CN103855384B - A kind of ternary cathode material of lithium ion battery of rare-earth-doped modification and preparation method thereof - Google Patents
A kind of ternary cathode material of lithium ion battery of rare-earth-doped modification and preparation method thereof Download PDFInfo
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- CN103855384B CN103855384B CN201410112765.4A CN201410112765A CN103855384B CN 103855384 B CN103855384 B CN 103855384B CN 201410112765 A CN201410112765 A CN 201410112765A CN 103855384 B CN103855384 B CN 103855384B
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- 230000004048 modification Effects 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000002715 modification method Methods 0.000 title abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000011247 coating layer Substances 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- -1 rare earth compound Chemical class 0.000 claims abstract description 9
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 4
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims description 27
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910013716 LiNi Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 150000001722 carbon compounds Chemical class 0.000 abstract description 7
- 238000005253 cladding Methods 0.000 abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-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
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 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
- H01M4/48—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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
Abstract
The present invention relates to ternary cathode material of lithium ion battery of a kind of rare-earth-doped modification and preparation method thereof, materials chemistry formula is: LiNiaCo1‑a‑bMnbRxO2/ M, wherein 0 < a < 1,0 <b < 1,0 < 1 a b < 1,0.005 < x < 0.1, R is one or more in Rare Earth Lanthanum, cerium, praseodymium and samarium, and M is the oxide compound coating layer with carbon of aluminum, titanium or magnesium.It is that the nickel salts of solubility, cobalt salt and manganese salt and rare earth compound are configured to mixing salt solution, the mixed ammonium/alkali solutions being configured to NaOH and ammonia reacts, after being filtered, washed and dried, uniformly mix with lithium salts powder ball milling, and through high-temperature calcination, cladding containing aluminum, the compound coating layer of oxide and the carbon of titanium or magnesium, then calcining at constant temperature and prepare.The present invention use rear-earth-doped after, use metal-oxide cheap and easy to get and carbon compound coating, while improving cycle performance and high rate performance, improve the efficiency for charge-discharge of material.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, particularly to the ternary cathode material of lithium ion battery and preparation method thereof of a kind of rare-earth-doped modification.
Background technology
Compared with other traditional secondary batteries, lithium ion battery has that volume is little, voltage is high, specific capacity is big and the plurality of advantages such as energy density is high, therefore, achieves bigger progress at 3C electronic applications.And positive electrode is the important component part of lithium ion battery, it also it is the part that in lithium ion battery, cost ratio is the highest.
Nickle cobalt lithium manganate tertiary cathode material as Olivine-type Cathode Material in Li-ion Batteries combines nickel, cobalt and the advantage of three kinds of elements of manganese, compares cobalt acid lithium, lithium nickelate and LiMn2O4, has higher specific capacity, longer cycle life and more preferable security performance.This material has good chemical property, but for its practicality, chemical property aspect still needs to be improved further.On the one hand, due to Ni2+With Li+Ionic radius be closer to that cation mixing phenomenon easily occurs so that material in atmosphere be susceptible to analyse lithium phenomenon, cause the chemical property of material to be deteriorated；On the other hand, ternary material and electrolyte contacts can make part metals ion-solubility, make material phenomenon of caving in occur, be unfavorable for the raising of cycle performance during repeated charge；Another further aspect, the lithium ion diffusion coefficient of material and electronic conductivity need to be improved further.
In order to improve the safety problem of ternary material, currently mainly improve in terms of doping and cladding etc., but single doping or cladding cannot prepare the ternary material of excellent combination property.Existing research uses different methods that ternary material carries out the element dopings such as magnesium, zirconium and aluminum, result shows, after doping, the most forthright of material increases, but cycle performance change is little, and use the Surface coating such as aluminium sesquioxide, titanium oxide and aluminum phosphate can improve cycle performance and the security performance of material, but can cause the specific capacity of material and the most forthright reduction.Also there is research that ternary material has carried out doping and cladding comprehensively modifying, but nonactive clad can affect the surface conductivity of material, causes the high rate performance of battery to reduce.
