CN104737334B - 涂布有金属的电极活性材料前体及其制备方法 - Google Patents
涂布有金属的电极活性材料前体及其制备方法 Download PDFInfo
- Publication number
- CN104737334B CN104737334B CN201380055182.6A CN201380055182A CN104737334B CN 104737334 B CN104737334 B CN 104737334B CN 201380055182 A CN201380055182 A CN 201380055182A CN 104737334 B CN104737334 B CN 104737334B
- Authority
- CN
- China
- Prior art keywords
- precursor
- metal
- electrode active
- coated
- metal material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 69
- 239000007772 electrode material Substances 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims description 30
- 239000002184 metal Substances 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title description 8
- 238000006263 metalation reaction Methods 0.000 title description 3
- 239000007769 metal material Substances 0.000 claims abstract description 30
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- 229910005565 NiaMnb Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- -1 transition metal gas hydrate Chemical class 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 239000011572 manganese Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910017095 Ni0.6Mn0.2Co0.2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910018039 Cu2V2O7 Inorganic materials 0.000 description 1
- 229910017354 Fe2(MoO4)3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910007969 Li-Co-Ni Inorganic materials 0.000 description 1
- 229910006570 Li1+xMn2-xO4 Inorganic materials 0.000 description 1
- 229910006628 Li1+xMn2−xO4 Inorganic materials 0.000 description 1
- 229910010228 Li2Mn3MO8 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014172 LiMn2-xMxO2 Inorganic materials 0.000 description 1
- 229910014774 LiMn2O3 Inorganic materials 0.000 description 1
- 229910014437 LiMn2−XMXO2 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910014713 LiMnO3 Inorganic materials 0.000 description 1
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- 229910014114 LiNi1-xMxO2 Inorganic materials 0.000 description 1
- 229910014907 LiNi1−xMxO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012967 LiV3O4 Inorganic materials 0.000 description 1
