasst mindestens eine Kathode, die das Kathodenaktivmaterial aufweist, und eine Anode, die mindestens ein Anodenaktivmaterial aufweist. Weiterhin kann die Lithiumionen-Batterie die an sich bekannten weiteren Bestandteile einer Lithiumionen-Batterie aufweisen, insbesondere Stromkollektoren, einen Separator und einen Elektrolyten. A lithium-ion battery is also proposed which has a cathode with the cathode active material described above. The cathode can be produced, for example, from a coating composition which contains the cathode active material with the first particles and the second particles, an electrode binder and an electrically conductive additive such as e.g. B. includes conductive carbon black. The lithium-ion battery can, for example, only include a single battery cell or alternatively include one or more modules with multiple battery cells, it being possible for the battery cells to be connected in series and/or in parallel. The lithium ion battery includes at least one cathode having the cathode active material and an anode having at least one anode active material. Furthermore, the lithium-ion battery can have the other components of a lithium-ion battery known per se, in particular current collectors, a separator and an electrolyte.
Die erfindungsgemäße Lithiumionen-Batterie kann insbesondere in einem Kraftfahrzeug oder in einem tragbaren Gerät vorgesehen sein. Das tragbare Gerät kann insbesondere ein Smartphone, ein Elektrowerkzeug bzw. Powertool, ein Tablet oder ein Wearable sein. Alternativ kann die Lithiumionen-Batterie auch in einem stationären Energiespeicher eingesetzt werden. The lithium-ion battery according to the invention can be provided in particular in a motor vehicle or in a portable device. The portable device can in particular be a smartphone, an electric tool or power tool, a tablet or a wearable. Alternatively, the lithium-ion battery can also be used in a stationary energy store.
Weitere Vorteile und Eigenschaften der Erfindung ergeben sich aus der nachfolgenden Beschreibung eines Ausführungsbeispiels im Zusammenhang mit den Figuren.
Im Einzelnen zeigen schematisch Further advantages and properties of the invention result from the following description of an exemplary embodiment in connection with the figures. Specifically show schematic
Fig. 1 den Aufbau einer Lithiumionen-Batterie gemäß einem Ausführungsbeispiel, und 1 shows the structure of a lithium-ion battery according to an embodiment, and
Fig. 2 das auf einen Stromkollektor aufgebrachte Kathodenaktivmaterial bei dem Ausführungsbeispiel. 2 shows the cathode active material applied to a current collector in the exemplary embodiment.
Die dargestellten Bestandteile sowie die Größenverhältnisse der Bestandteile untereinander sind nicht als maßstabsgerecht anzusehen. The components shown and the proportions of the components among one another are not to be regarded as true to scale.
Die in Fig. 1 rein schematisch dargestellte Lithiumionen-Batterie 10 weist eine Kathode 2 und eine Anode 5 auf. Die Kathode 2 und die Anode 5 weisen jeweils einen Stromkollektor 1 , 6 auf, wobei die Stromkollektoren als Metallfolien ausgeführt sein können. Der Stromkollektor 1 der Kathode 2 weist zum Beispiel Aluminium und der Stromkollektor 6 der Anode 5 Kupfer auf. The lithium-ion battery 10 shown purely schematically in FIG. 1 has a cathode 2 and an anode 5 . The cathode 2 and the anode 5 each have a current collector 1, 6, it being possible for the current collectors to be in the form of metal foils. The current collector 1 of the cathode 2 has, for example, aluminum and the current collector 6 of the anode 5 has copper.