Summary of the invention
The present invention provides ternary cathode material of lithium ion battery of a kind of rare-earth-doped modification and preparation method thereof, overcomes the deficiencies in the prior art, uses doping and compound coating simultaneously, improves the cycle performance of material and the most forthright.
It is an object of the invention to be achieved through the following technical solutions:
First aspect, the ternary cathode material of lithium ion battery of a kind of rare-earth-doped modification, chemical general formula is: LiNiaCo1-a-bMnbRxO2/ M, wherein 0 < a < 1,0 <b < 1,0 < 1-a-b < 1,0.005 < x < 0.1, R is one or more in Rare Earth Lanthanum, cerium, praseodymium and samarium, and M is the oxide compound coating layer with carbon of aluminum, titanium or magnesium.
As preferably, described compound coating layer and LiNiaCo1-a-bMnbRxO2Mass ratio be 0.001～0.05:1；In described compound coating layer, carbon is 1～10:1 with the mass ratio of metal-oxide.
As the most preferred, described compound coating layer and LiNiaCo1-a-bMnbRxO2Mass ratio be 0.005～0.03:1.
Second aspect, the preparation method of the ternary cathode material of lithium ion battery of a kind of rare-earth-doped modification as described in terms of first, it is characterised in that comprise the following steps:
(1) the nickel salts of solubility, cobalt salt and manganese salt and rare earth compound are dissolved in a certain amount of deionized water according to predetermined mol ratio, are configured to mixing salt solution, NaOH and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Above-mentioned mixing salt solution and mixed ammonium/alkali solutions are added in deionized water with certain speed, after reaction a period of time, is filtered, washed and dried, obtains the ternary material precursor (Ni of rare-earth-doped modificationaCo1-a-bMnbRx)(OH)2, wherein 0 < a < 1,0 <b < 1,0 < 1-a-b < 1,0.005 < x < 0.1；
(2) the ternary material precursor powder of rare-earth-doped modification is uniformly mixed with lithium salts powder ball milling by a certain percentage, obtain the ternary material LiNi of rare-earth-doped modification through high-temperature calcinationaCo1-a-bMnbRxO2；
(3) the ternary material Surface coating at rare-earth-doped modification contains the oxide of aluminum, titanium or magnesium and the compound coating layer of carbon, then calcining at constant temperature, and obtains the ternary cathode material of lithium ion battery of rare-earth-doped modification through natural cooling.
As preferably, described nickel salts, cobalt salt and manganese salt are respectively one or more in nitrate, sulfate and chlorate；Any one as 5:2:3, in 2:2:1,8:1:1,2:1:2 and 1:1:1 of the mol ratio that described nickel salts, cobalt salt and manganese salt is counted with nickel cobalt manganese metal respectively；Described rare earth compound is one or more in the soluble nitrate of rare earth, carbonate, sulfate, acetate and chlorate；The mol ratio of described rare earth compound summation in terms of rare earth element and described nickel salts, cobalt salt and manganese salt summation in terms of nickel cobalt manganese metal respectively is 0.005～0.1:1；In described mixed ammonium/alkali solutions, NaOH is 2:1 with the mol ratio of ammonia.
As the most preferably, described rare earth compound summation in terms of rare earth element is 0.005～0.02:1 with the mol ratio of described nickel salts, cobalt salt and manganese salt summation in terms of nickel cobalt manganese metal.
As preferably, described lithium salts is one or more in lithium carbonate, Lithium hydrate, lithium acetate, lithium chloride and lithium sulfate；DescribedLithium saltsThe mol ratio of the ternary material precursor of the summation in terms of elemental lithium and rare-earth-doped modification summation in terms of nickel cobalt manganese metal is 1.01～1.10:1.
As preferably, one or more in sucrose, glucose, starch and Polyethylene Glycol of described carbon source；The oxide of described carbon and aluminum, titanium or magnesium is with Al2O3、TiO2Or the mass ratio of MgO meter is 1～10:1；The ternary material of described clad and rare-earth-doped modification is with LiNiaCo1-a-bMnbRxO2The mass ratio of meter is 0.001～0.05:1.
As the most preferably, the ternary material of described clad and rare-earth-doped modification is with LiNiaCo1-a-bMnbRxO2The mass ratio of meter is 0.005～0.03:1.