- 229910012970 LiV3O8 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910016622 LixFe2O3 Inorganic materials 0.000 description 1
- 229910015103 LixWO2 Inorganic materials 0.000 description 1
- 229910006555 Li—Co—Ni Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- VQWQYXBWRCCZGX-UHFFFAOYSA-N acetic acid;manganese Chemical compound [Mn].CC(O)=O.CC(O)=O VQWQYXBWRCCZGX-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/049—Processes for forming or storing electrodes in the battery container
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
-
- 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
-
- 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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本发明公开了锂二次电池用电极活性材料的前体及制备其的方法,其中通过电解分解可电离的金属材料均匀涂布在由过渡金属水合物形成的初级前体的表面上。
Description
技术领域
本发明涉及涂布有金属的电极活性材料前体及其制备方法。更特别地,本发明涉及锂二次电池用电极活性材料的前体及其制备方法,其中通过电解分解可电离的金属材料均匀涂布在由过渡金属水合物形成的初级前体的表面上。
背景技术
随着移动设备技术的持续发展和对其需求的持续增加,对于作为能源的二次电池的需求正在急剧增加。在这些二次电池中,对显示高能量密度和放电电压的锂二次电池的研究正在进行,且这种锂二次电池是市售并广泛使用的。锂二次电池具有长电极寿命和优异的高速充放电效率,因此使用得最广泛。
通常,锂二次电池具有其中电极组件被含有诸如LiPF6等的锂盐的非水电解液浸渍的结构,所述电极组件包含:正极,所述正极包含锂过渡金属氧化物作为电极活性材料;负极,所述负极包含碳基活性材料;聚烯烃基多孔隔膜,所述隔膜置于正极与负极之间。
就这一点而言,主要将锂钴基氧化物、锂锰基氧化物、锂镍基氧化物、锂复合氧化物等用作正极活性材料,且主要将碳基材料用作负极活性材料。在充电时正极活性材料的锂离子脱嵌然后嵌入到负极的碳层中,在放电时碳层的锂离子脱嵌然后嵌入到正极活性材料中,非水电解液充当介质,锂离子通过非水电解液在负极与正极之间移动。这种锂二次电池主要要求在电池操作电压范围内的稳定性和以足够快的速度传输离子的能力。
然而,在使用含氟(F)的电解液和碳材料作为负极活性材料的二次电池中,随着充电和放电过程的进行,正极活性材料的金属成分溶出到电解液中,且锂沉积在碳材料的表面上,因此电解液在碳材料处分解。当在高温下储存二次电池时,这种金属成分的沉积和电解液的分解更严重地发生,这导致电池剩余容量和恢复容量的减少。
同时,用作正极活性材料的锂过渡金属氧化物具有低导电性,且在高温下锂过渡金属氧化物与电解液间的反应加速,产生增加正极电阻的副产物,这导致高温下存储寿命的急剧减少。
为解决正极和负极的这些问题,现有技术公开了用预定材料涂布或处理正极或负极活性材料的表面的技术。
例如,日本专利申请公开号2000-12026公开了在碳基负极活性材料的表面上涂布金属诸如Ni、Co、Cu、Mo、W等的氧化物的方法。另外,作为用导电材料对正极活性材料进行涂布以减少正极活性材料与电解液之间的接触界面的电阻或在高温下产生的副产物的方法,用导电聚合物对正极活性材料进行涂布的方法是已知的。
另外,韩国专利申请公开号2003-0088247公开了一种制备锂二次电池用正极活性材料的方法,其包括:(a)通过将含金属的原料添加至含掺杂元素的涂布溶液中而对含金属的原料进行表面处理(其中含金属的原料为包含选自钴、锰、镍及其组合的金属且不包含锂的材料);(b)通过对经表面处理的含金属的原料进行干燥而制备活性材料前体;(c)将活性材料前体与含锂的原料进行混合并对所得混合物进行热处理。
然而,在经煅烧的电极活性材料的涂布过程中不能使用水溶性材料,且当使用氧化物时,难以用该氧化物对已经合成的材料进行顺利的涂布。
现有技术公开了用OH基进行的涂布,但难以用该方法形成均匀的膜,且仅可以使用根据pH等的限定材料,因此对涂布组成存在限制。
因此,非常需要开发可以根本上解决这些问题的技术。