Die Kathode 2 und die Anode 5 sind durch einen für Lithiumionen durchlässigen, aber für Elektronen undurchlässigen Separator 4 voneinander getrennt. Als Separatoren können Polymere eingesetzt werden, insbesondere ein Polymer ausgewählt aus der Gruppe bestehend aus Polyestern, insbesondere Polyethylenterephthalat, Polyolefinen, insbesondere Polyethylen und/oder Polypropylen, Polyacrylnitrilen, Polyvinylidenfluorid, Polyvinyliden-Hexafluoropropylen, Polyetherimid, Polyimid, Aramid, Polyether, Polyetherketon, synthetische Spinnenseide oder Mischungen davon. Der Separator kann optional zusätzlich mit keramischem Material und einem Binder beschichtet sein, beispielsweise basierend auf AI2O3. The cathode 2 and the anode 5 are separated from one another by a separator 4 which is permeable to lithium ions but impermeable to electrons. Polymers can be used as separators, in particular a polymer selected from the group consisting of polyesters, in particular polyethylene terephthalate, polyolefins, in particular polyethylene and/or polypropylene, polyacrylonitriles, polyvinylidene fluoride, polyvinylidene hexafluoropropylene, polyetherimide, polyimide, aramid, polyether, polyetherketone, synthetic spider silk or mixtures thereof. The separator can optionally also be coated with ceramic material and a binder, for example based on Al2O3.
Zudem weist die Lithiumionen-Batterie einen Elektrolyten 3 auf, der leitend für Lithiumionen ist und der ein Feststoffelektrolyt oder eine Flüssigkeit sein kann, die ein Lösungsmittel und zumindest ein darin gelöstes Lithium-Leitsalz, beispielsweise Lithium-Hexafluorophosphat (LiPFe), umfasst. Das Lösungsmittel ist vorzugsweise inert. Geeignete Lösungsmittel sind beispielsweise organische Lösungsmittel wie Ethylencarbonat, Propylencarbonat, Butylencarbonat, Dimethylcarbonat, Diethylcarbonat, Ethylmethylcarbonat, Fluorethylencarbonat (FEC), Sulfolane, 2-Methyltetrahydrofuran, Acetonitril und 1 ,3-Dioxolan. Als Lösungsmittel können auch ionische Flüssigkeiten verwendet werden. Solche ionischen Flüssigkeiten enthalten ausschließlich Ionen. Bevorzugte Kationen, die insbesondere alkyliert sein können, sind Imidazolium-, Pyridinium-, Pyrrolidinium-, Guanidinium-, Uronium-,
Thiuronium-, Piperidinium-, Morpholinium-, Sulfonium-, Ammonium- und Phosphonium- Kationen. Beispiele für verwendbare Anionen sind Halogenid-, Tetrafluoroborat-, Trifluoracetat-, Triflat-, Hexafluorophosphat-, Phosphinat- und Tosylat-Anionen. Als beispielhafte ionische Flüssigkeiten seien genannt: N-Methyl-N-propyl-piperidinium-bis(trifluormethylsulfonyl)imid, N- Methyl-N-butyl-pyrrolidinium-bis(tri-fluormethyl-sulfonyl)imid, N-Butyl-N-trimethyl-ammonium- bis(trifluormethyl-sulfonyl)imid, Triethylsulfonium-bis(trifluormethylsulfonyl)imid und N,N-Diethyl- N-methyl-N-(2-methoxyethyl)-ammonium-bis(trifluormethylsulfonyl)-imid. In einer Variante können zwei oder mehrere der oben genannten Flüssigkeiten verwendet werden. Bevorzugte Leitsalze sind Lithiumsalze, welche inerte Anionen aufweisen und welche vorzugsweise nicht toxisch sind. Geeignete Lithiumsalze sind insbesondere Lithiumhexafluorophosphat (LiPFe), Lithiumtetrafluoroborat (UBF4) und Mischungen dieser Salze. Der Separator 4 kann mit dem Lithiumsalz-Elektrolyt getränkt bzw. benetzt sein, wenn dieser flüssig ist. In addition, the lithium ion battery has an electrolyte 3 which is conductive for lithium ions and which can be a solid electrolyte or a liquid which includes a solvent and at least one lithium conducting salt, for example lithium hexafluorophosphate (LiPFe), dissolved therein. The solvent is preferably inert. Examples of suitable solvents are organic solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, fluoroethylene carbonate (FEC), sulpholane, 2-methyltetrahydrofuran, acetonitrile and 1,3-dioxolane. Ionic liquids can also be used as solvents. Such ionic liquids contain only ions. Preferred cations, which can be alkylated in particular, are imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, Thiuronium, piperidinium, morpholinium, sulfonium, ammonium and phosphonium cations. Examples of anions that can be used are halide, tetrafluoroborate, trifluoroacetate, triflate, hexafluorophosphate, phosphinate and tosylate anions. Examples of ionic liquids which may be mentioned are: N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide, N-methyl-N-butylpyrrolidinium bis(trifluoromethylsulfonyl)imide, N-butyl-N-trimethyl -ammonium bis(trifluoromethylsulfonyl)imide, triethylsulfonium bis(trifluoromethylsulfonyl)imide and N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide. In a variant, two or more of the above liquids can be used. Preferred conductive salts are lithium salts which have inert anions and which are preferably non-toxic. Suitable lithium salts are, in particular, lithium hexafluorophosphate (LiPFe), lithium tetrafluoroborate (UBF4) and mixtures of these salts. The separator 4 can be impregnated or wetted with the lithium salt electrolyte if it is liquid.