As preferably, the temperature of described high-temperature calcination is 800～1000 DEG C, and calcination time is 4～20h；The atmosphere of described calcining at constant temperature is nitrogen or argon, and calcining heat is 300～800 DEG C, and calcination time is 3～8h.
Compared with prior art, the great advantage of the present invention and having the beneficial effect that:
(1) the present invention uses the rare-earth metal doped element of wet chemical method simple to operate, that be easily controlled, and each element can mix on atomic level, makes product more uniform, easily realizes industrialized production.
(2) use rare earth ion that material is doped, can be with the structure of stabilizing material, it is to avoid Li during long-term charge and discharge cycles+Deintercalation destruction that material structure is produced, thus improve the electric conductivity of positive electrode.
(3) use metal-oxide that surface is coated with, it is possible to reduce active particle and the contact of electrolyte, the HF corrosion to tertiary cathode material produced by electrolyte in suppression cyclic process, thus lower the impedance of battery, improve the chemical property of material.
(4) the charge transfer resistance during the carbon of clad can reduce material charge and discharge process, improves the surface conductivity of tertiary cathode material, and carbon has loose structure under anoxia hot conditions simultaneously, can be Li+Improve unimpeded passage, be effectively increased the high rate performance of tertiary cathode material.
The present invention use rear-earth-doped after, use metal-oxide cheap and easy to get and carbon compound coating, while improving cycle performance and high rate performance, improve the efficiency for charge-discharge of material.
Documents:
CN103490060A discloses a kind of lithium nickel cobalt manganese positive electrode material and preparation method thereof, with metal or rare earth element ternary material is doped modified ternary material Surface coating one layer containing lithium, aluminum, magnesium, titanium, the oxide of zirconium, phosphate or the clad of fluoride, comprehensively improve cycle performance and the high rate performance of material；And the present invention use rear-earth-doped after, material surface is carried out metal-oxide and carbon compound coating, more effectively improves cycle performance and the most forthright.
CN102760884A discloses anode material for lithium-ion batteries that a kind of lithium fast-ionic conductor modifies mutually and preparation method thereof, rare earth element is used ternary material to be doped modified at one layer of lithium fast-ionic conductor compound of ternary material Surface coating, and the present invention unlike this invention uses metal-oxide cheap and easy to get and carbon compound coating, while improving cycle performance and high rate performance, improve the efficiency for charge-discharge of material.
CN102088087A discloses anode material for lithium-ion batteries of a kind of doped with rare-earth elements and preparation method thereof, with rare earth element, LiMn2O4 is doped modification, and modified cycle performance is greatly improved, but first discharge specific capacity is relatively low.
CN201310397441 discloses the method for modifying of a kind of tertiary cathode material, uses Rare Earth Lanthanum that ternary material is carried out coating modification, has only been by single coating modification；And the present invention is to use rear-earth-doped, oxide covered composite yarn modification.
CN103280572A discloses a kind of lithium ion cell positive ternary material and preparation method, uses lutecium element ternary material to be doped modification, has only been by single doping vario-property；And the present invention is to use rear-earth-doped, oxide covered composite yarn modification.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve chart of the tertiary cathode material of embodiment 1.
Fig. 2 is the cycle charge-discharge curve chart of the tertiary cathode material of embodiment 1.
Fig. 3 is the X ray diffracting spectrum of the tertiary cathode material of embodiment 1.
Fig. 4 is the scanning electron microscope diagram of the tertiary cathode material of embodiment 1.
Detailed description of the invention
In order to the present invention there being deeper understanding; below in conjunction with in embodiment, technical scheme is clearly and completely described; but embodiments of the invention are only used to explain the present invention; and the unrestricted present invention; the every other case study on implementation that those skilled in the art are obtained on the premise of not making creative work, belongs to protection scope of the present invention.
Embodiment 1:
Ni:Mn:Co:La=1:1:1:0.005 preparing metal total concentration is the nickel nitrate of 2mol/L, manganese nitrate, cobalt nitrate, Lanthanum (III) nitrate mixed aqueous solution in molar ratio；Preparation total concentration is NaOH and the mixed solution of ammonia of 10mol/L, and wherein the mol ratio of NaOH and ammonia is 2:1.