发明内容
技术问题
因此,已经完成了本发明以解决以上问题和其它尚未解决的技术问题。
作为各种大量研究和各种实验的结果,本发明的发明人发现,当通过电解分解将金属材料涂布在由过渡金属水合物形成的初级前体上时,该涂布材料不渗透到初级前体的内部且在电极活性材料合成过程中在其表面上形成均匀的膜,由此完成了本发明。
因此,本发明的目的是提供通过电解分解用金属材料均匀涂布的电极活性材料前体及其制备方法。
技术方案
根据本发明的一方面,提供锂二次电池用电极活性材料前体,其中通过电解分解可电离的金属材料被均匀涂布在由过渡金属水合物形成的初级前体的表面上。
在一个具体实施方案中,可以实施所述电解分解,使得所述金属材料在酸性水溶液中电离,形成中间体,随后进行还原。
特别地,当在被浸入酸性水溶液诸如硫酸水溶液等的状态下,使用要涂布的金属材料在正(+)与负(-)电极板间施加电时,金属材料的金属在正极(+)处失去电子以电离为金属离子,所述金属离子与硫酸水溶液的硫酸离子反应以形成作为中间体的金属盐,金属盐从负极(-)接收电子以还原为金属。通过还原获得的金属被吸附在初级前体粒子上,因此所述金属可以被涂布在初级前体粒子上。
在电解分解过程中形成的中间体可以特别地为金属盐,例如硫酸盐或硝酸盐,但本发明的实施方案不限于此。即,可以使用酸式盐形式的各种材料。
当通过如上所述的电解分解对初级前体进行涂布时,金属形式被涂布在初级前体上,由此具有不同于-OH或-OOH的合成温度,因此即使通过随后的煅烧过程该金属形式也不渗透进初级前体的内部,且形成不同于其内部的表面,从而可以形成均匀的膜。
此外,可电解分解的金属不受pH等的影响,因此各种金属组成的涂布是可能的。在一个具体实施方案中,所述金属材料可以为包含选自可电解分解的过渡金属、P和Al中的至少一种元素的材料。特别地,所述过渡金属可以为选自Ni、Co、Mn、Fe、Sn、Mo、Nd、Zr和Zn中的至少一种元素。
然而,当涂布具有高氧化电位的金属材料诸如Mn时,电解分解不容易实施且产生氧化物诸如MnO2,由此可能不能获得期望的产物。因此,在一个具体实施方案中,可以使用催化剂实施所述电解分解。特别地,所述催化剂可以为选自ZnCl2基催化剂、CoCl2基催化剂、MnCl2基催化剂、NiCl2基催化剂和SnCl2基催化剂中的至少一种。更特别地,可以使用ZnCl2基催化剂。
在一个具体实施方案中,所述金属材料的涂布厚度可以为0.1μm~1μm。当所述涂布厚度低于0.1μm时,可能难以实现均匀的涂布,且可能通过金属涂布不能获得期望的效果诸如期望的导电性等。另一方面,如果涂布厚度超过1μm,则可能会妨碍锂离子的嵌入和脱嵌。
另外,基于电极活性材料前体的总重量,所述金属材料的量可以为0.01%~5%。可以将所述金属材料完全地或部分地涂布在所述初级前体的表面上。优选地,可以将所述金属材料完全地涂布在所述初级前体的表面上。
当基于电极活性材料前体的总重量,所述金属材料的量为低于0.01%时,可能不能防止因正极活性材料与电解质之间的反应而产生的问题,且可能不能获得优异的导电性。当所述金属材料的量超过5%时,电极活性材料的量相对降低,且由此容量会减少。
在一个具体实施方案中,所述初级前体可以为由下式1表示的材料:
M(OH1-z)2(1)
其中0.5<z<1,M可以包含选自Ni、Mn、Co、Al、Mg、Ti和Fe中的至少一种元素作为主要成分,其中基于全部元素,M的摩尔分数可以例如为80摩尔%。
在一个具体实施方案中,M可以为NiaMnbMec,其中a+b≤1,0.3≤a≤0.9,0.1≤b≤0.8,0≤c≤0.2,Me可以为选自Co、Al、Mg、Ti、Sr、Zn、B、Ca、Cr、Si、Ga、Sn、P、V、Sb、Nb、Ta、Mo、W、Zr、Y和Fe中的至少一种元素。特别地,M可以为NiaMnbMec的三组分基材料,其中Me为Co。
即,所述初级前体可以为过渡金属氧化物前体的水合物形式,所述过渡金属氧化物前体具有30%~90%的Ni摩尔分数,且包含Mn和预定的金属元素(Me)。这种复合过渡金属氧化物前体会比由单一元素组成的过渡金属氧化物前体更适用于制备具有高容量和优异结构稳定性的锂二次电池用电极活性材料。
此外,当与其中制备正极活性材料然后通过电解分解对正极活性材料进行涂布的情况相比时,当通过电解分解将金属材料涂布在初级前体上时,可以防止在使用水溶性溶液时可能发生的电极活性材料表面的损坏,且可以减少在电解分解时可能发生的诸如电极活性材料的电荷转移等的Li损失。
本发明还提供制备所述电极活性材料的前体的方法,其包括:
(i)制备水合物形式的初级前体;
(ii)通过电解分解用金属材料对所述初级前体进行涂布;以及
(iii)对经涂布的初级前体进行干燥。
在所述过程(i)中,可以通过混合过渡金属原料和溶剂制备初级前体。例如,过渡金属原料可以为镍原料、钴原料和锰原料中的至少一种,但本发明的实施方案不限制于此。即,在初级前体的制备中,可以进一步添加过渡金属原料。
所述溶剂可以为水、乙醇、甲醇或其组合。