Die Anode 5 weist ein Anodenaktivmaterial auf. Das Anodenaktivmaterial kann ausgewählt sein aus der Gruppe bestehend aus kohlenstoffhaltigen Materialien, Silizium, Silizium-Suboxid, Siliziumlegierungen, Aluminiumlegierungen, Indium, Indiumlegierungen, Zinn, Zinnlegierungen, Kobaltlegierungen und Mischungen davon. Bevorzugt ist das Anodenaktivmaterial ausgewählt aus der Gruppe bestehend aus synthetischem Graphit, Naturgraphit, Graphen, Mesokohlenstoff, dotiertem Kohlenstoff, Hardcarbon, Softcarbon, Fulleren, Silizium-Kohlenstoff- Komposit, Silizium, oberflächenbeschichteten Silizium, Silizium-Suboxid, Siliziumlegierungen, Lithium, Aluminiumlegierungen, Indium, Zinnlegierungen, Kobaltlegierungen und Mischungen davon. Grundsätzlich eignen sich auch weitere an sich aus dem Stand der Technik bekannten Anodenaktivmaterialien, beispielsweise auch Niobpentoxid, Titandioxid, Titanate wie Lithium- Titanat (Li4TisOi2), Zinndioxid, Lithium, Lithiumlegierungen und/oder Mischungen davon. The anode 5 has an anode active material. The anode active material may be selected from the group consisting of carbonaceous materials, silicon, silicon suboxide, silicon alloys, aluminum alloys, indium, indium alloys, tin, tin alloys, cobalt alloys, and mixtures thereof. The anode active material is preferably selected from the group consisting of synthetic graphite, natural graphite, graphene, mesocarbon, doped carbon, hard carbon, soft carbon, fullerene, silicon-carbon composite, silicon, surface-coated silicon, silicon suboxide, silicon alloys, lithium, aluminum alloys, indium , tin alloys, cobalt alloys and mixtures thereof. In principle, other anode active materials known from the prior art are also suitable, for example niobium pentoxide, titanium dioxide, titanates such as lithium titanate (Li4TisOi2), tin dioxide, lithium, lithium alloys and/or mixtures thereof.
Die Figur 2 zeigt eine schematische Darstellung der Kathode 2 auf dem Stromkollektor 1 , der insbesondere eine Aluminiumfolie sein kann. Die Kathode 2 weist ein Kathodenaktivmaterial auf. Das Kathodenaktivmaterial weist eine Vielzahl von ersten Partikeln 11 und zweiten Partikeln 12 auf. Die Partikel 11, 12 können in einen Elektrodenbinder 13, ggf. mit einem die Leitfähigkeit erhöhenden Additiv wie zum Beispiel einem Leitruß, eingebunden sein. FIG. 2 shows a schematic representation of the cathode 2 on the current collector 1, which can in particular be an aluminum foil. The cathode 2 has a cathode active material. The cathode active material has a multiplicity of first particles 11 and second particles 12 . The particles 11, 12 can be bound into an electrode binder 13, possibly with an additive that increases the conductivity, such as a conductive carbon black.
