WO2017037179A1 - Oxyde mixte revêtu d'une enveloppe, contenant du lithium et du manganèse - Google Patents
Oxyde mixte revêtu d'une enveloppe, contenant du lithium et du manganèse Download PDFInfo
- Publication number
- WO2017037179A1 WO2017037179A1 PCT/EP2016/070620 EP2016070620W WO2017037179A1 WO 2017037179 A1 WO2017037179 A1 WO 2017037179A1 EP 2016070620 W EP2016070620 W EP 2016070620W WO 2017037179 A1 WO2017037179 A1 WO 2017037179A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- core
- shell
- shell particles
- compound
- mol
- Prior art date
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 14
- 239000011572 manganese Substances 0.000 title claims description 12
- 229910052748 manganese Inorganic materials 0.000 title claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 41
- 239000011258 core-shell material Substances 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 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 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 150000002736 metal compounds Chemical class 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 aluminum compound Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000000443 aerosol Substances 0.000 claims description 9
- 150000003377 silicon compounds Chemical class 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 150000001869 cobalt compounds Chemical class 0.000 claims description 6
- 239000002737 fuel gas Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 150000002642 lithium compounds Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 101150103023 ddo-2 gene Proteins 0.000 claims description 3
- 150000002697 manganese compounds Chemical class 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910004028 SiCU Inorganic materials 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 229910052810 boron oxide Inorganic materials 0.000 claims 1
- 150000001649 bromium compounds Chemical class 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005118 spray pyrolysis Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910014549 LiMn204 Inorganic materials 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- VAROLYSFQDGFMV-UHFFFAOYSA-K di(octanoyloxy)alumanyl octanoate Chemical compound [Al+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VAROLYSFQDGFMV-UHFFFAOYSA-K 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000006199 nebulizer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
- C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
- C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
-
- 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
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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 sheath surrounded, containing lithium and manganese mixed oxide, its preparation and use.
- US2005 / 106463 discloses an electrode material for a lithium secondary battery containing mixed lithium / transition metal oxides and boron.
- the electrode material has a specific surface area of 0.1 to 8 m 2 / g and a tamped density of 1.6 g to 3.0 g / cm 3 .
- the electrode material is prepared by mixing a mixture of a lithium, nickel, manganese and cobalt compound and boric acid in the desired stoichiometric ratio with each other, from which produces a dispersion in water, the dispersion milled until a particle diameter of 30 ⁇ is reached. This is followed by spray drying.
- the material thus obtained is thermally treated at elevated temperature.
- the tamped density varies with the type of thermal treatment.
- the method mentioned in US2005 / 106463 comprises many steps. It is known to produce electrode materials in a simpler way via a flame spray pyrolysis. Thus, in WO 201 1/160940 a process for the preparation of a lithium
- Metal compound containing as metal component Ag, Al, B, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, In, Mg, Mn, Mo, Nb, Ni, Pd, Rh, Ru, Sc, Sn, Ti , V, Y or Zn is atomized by means of a nebulizer gas to an aerosol and burned in an oxygen / hydrogen flame.
- EP-A-3026019 discloses a powdered cathode material in the form of aggregated primary particles comprising a mixed oxide powder which has a composition corresponding to
- Lii + x (Ni a CobMn c ) DdO 2, and H and N as a non-metal component, having a content of H 0.01 - 0, 1 wt .-% and a content of N of 0.002-0.05 wt .-% and wherein D Ag, Al, B, Ca, Cr, Cu, Fe, Ga, Ge, In, K, Mg, Mo, Na, Nb, Si, Sn, Ta, Ti, Ti, V, and Zr and 0 ⁇ x ⁇ 0.2; 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 1; 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 0.2. It is prepared by adding a solution containing a lithium compound and at least one other metal compound selected from the group consisting of Mn, Ni and Co and an ammonia-containing aerosol in one
- all soluble doping compounds which are oxidizable can be used. These may be inorganic metal compounds or organic metal compounds.
- a particularly preferred doping component is Al.
- the doping compound is preferably used in an amount such that the later cathode material does not contain more than 10% by weight of doping component, more preferably 0.1 to 5% by weight.
- Kalaignan et al. in Journal of Power Sources 196 (201 1) 3640-3645 describe the preparation of silica-clad LiMn204 cathode material via a gel route and subsequent thermal treatment. Accordingly, the crystal structure is not changed by the shell, the electrochemical properties improved.
- Park et al. in Journal of Power Sources 126 (2004) 150-155 describe the preparation of alumina-clad LiMn2-xZr x 04 via a sol-gel route. Again, the cladding leads to improved electrochemical properties, as compared to the non-clad material.
- the object of the present invention was to provide cathode materials which have again improved electrochemical properties compared with this prior art. Another object was to provide a method for these cathode materials.