所述镍原料可以为硫酸镍、硝酸镍、乙酸镍、氯化镍、磷酸镍或其组合。钴原料可以为硫酸钴、硝酸钴、乙酸钴、氯化钴、磷酸钴或其组合。锰原料可以为硫酸锰、硝酸锰、乙酸锰、氯化锰、磷酸锰或其组合。
过渡金属原料可以为过渡金属的硫氧化物、过渡金属的氮氧化物过渡金属的乙酸酐、过渡金属的氯化物、过渡金属的磷氧化物或其组合。
本发明还提供电极活性材料,所述电极活性材料通过将电极活性材料的前体和锂前体进行混合,并对所得混合物进行热处理而制备。
在一个具体实施方案中,所述锂前体可以为选自LiOH和Li2CO3中的至少一种。
就这一点而言,可以将热处理温度和气氛可以设定为本领域内已知的条件。
所述电极活性材料可以例如为正极活性材料或负极活性材料。更特别地,所述电极活性材料可以为正极活性材料。
例如,电极活性材料可以为正极活性材料,所述正极活性材料通过将金属材料涂布在例如以下化合物上而形成:层状化合物诸如锂镍锰复合氧化物(LNMO)、锂钴氧化物(LiCoO2)、锂镍氧化物(LiNiO2)等或用一种以上过渡金属取代的化合物;式Li1+xMn2-xO4的锂锰氧化物(其中0≤x≤0.33),诸如LiMnO3、LiMn2O3、LiMnO2等;锂铜氧化物(Li2CuO2);钒氧化物诸如LiV3O8、LiV3O4、V2O5、Cu2V2O7等;式LiNi1-xMxO2的镍位点型锂镍氧化物,其中M=Co、Mn、Al、Cu、Fe、Mg、B或Ga,0.01≤x≤0.3;式LiMn2-xMxO2(其中M=Co、Ni、Fe、Cr、Zn或Ta,0.01≤x≤0.1)或式Li2Mn3MO8(其中M=Fe、Co、Ni、Cu或Zn)的锂锰复合氧化物;其中一些Li原子被用碱土金属离子取代的LiMn2O4;二硫化物化合物;Fe2(MoO4)3等。在另一个实施方案中,电极活性材料可以为负极活性材料,所述负极活性材料通过将金属材料涂布在化合物上而形成,所述化合物为例如:金属复合氧化物诸如LixFe2O3(其中0≤x≤1)、LixWO2(其中0≤x≤1)、SnxMe1-xMe’yOz(其中Me:Mn、Fe、Pb或Ge;Me’:Al、B、P、Si、I族、II族或III族元素、卤素,0<x≤1;1≤y≤3;1≤z≤8);Li-Co-Ni基材料等。
附图说明
图1为根据实施例1制备的正极活性材料的扫描电子显微镜(SEM)图;
图2为根据比较例1制备的正极活性材料的SEM图;
图3为实施例1的正极活性材料的SEM横截面图。
具体实施方式
现在将参考以下实施例对本发明进行更详细的说明。提供这些实施例仅用于解释本发明且不应解释为限制本发明的范围和主旨。
<实施例1>
准备作为初级前体的由过渡金属水合物形成的金属氢氧化物M(OH0.6)2(其中M=Ni0.6Mn0.2Co0.2)和作为金属材料的Co,通过电解分解用3重量%的Co对所述金属氢氧化物进行涂布,且在空气中于890℃~930℃的温度下将经涂布的金属氢氧化物烧结10小时,从而完成经Co涂布的正极活性材料的制备。
<比较例1>
在不通过电解进行镀敷的情况下,对作为初级前体的金属氢氧化物M(OH0.6)2(其中M=Ni0.6Mn0.2Co0.2)进行煅烧,以制备作为锂二次电池用正极活性材料的LiNi0.6Mn0.2Co0.2O2。
<实验例1>
使用SEM对制备的正极活性材料的观察和使用EDX对其的分析
使用扫描电子显微镜(SEM)对根据实施例1和比较例1制备的Ni基正极活性材料进行观察,并且将观察结果示于图1和图2中。另外,将实施例1的正极活性材料的能量分散X射线光谱(EDX)分析结果示于下表1中,对在表1中所示的区域1和区域2在图3的实施例1的正极活性材料SEM横截面图中进行说明。
表1
重量% | Mn | Co | Ni |
区域1 | 14.8 | 25.1 | 60.2 |
区域2 | 16.8 | 22.4 | 60.8 |
参考图1可以确认,Co被顺利地涂布在实施例1的锂镍钴锰氧化物的表面上。另外,参考图3和表1可以确认,在正极活性材料的表面上Co的量大于正极活性材料内部的量。这是因为正极活性材料内部的Co和初级前体具有不同的合成温度,因此即使在煅烧后Co也不渗透进初级前体中,而是形成不同于其内部表面的表面。
本领域技术人员可以以上述内容为基础,在本发明的范围内进行各种应用和变化。
工业实用性
如上所述,在根据本发明的电极活性材料的前体中,即使对用金属材料涂布的初级前体实施随后的合成过程,涂层材料也不渗透进电极活性材料的内部,而是残留在其表面上,从而形成均匀的金属涂层膜。另外,可以用各种金属对电极活性材料的前体进行涂布。
另外,根据制备电极活性材料的前体的方法,可以用均匀量的金属材料对大量的初级前体进行涂布,且可以用不能通过共沉淀进行涂布的材料对其进行涂布。
Claims (15)
1.一种锂二次电池用电极活性材料的前体,其中可电离的金属材料通过电解分解而均匀涂布在初级前体的表面上,所述初级前体由下式1表示:
M(OH1-z)2 (1)
其中0.5<z<1;且
M包含选自Ni、Mn、Co、Al、Mg、Ti和Fe中的至少一种元素作为主要成分,