Die ersten Partikel 11 weisen ein Cobalt-freies Schichtoxid auf, insbesondere Li(Nii-xMnx)O2 mit 0 < x < 1. Für dem Mangan-Anteil x gilt vorzugsweise x > 0,5, besonders bevorzugt x > 0,6. Die zweiten Partikel 12 weisen einen Phospho-Olivin auf, insbesondere LiFei.yMnyPO4 mit 0 < y < 1.
Ein besonders gutes Verhältnis von Kosten und Energiedichte wird erzielt, wenn die ersten Partikel 11 ein Mangan-reiches Schichtoxid, insbesondere Li(Nii.xMnx)O2 mit x > 0,5, vorzugsweise x > 0,6, und die zweiten Partikel 12 ein Mangan-reiches Lithium-Eisen-Mangan- Phosphat, insbesondere LiFei.yMnyPO4 mit 0,5 < y < 0,9, aufweisen. The first particles 11 have a cobalt-free layered oxide, in particular Li(Nii-xMn x )O2 with 0<x<1. For the manganese proportion x, x>0.5 preferably applies, particularly preferably x>0.6. The second particles 12 have a phospho-olivine, in particular LiFel. y Mn y PO4 with 0 < y < 1. A particularly good ratio of costs and energy density is achieved when the first particles 11 are a manganese-rich layer oxide, in particular Li( Ni.xMnx )O2 with x >0.5, preferably x>0.6, and the second particles 12 a manganese-rich lithium-iron-manganese phosphate, in particular LiFei. y Mn y PO4 with 0.5 < y < 0.9.
Die der Anteil der ersten Partikel 11 an der Gesamtheit der Partikel 11 , 12 kann zwischen einschließlich 10% und einschließlich 90%, insbesondere zwischen einschließlich 20% und einschließlich 80%, betragen. Bei einer Ausgestaltung, bei der eine möglichst hohe Energiedichte bei noch moderaten Kosten erzielt werden soll, beträgt der Anteil der ersten Partikel 11 zwischen einschließlich 70% und einschließlich 90%, beispielsweise etwa 85%. Der Anteil der zweiten Partikel 12 beträgt in diesem Fall entsprechend zwischen einschließlich 10% und einschließlich 30%, beispielsweise etwa 15%. The proportion of the first particles 11 in the totality of the particles 11 , 12 can be between 10% and 90% inclusive, in particular between 20% and 80% inclusive. In an embodiment in which the highest possible energy density is to be achieved at still moderate costs, the proportion of the first particles 11 is between 70% and 90% inclusive, for example approximately 85%. In this case, the proportion of the second particles 12 is between 10% and 30% inclusive, for example approximately 15%.
Bei einer alternativen Ausgestaltung, bei der möglichst niedrige Kosten bei einer noch guten Energiedichte erzielt werden sollen, beträgt der Anteil der ersten Partikel 11 zwischen einschließlich 10% und einschließlich 50%, beispielsweise etwa 30%. Der Anteil der zweiten Partikel 12 beträgt in diesem Fall entsprechend zwischen einschließlich 50% und einschließlich 90%, beispielsweise etwa 70%. In an alternative embodiment, in which the lowest possible costs are to be achieved with an energy density that is still good, the proportion of the first particles 11 is between 10% and 50% inclusive, for example approximately 30%. In this case, the proportion of the second particles 12 is between 50% and 90% inclusive, for example approximately 70%.
Obwohl die Erfindung im Detail anhand von Ausführungsbeispielen illustriert und beschrieben wurde, so ist die Erfindung nicht durch die Ausführungsbeispiele eingeschränkt. Vielmehr können andere Variationen der Erfindung vom Fachmann hieraus abgeleitet werden, ohne den durch die Ansprüche definierten Schutzumfang der Erfindung zu verlassen.
Although the invention has been illustrated and described in detail using exemplary embodiments, the invention is not restricted by the exemplary embodiments. On the contrary, other variations of the invention can be derived therefrom by a person skilled in the art without departing from the protective scope of the invention as defined by the claims.