With certain speed, above two solution is added simultaneously to reactor, and the pH value controlling reaction is 12, and reaction temperature is 50 DEG C, is aged 8h, obtains the nickel-cobalt-manganese ternary material precursor of La doped after filtering, wash, drying after reaction 6h.
By the nickel-cobalt-manganese ternary material precursor of above-mentioned La doped with lithium carbonate according to Li:(Ni+Mn+Co) after the ratio of=1.01:1 mixs homogeneously, in 1000 DEG C of high-temperature calcination 8h, cooling, pulverize, sieving obtains the cobalt nickel lithium manganate ternary material of La doped.
To the cobalt nickel lithium manganate ternary material of above-mentioned La doped based on 100% mass parts, with the Al of 0.2% mass parts2O3Carry out surface recombination cladding with the C of 1% mass parts, after drying 700 DEG C, constant temperature processes 8h in argon gas atmosphere, obtains aluminium oxide and the tertiary cathode material of carbon compound coating.
The electrochemical property test of material uses blue electricity battery test system to test at 25 DEG C, and test voltage scope is 2.7V～4.3V；High rate performance test condition: once, once, 0.2C charging 1C discharges once in 0.2C discharge and recharge in 0.1C discharge and recharge；Cycle performance test condition: carry out discharge and recharge with 1C multiplying power, circulates 50 weeks, investigates capability retention.Material specific discharge capacity under 0.1C multiplying power is that under 195.0mAh/g, 0.2C multiplying power, specific discharge capacity is 190.9 mAh/g, and the specific discharge capacity under 1C multiplying power is 182.1 mAh/g, and 1C/0.1C electric discharge ratio is 93.3%, and high rate performance is preferable.1C charge and discharge circulates 50 weeks capability retentions and is more than 98%, and cycle performance is preferable.
Embodiment 2:
Ni:Mn:Co:Pr=5:3:2:0.01 preparing metal total concentration is the nickel nitrate of 1mol/L, manganese nitrate, cobalt nitrate, praseodymium nitrate mixed aqueous solution in molar ratio；Preparation total concentration is NaOH and the mixed solution of ammonia of 10mol/L, and wherein the mol ratio of NaOH and ammonia is 2:1.
With certain speed, above two solution is added simultaneously to reactor, and the pH value controlling reaction is 12, and reaction temperature is 45 DEG C, is aged 8h, obtains the nickel-cobalt-manganese ternary material precursor of praseodymium doped after filtering, wash, drying after reaction 6h.
By the nickel-cobalt-manganese ternary material precursor of above-mentioned praseodymium doped with lithium carbonate according to Li:(Ni+Mn+Co) after the ratio of=1.02:1 mixs homogeneously, in 1000 DEG C of high-temperature calcination 8h, cooling, pulverize, sieving obtains the cobalt nickel lithium manganate ternary material of praseodymium doped.
To the cobalt nickel lithium manganate ternary material of above-mentioned praseodymium doped based on 100% mass parts, surface recombination cladding is carried out with the MgO of 0.1% mass parts and the C of 1% mass parts, after drying 800 DEG C, constant temperature processes 7h in argon gas atmosphere, obtains magnesium oxide and the tertiary cathode material of carbon compound coating.
Embodiment 3:
Ni:Mn:Co:Ce=4:4:2:0.001 preparing metal total concentration is the nickel nitrate of 2mol/L, manganese nitrate, cobalt nitrate, cerous nitrate mixed aqueous solution in molar ratio；Preparation total concentration is NaOH and the mixed solution of ammonia of 10mol/L, and wherein the mol ratio of NaOH and ammonia is 2:1.
With certain speed, above two solution is added simultaneously to reactor, and the pH value controlling reaction is 12, and reaction temperature is 50 DEG C, is aged 8h, obtains the nickel-cobalt-manganese ternary material precursor of cerium dopping after filtering, wash, drying after reaction 6h.