其中实施所述电解分解,使得所述金属材料在酸性水溶液中电离,形成中间体,随后进行还原。
2.根据权利要求1的前体,其中所述中间体为金属盐。
3.根据权利要求2的前体,其中所述金属盐为硫酸盐或硝酸盐。
4.根据权利要求1的前体,其中使用催化剂实施所述电解分解。
5.根据权利要求4的前体,其中所述催化剂为选自ZnCl2基催化剂、CoCl2基催化剂、MnCl2基催化剂、NiCl2基催化剂和SnCl2基催化剂中的至少一种。
6.根据权利要求1的前体,其中在式1中,M为NiaMnbMec,其中a+b≤1,0.3≤a≤0.9,0.1≤b≤0.8,0≤c≤0.2;Me为选自Co、Al、Mg、Ti、Sr、Zn、B、Ca、Cr、Si、Ga、Sn、P、V、Sb、Nb、Ta、Mo、W、Zr、Y和Fe中的至少一种元素。
7.根据权利要求6的前体,其中Me包含Co。
8.根据权利要求1的前体,其中所述金属材料包含选自可电解分解的过渡金属和Al中的至少一种元素。
9.根据权利要求8的前体,其中所述可电解分解的过渡金属为选自Ni、Co、Mn、Fe、Sn、Mo、Nd、Zr和Zn中的至少一种元素。
10.根据权利要求1的前体,其中所述金属材料的涂布厚度为0.1μm~1μm。
11.根据权利要求1的前体,其中基于所述前体的总重量,所述金属材料的量为0.01%~5%。
12.根据权利要求1的前体,其中所述金属材料完全地或部分地涂布在初级前体的表面上。
13.一种制备权利要求1的前体的方法,其包括:
制备初级前体,所述初级前体由下式1表示:
M(OH1-z)2 (1)
其中0.5<z<1;且
M包含选自Ni、Mn、Co、Al、Mg、Ti和Fe中的至少一种元素作为主要成分;
使用可电离的金属材料通过电解分解对所述初级前体进行涂布;以及
对经涂布的初级前体进行干燥,
其中实施所述电解分解,使得所述金属材料在酸性水溶液中电离,形成中间体,随后进行还原。
14.一种电极活性材料,其通过将权利要求1的前体和锂前体进行混合,并对混合物进行热处理而制备。
15.根据权利要求14的电极活性材料,其中所述锂前体为选自LiOH和Li2CO3中的至少一种。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2012-0134343 | 2012-11-26 | ||
KR1020120134343A KR101584114B1 (ko) | 2012-11-26 | 2012-11-26 | 금속이 코팅된 전극 활물질의 전구체 및 그의 제조방법 |
PCT/KR2013/010794 WO2014081269A1 (ko) | 2012-11-26 | 2013-11-26 | 금속이 코팅된 전극 활물질의 전구체 및 그의 제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104737334A CN104737334A (zh) | 2015-06-24 |
CN104737334B true CN104737334B (zh) | 2018-03-23 |
Family
ID=50776362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380055182.6A Active CN104737334B (zh) | 2012-11-26 | 2013-11-26 | 涂布有金属的电极活性材料前体及其制备方法 |
Country Status (9)
Country | Link |
---|---|
US (1) | US10243208B2 (zh) |
EP (1) | EP2884567B1 (zh) |
JP (1) | JP5982577B2 (zh) |
KR (1) | KR101584114B1 (zh) |
CN (1) | CN104737334B (zh) |
BR (1) | BR112015007990B8 (zh) |
IN (1) | IN2015DN02619A (zh) |
TW (1) | TWI536641B (zh) |
WO (1) | WO2014081269A1 (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101970207B1 (ko) * | 2016-01-05 | 2019-04-18 | 주식회사 에코프로비엠 | 코발트 코팅 전구체의 제조 방법, 이에 의하여 제조된 코발트 코팅 전구체 및 이를 이용하여 제조된 양극활물질 |
WO2018117635A1 (ko) * | 2016-12-21 | 2018-06-28 | 주식회사 엘지화학 | 금속이 도핑된 이차전지용 양극 활물질 제조용 코발트 전구체 |
WO2019103461A2 (ko) | 2017-11-21 | 2019-05-31 | 주식회사 엘지화학 | 양극활물질 전구체, 그 제조 방법, 이를 이용해 제조된 양극 활물질, 양극 및 이차전지 |