Bezugszeichenliste Reference List
1 Stromkollektor 1 current collector
2 Kathode 3 Elektrolyt 2 cathode 3 electrolyte
4 Separator 4 separators
5 Anode 5 anode
6 Stromkollektor 6 current collector
10 Lithiumionen-Batterie 11 erste Partikel 10 lithium ion battery 11 first particles
12 zweite Partikel 12 second particles
13 Elektrodenbinder
13 electrode ties
Claims
1. Kathodenaktivmaterial für eine Lithiumionen-Batterie (10), umfassend A cathode active material for a lithium ion battery (10) comprising
- eine Vielzahl erster Partikel (11), die ein Cobalt-freies Lithium-Schichtoxid aufweisen und - A multiplicity of first particles (11) which have a cobalt-free layered lithium oxide and
- eine Vielzahl zweiter Partikel (12), die ein Phopsho-Olivin aufweisen. - a plurality of second particles (12) comprising a phospho-olivine.
2. Kathodenaktivmaterial nach Anspruch 1 , wobei die ersten Partikel (11) Liy(Nii.xMnx)O2 mit 0 < x < 1 und 0.9 < y < 1.3 aufweisen. 2. Cathode active material according to claim 1, wherein the first particles (11) have Li y (Nii.xMn x )O 2 with 0<x<1 and 0.9<y<1.3.
3. Kathodenaktivmaterial nach Anspruch 2, wobei x > 0,5 ist. 3. Cathode active material according to claim 2, wherein x> 0.5.
4. Kathodenaktivmaterial nach Anspruch 3, wobei x > 0,6 ist. 4. Cathode active material according to claim 3, wherein x> 0.6.
5. Kathodenaktivmaterial nach einem der vorhergehenden Ansprüche, wobei die zweiten Partikel (12) LiFei.yMnyPC mit 0 < y < 1 aufweisen. 5. Cathode active material according to one of the preceding claims, wherein the second particles (12) have LiFei.yMnyPC with 0<y<1.
6. Kathodenaktivmaterial nach einem der vorhergehenden Ansprüche, wobei die zweiten Partikel (12) LiFei.yMnyPO4 mit 0,5 < y < 0,9 aufweisen. 6. cathode active material according to any one of the preceding claims, wherein the second particles (12) LiFei. y Mn y PO4 with 0.5 < y < 0.9.
7. Kathodenaktivmaterial nach einem der vorhergehenden Ansprüche, wobei ein Anteil der ersten Partikel (11) an der Gesamtheit der ersten und zweiten Partikel (11 , 12) zwischen einschließlich 10 Gew.-% und einschließlich 90 Gew.-% beträgt. 7. Cathode active material according to one of the preceding claims, wherein a proportion of the first particles (11) in the totality of the first and second particles (11, 12) is between 10% by weight and 90% by weight inclusive.
8. Kathodenaktivmaterial nach einem der vorhergehenden Ansprüche, wobei ein Anteil der ersten Partikel (11) an der Gesamtheit der ersten und zweiten Partikel (11 , 12) zwischen einschließlich 70 Gew.-% und einschließlich 90 Gew.-% beträgt. 8. Cathode active material according to one of the preceding claims, wherein a proportion of the first particles (11) in the totality of the first and second particles (11, 12) is between 70% by weight and 90% by weight inclusive.
9. Kathodenaktivmaterial nach einem der Ansprüche 1 bis 7, wobei ein Anteil der ersten Partikel (11) an der Gesamtheit der ersten und zweiten
Partikel (11, 12) zwischen einschließlich 10 Gew.-% und einschließlich 50 Gew.-% beträgt. Lithiumionen-Batterie (10), umfassend mindestens eine Kathode (2) mit einem Kathodenaktivmaterial nach einem der Ansprüche 1 bis 9.
9. cathode active material according to any one of claims 1 to 7, wherein a proportion of the first particles (11) in the totality of the first and second particles (11, 12) is between 10% by weight and 50% by weight inclusive. A lithium ion battery (10) comprising at least one cathode (2) having a cathode active material according to any one of claims 1 to 9.
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EP0017400B1 (en) | 1979-04-05 | 1984-05-30 | United Kingdom Atomic Energy Authority | Electrochemical cell and method of making ion conductors for said cell |
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