- the invention relates to core-shell particles (1), wherein the core comprises a mixed oxide containing lithium and manganese, characterized in that
- the shell largely consists of silica and alumina or
- the shell consists largely of silica or alumina and
- the BET surface area is 10 to 30 m 2 / g, preferably 15 to 25 m 2 / g.
- the silica is an X-ray amorphous silica. Boron should be considered as metal in the context of this invention.
- the present invention claims two types of core shell particles.
- the core-shell particles (1) have, for example, a higher BET surface area than the core-shell particles (2).
- the core-shell particles (1) are the product of flame spray pyrolysis.
- the core-shell particles (2) can be obtained by thermal aftertreatment of the core-shell particles (1).
- Mixed oxide is the intimate mixing of all mixed oxide components to understand. It is therefore largely a mixture at the atomic level, not a physical mixture of oxides.
- the mixed oxide particles are generally present in the form of aggregated primary particles.
- Composition contains.
- the presence of Lio, 78Mno, 8s02 or Lio, 96Mno, 7402 besides the main phase is called LiMri204.
- the coating constituents contain only conventional, due to the production of these products impurities in conventional amounts.
- Impurities from silica may be iron oxides, titania, alumina or hydrochloric acid.
- Impurities from alumina can be iron oxides, titanium oxide,
- Be silica or hydrochloric acid The usual amount is understood to mean that the proportion of the coating constituents silicon dioxide and aluminum oxide is at least 98% by weight, generally at least 99% by weight or 99.5% by weight.
- the core-shell particles (1) generally have an acceptable tamped density of 300-600 g / l.
- the BET surface area is determined according to DIN ISO 9277.
- the tamped density is determined according to DIN EN ISO 787/1 1.
- the shell consists essentially of silica and alumina
- a ratio Si / Al of 0, 1-100 mol / mol has been found to be preferred and 0.2-10 mol / mol is particularly preferred.
- the ratio M / (Li + Mn) is preferably 0.001-0.5 mol / mol, and more preferably 0.005-0.03 mol / mol.
- Alumina and / or boria are the preferred additional metal oxides in the core.
- the core may also contain nickel and / or cobalt.
- Another object of the invention is a process for the preparation of the core-shell particles (1), wherein
- metal M Al, B, Ca, Nb, Ta, Ti and V,
- the aerosol can be prepared by co-sputtering a metal compound and a
- Atomizing gas can be obtained by means of one or more nozzles.
- Lithium, manganese, nickel and cobalt compound, and the metal compound can be used as such even in liquid form or in the form of a solution.
- the nature of the metal compounds is not limited as long as they are hydrolyzable or pyrolyzable under the reaction conditions to form the metal oxides.
- chlorides, nitrates or organometallic compounds can be used.
- the solution contains different metal compounds of one metal or more metal compounds with different metal components. In the latter case mixed metal oxides are formed.
- air, oxygen-enriched air and / or an inert gas such as nitrogen can be used as sputtering gas.
- Cobalt compound as well as the metal compound in a solution.
- the solution can be heated. Particular preference may be given to using water or a mixture of water and an organic solvent.
- organic solvents include water or a mixture of water and an organic solvent.
- alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol or tert-butanol
- diols such as ethanediol, pentanediol, 2-methyl-2,4-pentanediol
- C1- C12 carboxylic acids such as acetic, propionic, butanoic, hexanoic, oxalic, malonic, succinic, glutaric, adipic, octanoic, 2-ethylhexanoic, valeric, capric,
- Lauric acid can be used. Furthermore, benzene, toluene, naphtha and / or gasoline can be used. Preferably, an aqueous solvent is used.
- a silicon compound and / or aluminum compound each of which is hydrolyzable or pyrolyzable, is added to the reaction mixture from the first zone.
- SiCU preferably selected from the group consisting of SiCU, CH 3 SCl 3 , (Ch 2 SiCk, (CH 2 SiCl, HSiCIs, (CH 3 ) 2 HSiCl and CH 3 C 2 H 5 SCl 2, H 4 Si, Si (OC 2 H 5 ) 4 and Si (OCH 3 ) 4 and the
- the timing of addition of the silicon compound and / or aluminum compound is to be chosen so that the particle formation of the core constituents in the first zone is well advanced or already completed. This time depends among other things on the execution of the
- the average residence time in the first zone and the second zone is independently 0.1 - 10 s.
- a particular embodiment provides that ammonia is introduced into the reaction space. This can be achieved, for example, by adding ammonia to the aerosol.
- concentration of ammonia is preferably 0.01-2 Nm 3 / mol (Li + Mn), more preferably 0.05-1.5 Nim 3 / mol (Li + Mn). The addition of ammonia seems to affect the
- Another object of the invention are core-shell particles (2), wherein the core comprises a lithium and manganese-containing mixed oxide, and
- the shell largely consists of silica and alumina or
- the shell consists largely of silica or alumina and
- the BET surface area is less than 10 m 2 / g.