TWI663128B (zh) | 2018-03-27 | 2019-06-21 | 國立清華大學 | 二次電池用電極材料及二次電池 |
WO2021145493A1 (ko) * | 2020-01-17 | 2021-07-22 | 주식회사 엘 앤 에프 | 코팅층을 포함하고 있는 양극 활물질 제조용 전구체 입자 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101510606A (zh) * | 2009-03-27 | 2009-08-19 | 北京化工大学 | 复合金属氧化物包覆尖晶石型LiMn2O4正极材料及制备方法 |
CN101998932A (zh) * | 2008-04-03 | 2011-03-30 | 株式会社Lg化学 | 用于制备锂复合过渡金属氧化物的新前体 |
CN102386391A (zh) * | 2011-10-27 | 2012-03-21 | 中南大学 | 一种制备三元复合正极材料LiNixCoyMn1-x-yO2的方法 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3489396B2 (ja) | 1997-06-18 | 2004-01-19 | 住友金属鉱山株式会社 | 正極材料用メタル被覆水酸化ニッケルおよびその製造方法 |
JP4177480B2 (ja) | 1998-05-15 | 2008-11-05 | インターナショナル ソーラー エレクトリック テクノロジー,インコーポレイテッド | 化合物半導体フィルムおよび関連電子装置の製造方法 |
JP2000012026A (ja) | 1998-06-24 | 2000-01-14 | Shin Kobe Electric Mach Co Ltd | 非水電解液二次電池 |
JP3956765B2 (ja) | 2002-04-30 | 2007-08-08 | 住友電気工業株式会社 | 合金微粉末とそれを用いた導電ペースト、およびエレクトロルミネッセンス素子 |
KR100437340B1 (ko) * | 2002-05-13 | 2004-06-25 | 삼성에스디아이 주식회사 | 리튬 이차 전지용 양극 활물질의 제조 방법 |
US7258778B2 (en) * | 2003-03-24 | 2007-08-21 | Eltech Systems Corporation | Electrocatalytic coating with lower platinum group metals and electrode made therefrom |
CN1540037A (zh) | 2003-10-31 | 2004-10-27 | 北京航空航天大学 | 一种采用电沉积法制备氧化钴材料的方法 |
US7335245B2 (en) | 2004-04-22 | 2008-02-26 | Honda Motor Co., Ltd. | Metal and alloy nanoparticles and synthesis methods thereof |
US7682739B2 (en) | 2004-05-12 | 2010-03-23 | Mitsui Mining & Smelting Co., Ltd. | Negative electrode for nonaqueous secondary battery and process of producing the same |
US20070298512A1 (en) | 2005-04-13 | 2007-12-27 | Lg Chem, Ltd. | Material for lithium secondary battery of high performance |
JP5435063B2 (ja) | 2005-11-11 | 2014-03-05 | 三菱マテリアル株式会社 | 太陽電池の電極形成用組成物の製造方法及び該電極の形成方法 |
KR100752703B1 (ko) * | 2006-06-29 | 2007-08-29 | 한양대학교 산학협력단 | 리튬 이차 전지용 양극 활물질, 그 제조 방법 및 그를사용한 리튬 이차 전지 |
KR100836659B1 (ko) | 2006-07-06 | 2008-06-10 | 삼성전기주식회사 | 금속 및 금속 산화물 나노입자의 제조방법 |
KR100813014B1 (ko) | 2006-10-12 | 2008-03-13 | 한국과학기술연구원 | 수계 알루미나 졸로 표면 개질된 리튬 이차전지용양극활물질 및 그의 제조 방법 |
JP2008138268A (ja) | 2006-12-04 | 2008-06-19 | Asahi Kasei Chemicals Corp | 薄膜を有する基板の製造方法 |