By the nickel-cobalt-manganese ternary material precursor of above-mentioned cerium dopping with lithium carbonate according to Li:(Ni+Mn+Co) after the ratio of=1.01:1 mixs homogeneously, in 1000 DEG C of high-temperature calcination 8h, cooling, pulverize, sieving obtains the cobalt nickel lithium manganate ternary material of cerium dopping.
To the cobalt nickel lithium manganate ternary material of above-mentioned cerium dopping based on 100% mass parts, with the TiO of 0.5% mass parts2Carry out surface recombination cladding with the C of 0.5% mass parts, after drying 700 DEG C, constant temperature processes 8h in argon gas atmosphere, obtains titanium oxide and the tertiary cathode material of carbon compound coating.
Claims (4)
1. the preparation method of the ternary cathode material of lithium ion battery of a rare-earth-doped modification, it is characterised in that comprise the following steps:
(1) the nickel salts of solubility, cobalt salt and manganese salt and rare earth compound are dissolved in a certain amount of deionized water according to predetermined mol ratio, are configured to mixing salt solution, NaOH and ammonia solvent are configured to mixed ammonium/alkali solutions in deionized water；Above-mentioned mixing salt solution and mixed ammonium/alkali solutions are added in deionized water with certain speed, after reaction a period of time, is filtered, washed and dried, obtains the ternary material precursor (Ni of rare-earth-doped modificationaCo1-a-bMnbRx)(OH)2, wherein 0 < a < 1,0 <b < 1,0 < 1-a-b < 1,0.005 < x < 0.1；
(2) the ternary material precursor powder of rare-earth-doped modification is uniformly mixed with lithium salts powder ball milling by a certain percentage, obtain the ternary material LiNi of rare-earth-doped modification through high-temperature calcinationaCo1-a-bMnbRxO2；
(3) the ternary material Surface coating at rare-earth-doped modification contains the oxide of aluminum, titanium or magnesium and the compound coating layer of carbon, then calcining at constant temperature, and obtains the ternary cathode material of lithium ion battery of rare-earth-doped modification through natural cooling；The chemical general formula of the ternary cathode material of lithium ion battery of described rare-earth-doped modification is: LiNiaCo1-a-bMnbRxO2/ M, wherein 0 < a < 1,0 <b < 1,0 < 1-a-b < 1,0.005 < x < 0.1, R is one or more in Rare Earth Lanthanum, praseodymium and samarium, and M is the oxide compound coating layer with carbon of aluminum, titanium or magnesium；In described compound coating layer, carbon is 1～10:1 with the mass ratio of metal-oxide；
One or more in sucrose, glucose, starch and Polyethylene Glycol of described carbon source；The oxide of described carbon and aluminum, titanium or magnesium is with Al2O3、TiO2Or the mass ratio of MgO meter is 1～10:1；
The temperature of described high-temperature calcination is 800～1000 DEG C, and calcination time is 4～20h；The atmosphere of described calcining at constant temperature is nitrogen or argon, and calcining heat is 300～800 DEG C, and calcination time is 3～8h.
2. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 1, it is characterized in that, the mol ratio of described rare earth compound summation in terms of rare earth element and described nickel salts, cobalt salt and manganese salt summation in terms of nickel cobalt manganese metal respectively is 0.005～0.1:1；In described mixed ammonium/alkali solutions, NaOH is 2:1 with the mol ratio of ammonia.
3. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 2, it is characterized in that, described rare earth compound summation in terms of rare earth element is 0.005～0.02:1 with the mol ratio of described nickel salts, cobalt salt and manganese salt summation in terms of nickel cobalt manganese metal.
4. the ternary cathode material of lithium ion battery of rare-earth-doped modification prepared by the method for claim 1, it is characterised in that chemical general formula is: LiNiaCo1-a-bMnbRxO2/ M, wherein 0 < a < 1,0 <b < 1,0 < 1-a-b < 1,0.005 < x < 0.1, R is one or more in Rare Earth Lanthanum, praseodymium and samarium, and M is the oxide compound coating layer with carbon of aluminum, titanium or magnesium；In described compound coating layer, carbon is 1～10:1 with the mass ratio of metal-oxide.
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