- core-shell particles (2) These particles are to be referred to in the context of the present invention as core-shell particles (2). They differ from the core-shell particles (1), inter alia, in a lower BET surface area and a higher crystallinity.
- the further metal oxide is alumina and the tamped density of the core-shell particles (2) is 700-1500 g / l.
- Another object of the invention is a process for the preparation of the core-shell particles (2) in which the core-shell particles (1) are thermally treated. Preferably, this is done at 800 to 1000 ° C and over a period of 1 to 10 hours.
- the production of the core-shell particles (2) comprises the process steps for the production of the core-shell particles (1).
- the production of the core-shell particles (2) includes a
- metal M Al, B, Ca, Nb, Ta, Ti and V,
- Another object of the invention is the use of the core-shell particles (2) produced by the novel process as the cathode material in lithium-ion batteries.
- an aerosol is generated by means of a nozzle, which is atomized into a reaction space.
- a blast gas flame burns out of hydrogen and air, in which the aerosol is brought to the reaction.
- the mean residence time of the reaction mixture in the first zone is 0.75 s in Examples 1 and 2 and 1.75 s in Examples 3-6.
- vapor Si (OC2Hs) 4 and / or vaporous Al (OiBu) 3 is added to the stream of the reaction mixture from the first zone, in each case together with nitrogen, and separately 2.5 kg / h of steam.
- the average residence time of the reaction mixture in the second zone is 0.9 s in Examples 3-6.
- the solid After cooling, the solid is separated on a filter of gaseous substances.
- Comparative Example 1 has neither a shell nor an additional metal oxide.
- Comparative Example 2 has a SiC shell, but no additional metal oxide in the core.
- Inventive Example 3 has an SiC shell and Al 2 O 3 as an additional metal oxide in the core.
- Inventive Examples 4-6 have a shell of S1O2 and Al2O3 and Al2O3 as an additional metal oxide in the core.
- the proportion of Al2O3 in Examples 4-6 increases.
- Table 2 shows that the shell and the additional AI2O3 in the core leads to an improvement of the electrochemical data.
- Table 1 Starting materials and reaction conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Catalysts (AREA)
Abstract
Particule cœur-écorce (1) dont le cœur comprend un oxyde mixte contenant du lithium et du manganèse, et se caractérisant en ce que a) l'enveloppe se compose majoritairement de dioxyde de silicium et d'oxyde d'aluminium ou b) l'enveloppe se compose majoritairement de dioxyde de silicium ou d'oxyde d'aluminium et le noyau contient en complément au moins un autre oxyde d'un métal M tel que M = AI, B, Ca, Nb, Ta, Ti et V, et c) la surface BET vaut 10-30 m2/g.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102015216901.4 | 2015-09-03 | ||
DE102015216901.4A DE102015216901A1 (de) | 2015-09-03 | 2015-09-03 | Mit einer Hülle umgebenes Lithium und Mangan enthaltendes Mischoxid |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017037179A1 true WO2017037179A1 (fr) | 2017-03-09 |
Family
ID=56896520
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2016/070620 WO2017037179A1 (fr) | 2015-09-03 | 2016-09-01 | Oxyde mixte revêtu d'une enveloppe, contenant du lithium et du manganèse |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE102015216901A1 (fr) |
WO (1) | WO2017037179A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111193019A (zh) * | 2020-01-13 | 2020-05-22 | 惠州亿纬锂能股份有限公司 | 一种补锂添加剂及其制备方法和锂离子电池 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2399867A1 (fr) * | 2010-06-25 | 2011-12-28 | Evonik Degussa GmbH | Procédé de fabrication d'oxydes mixtes contenant du lithium |
US20120040247A1 (en) * | 2010-07-16 | 2012-02-16 | Colorado State University Research Foundation | LAYERED COMPOSITE MATERIALS HAVING THE COMPOSITION: (1-x-y)LiNiO2(xLi2Mn03)(yLiCoO2), AND SURFACE COATINGS THEREFOR |
WO2014142803A1 (fr) * | 2013-03-12 | 2014-09-18 | Sachem, Inc. | Formation d'une coque d'oxyde sur des substrats inorganiques par déposition de sel de polyoxoanion de lithium |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7241532B2 (en) | 2002-03-28 | 2007-07-10 | Mitsubishi Chemical Corporation | Positive-electrode material for lithium secondary battery, secondary battery employing the same, and process for producing positive-electrode material for lithium secondary battery |