KR20100053758A (ko) * | 2008-11-13 | 2010-05-24 | 한국전자통신연구원 | 리튬이차전지용 양극활물질 분말의 제조 방법 및 이에 의해제조된 리튬이차전지용 양극활물질 분말 |
KR101190226B1 (ko) | 2008-11-19 | 2012-10-11 | 코스모신소재 주식회사 | 리튬 이차전지용 양극활물질, 그의 제조방법 및 이를 포함한 리튬 이차전지 |
KR101147601B1 (ko) | 2008-12-17 | 2012-05-21 | 주식회사 엘지화학 | 표면이 개질되어 있는 양극 활물질 |
KR101407859B1 (ko) | 2009-02-04 | 2014-06-16 | 카와사키 주코교 카부시키 카이샤 | 리튬 2차 전지용 섬유 전극, 그 제조 방법 및 섬유 전극을 구비한 리튬 2차 전지 |
JP5720909B2 (ja) * | 2010-08-17 | 2015-05-20 | ユミコア | アルミニウム乾式被覆および熱処理が施されたカソード材料前駆体 |
US20130221489A1 (en) | 2010-11-22 | 2013-08-29 | E I Du Pont De Nemours And Company | Inks and processes to make a chalcogen-containing semiconductor |
WO2012174235A1 (en) | 2011-06-14 | 2012-12-20 | Brookhaven Science Associates, Llc | INTERMETALLIC M-Sn5 (M=Fe, Cu, Co, Ni) COMPOUND AND A METHOD OF SYNTHESIS THEREOF |
-
2012
- 2012-11-26 KR KR1020120134343A patent/KR101584114B1/ko active IP Right Grant
-
2013
- 2013-11-26 US US14/440,194 patent/US10243208B2/en active Active
- 2013-11-26 WO PCT/KR2013/010794 patent/WO2014081269A1/ko active Application Filing
- 2013-11-26 BR BR112015007990A patent/BR112015007990B8/pt active IP Right Grant
- 2013-11-26 EP EP13856813.4A patent/EP2884567B1/en active Active
- 2013-11-26 JP JP2015532982A patent/JP5982577B2/ja active Active
- 2013-11-26 CN CN201380055182.6A patent/CN104737334B/zh active Active
- 2013-11-26 TW TW102143155A patent/TWI536641B/zh active
- 2013-11-26 IN IN2619DEN2015 patent/IN2015DN02619A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101998932A (zh) * | 2008-04-03 | 2011-03-30 | 株式会社Lg化学 | 用于制备锂复合过渡金属氧化物的新前体 |
CN101510606A (zh) * | 2009-03-27 | 2009-08-19 | 北京化工大学 | 复合金属氧化物包覆尖晶石型LiMn2O4正极材料及制备方法 |
CN102386391A (zh) * | 2011-10-27 | 2012-03-21 | 中南大学 | 一种制备三元复合正极材料LiNixCoyMn1-x-yO2的方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2884567A1 (en) | 2015-06-17 |
WO2014081269A1 (ko) | 2014-05-30 |
BR112015007990B8 (pt) | 2023-01-10 |
BR112015007990B1 (pt) | 2021-09-14 |
BR112015007990A2 (pt) | 2017-07-04 |
JP2015536018A (ja) | 2015-12-17 |
KR20140073607A (ko) | 2014-06-17 |
CN104737334A (zh) | 2015-06-24 |
EP2884567B1 (en) | 2018-01-03 |
TWI536641B (zh) | 2016-06-01 |
IN2015DN02619A (zh) | 2015-09-18 |
TW201434196A (zh) | 2014-09-01 |
KR101584114B1 (ko) | 2016-01-13 |
US10243208B2 (en) | 2019-03-26 |
JP5982577B2 (ja) | 2016-08-31 |
US20150280225A1 (en) | 2015-10-01 |
EP2884567A4 (en) | 2016-03-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107004852B (zh) | 具有多孔结构的锂电池用正极活性物质及其制造方法 | |
KR101577180B1 (ko) | 고에너지 밀도의 혼합 양극활물질 | |
US10164249B2 (en) | Positive active material for secondary lithium battery, method for preparing the same and secondary lithium battery containing the positive active material | |
CN102782911B (zh) | 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池 | |
CN102782913B (zh) | 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池 | |
CN103872316B (zh) | 正极活性物质及其制备方法、以及包括其的锂二次电池 | |
CN102782909B (zh) | 锂离子电池用正极活性物质、锂离子电池用正极及锂离子电池 | |
CN111224093A (zh) | 具有锰浓度梯度的电极材料及其制备方法和钠离子电池 | |
WO2011162178A1 (ja) | リチウムイオン二次電池 | |
US20150311522A1 (en) | Positive active material for use in a lithium ion battery and method for preparing the same | |
JP6058671B2 (ja) | リチウムイオン電気化学セルに使用される大容量正極及び該正極の製造方法 | |
CN106299328B (zh) | 对富锂层状氧化物正极材料的掺杂方法、材料和制备方法 | |
KR101977995B1 (ko) | 붕소 화합물이 코팅된 리튬 이차 전지용 양극 활물질 및 이의 제조 방법 | |
CN104160530B (zh) | 非水电解液二次电池 | |
CN104737334B (zh) | 涂布有金属的电极活性材料前体及其制备方法 | |
KR100805910B1 (ko) | 리튬 전지용 올리빈형 양극 활물질, 이의 제조 방법, 및이를 포함하는 리튬 전지 | |
KR100946387B1 (ko) | 리튬 전지용 올리빈형 양극 활물질 전구체, 리튬 전지용올리빈형 양극 활물질, 이의 제조 방법, 및 이를 포함하는리튬 전지 | |
JP2021048137A (ja) | リチウム二次電池用正極活物質 | |
JP2014072025A (ja) | 非水電解質二次電池及びその製造方法 | |
JP2008130287A (ja) | 非水電解質二次電池用正極活物質の製造方法および非水電解質二次電池 | |
JP2015144119A (ja) | 非水電解液二次電池用正極活物質及びその製造方法 | |
KR20150064320A (ko) | 리튬 이차 전지용 양극 활물질 및 이의 제조 방법 | |
KR101991254B1 (ko) | 고출력 장수명을 나타내는 혼합 양극활물질 | |
JP2013037879A (ja) | リチウムイオン二次電池用正極活物質、その正極活物質を用いたリチウムイオン二次電池及びリチウムマンガン銀複合酸化物の製造方法 | |
JP2017004770A (ja) | マグネシウム二次電池用正極活物質、マグネシウム二次電池用正極、及びマグネシウム二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20211208 Address after: Seoul, South Kerean Patentee after: LG Energy Solution Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |
|
TR01 | Transfer of patent right |