EP3026019A1 (fr) | 2014-11-25 | 2016-06-01 | Evonik Degussa GmbH | Procédé de fabrication d'un matériau de cathode et matériau de cathode spécial |
-
2015
- 2015-09-03 DE DE102015216901.4A patent/DE102015216901A1/de not_active Withdrawn
-
2016
- 2016-09-01 WO PCT/EP2016/070620 patent/WO2017037179A1/fr active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2399867A1 (fr) * | 2010-06-25 | 2011-12-28 | Evonik Degussa GmbH | Procédé de fabrication d'oxydes mixtes contenant du lithium |
US20120040247A1 (en) * | 2010-07-16 | 2012-02-16 | Colorado State University Research Foundation | LAYERED COMPOSITE MATERIALS HAVING THE COMPOSITION: (1-x-y)LiNiO2(xLi2Mn03)(yLiCoO2), AND SURFACE COATINGS THEREFOR |
WO2014142803A1 (fr) * | 2013-03-12 | 2014-09-18 | Sachem, Inc. | Formation d'une coque d'oxyde sur des substrats inorganiques par déposition de sel de polyoxoanion de lithium |
Non-Patent Citations (1)
Title |
---|
J.-S. KIM ET AL: "The Electrochemical Stability of Spinel Electrodes Coated with ZrO[sub 2], Al[sub 2]O[sub 3], and SiO[sub 2] from Colloidal Suspensions", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 151, no. 10, 1 January 2004 (2004-01-01), US, pages A1755, XP055310521, ISSN: 0013-4651, DOI: 10.1149/1.1793713 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111193019A (zh) * | 2020-01-13 | 2020-05-22 | 惠州亿纬锂能股份有限公司 | 一种补锂添加剂及其制备方法和锂离子电池 |
Also Published As
Publication number | Publication date |
---|---|
DE102015216901A1 (de) | 2017-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2399867B1 (fr) | Procédé de fabrication d'oxydes mixtes contenant du lithium | |
EP2303780B1 (fr) | Procédé de préparation d'un spinelle de lithium-titane | |
EP3337764B1 (fr) | Particules d'oxyde de métaux de transition à base de lithium-nickel-manganèse, leur production ainsi que leur utilisation en tant que matériau d'électrode | |
EP2399869B1 (fr) | Poudre d'oxyde mixte contenant les éléments lithium, manganèse, nickel et cobalt et leur procédé de fabrication | |
WO2015173114A1 (fr) | Procédé de production de poudre d'oxyde mixte contenant du lithium, du lanthane et du zirconium | |
EP1791785A2 (fr) | Procede pour produire des composes d'oxydes metalliques, a plusieurs constituants, renfermant des metaux alcalins, et composes d'oxydes metalliques ainsi produits | |
EP3224200B1 (fr) | Procédé de fabrication d'oxydes métalliques par pyrolyse par pulvérisation | |
WO2016083142A1 (fr) | Procédé de production d'un matériau cathodique et matériau cathodique spécial | |
EP3565784B1 (fr) | Procédé de fabrication d'oxydes métalliques au moyen de pyrolyse par pulvérisation | |
WO2018024661A1 (fr) | Procédé de fabrication d'un matériau de cathode à faible surface bet et à masse volumique tassée élevée et matériau de cathode spécial | |
WO2017148911A1 (fr) | Procédé de fabrication d'un matériau composite silicium-carbone | |
DE102012204148A1 (de) | Calciumoxid enthaltendes Pulver, seine Herstellung und Verwendung | |
EP1785395B1 (fr) | Procédé de préparation de particules d'oxyde métallique dopé | |
EP3807214B1 (fr) | Traitement thermique de particules de silicium | |
EP2944611A1 (fr) | Procédé de fabrication d'un systèmes d'oxydes mixtes cristallins cubiques, contenant de l'aluminium, du lithium, du lanthane et du zircon ayant une structure à grenat | |
WO2016169842A1 (fr) | Procédé de fabrication d'une matière de cathode à faible surface bet et à haute densité de la matière tassée | |
DE102004039139A1 (de) | Yttrium-Zirkon-Mischoxidpulver | |
WO2017037179A1 (fr) | Oxyde mixte revêtu d'une enveloppe, contenant du lithium et du manganèse | |
DE10317067A1 (de) | Domänen in einer Metalloxid-Matrix | |
WO2013092110A1 (fr) | Oxyde mixte contenant les éléments lithium, nickel, cobalt et manganèse et son procédé de fabrication | |
EP2556028B1 (fr) | Particules d'oxyde de fer-silicium de type janus | |
DE102005037772B3 (de) | Verfahren zur Herstellung eines Wasserstoff-Speichermaterials | |
WO2021164846A1 (fr) | Matériaux actifs d'anode pour batteries au lithium-ion |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16763475 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16763475 Country of ref document: EP Kind code of ref document: A1 |