CN103855384A - Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof - Google Patents
Rare-earth doping modified lithium ion battery ternary positive electrode material and preparation method thereof Download PDFInfo
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- CN103855384A CN103855384A CN201410112765.4A CN201410112765A CN103855384A CN 103855384 A CN103855384 A CN 103855384A CN 201410112765 A CN201410112765 A CN 201410112765A CN 103855384 A CN103855384 A CN 103855384A
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- rare
- earth
- ion battery
- lithium ion
- lithium
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical class [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- -1 rare-earth compound Chemical class 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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 claims abstract 2
- 230000004048 modification Effects 0.000 claims description 34
- 238000012986 modification Methods 0.000 claims description 31
- 239000010406 cathode material Substances 0.000 claims description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 229910020632 Co Mn Inorganic materials 0.000 claims description 8
- 229910020678 Co—Mn Inorganic materials 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 7
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 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
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 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
- 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
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 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
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 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
- 239000002243 precursor Substances 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
- 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 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000000395 magnesium oxide Substances 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 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 7
- 239000011572 manganese Substances 0.000 description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 6
- 150000001722 carbon compounds Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 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
- 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
- 238000002715 modification method Methods 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
- 238000005406 washing Methods 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010416 ion conductor Substances 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical group 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
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 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
- 230000000694 effects 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
- 230000007774 longterm Effects 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 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
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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 invention relates to a rare-earth doping modified lithium ion battery ternary positive electrode material and a preparation method of the rare-earth doping modified lithium ion battery ternary positive electrode material. The chemical general formula of the material is as follows: LiNiaCo<1-a-b>MnbRxO2/M, wherein a is more than 0 and less than 1, b is more than 0 and less than 1, (1-a-b) is more than 0 and less than 1, x is more than 0.005 and less than 0.1, R is one or more of rare-earth lanthanum, cerium, praseodymium and samarium, and M is a composite cladding layer of oxide of aluminum, titanium or magnesium and carbon. The soluble metal nickel salt, cobalt salt, manganese salt and rare-earth compound are mixed to prepare a mixed salt solution, the mixed salt solution is reacted with a mixed alkaline solution prepared by mixing NaOH and ammonium hydroxide, after the reaction solution is filtered, washed and dried, the obtained product is uniformly mixed with lithium salt powder to be ball milled, then the mixture is calcined at the high temperature and coated with the composite cladding layer of the aluminum, titanium or magnesium oxide and carbon, and finally the calcined mixture is calcined at a constant temperature to obtain the rare-earth doping modified lithium ion battery ternary positive electrode material. After doping the rare earth, the metal oxide and carbon composite cladding layer, which are cheap and easy to obtain, are adopted, so that the cycling performance and the rate performance can be improved, and the charging-discharging efficiency of the material also can be improved.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, particularly ternary cathode material of lithium ion battery of a kind of rare-earth-doped modification and preparation method thereof.
Background technology
Compared with other traditional secondary batteries, lithium ion battery has that volume is little, voltage is high, specific capacity is large and the plurality of advantages such as energy density is high, therefore, has obtained larger progress at 3C electronic applications.And positive electrode is the important component part of lithium ion battery, it is also the highest part of cost ratio in lithium ion battery.
Combine the advantage of nickel, cobalt and three kinds of elements of manganese as the nickle cobalt lithium manganate tertiary cathode material of Olivine-type Cathode Material in Li-ion Batteries, compare cobalt acid lithium, lithium nickelate and LiMn2O4, there is higher specific capacity, longer cycle life and better security performance.This material has good chemical property, but with regard to its practicality, chemical property aspect still needs further to be improved.On the one hand, due to Ni
2+with Li
+ionic radius approach easily there is cation mixing phenomenon, make material easily analyse lithium phenomenon in air, cause the chemical property variation of material; On the other hand, ternary material contacts with electrolyte and can make part metals ion dissolve, and in repeated charge process, makes material occur the phenomenon of caving in, and is unfavorable for the raising of cycle performance; Again on the one hand, the lithium ion diffusion coefficient of material and electronic conductivity need further to be improved.
In order to improve the safety problem of ternary material, mainly improve from doping and the aspect such as coated at present, but single doping or the coated ternary material that cannot prepare excellent combination property.Existing research adopts diverse ways ternary material to be carried out to the element dopings such as magnesium, zirconium and aluminium, result shows, doubly forthright the increasing of material after doping, but cycle performance changes little, and adopt coated cycle performance and the security performance that can improve material in the surfaces such as alundum (Al2O3), titanium oxide and aluminum phosphate, but can cause the specific capacity of material and doubly forthright reduction.Also have research to carry out doping and coated comprehensively modifying to ternary material, but nonactive coating layer can affect the surface conductivity of material, cause the high rate performance of battery to reduce.
Summary of the invention
The invention provides ternary cathode material of lithium ion battery of a kind of rare-earth-doped modification and preparation method thereof, overcome the deficiencies in the prior art, adopt doping and compound coating simultaneously, improved the cycle performance of material and doubly forthright.
The object of the invention is to be achieved through the following technical solutions:
First aspect, a kind of ternary cathode material of lithium ion battery of rare-earth-doped modification, chemical general formula is: LiNi
aco
1-a-bmn
br
xo
2/ 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 of aluminium, titanium or magnesium and the superpacket coating of carbon.
As preferably, described superpacket coating and LiNi
aco
1-a-bmn
br
xo
2mass ratio be 0.001～0.05:1; In described superpacket coating, the mass ratio of carbon and metal oxide is 1～10:1.
As further preferred, described superpacket coating and LiNi
aco
1-a-bmn
br
xo
2mass ratio be 0.005～0.03:1.
Second aspect, a kind of preparation method of ternary cathode material of lithium ion battery of the rare-earth-doped modification as described in first aspect, is characterized in that, comprises 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 mixed with mixing salt solution, NaOH and ammonia solvent are mixed with 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, through filtering, wash and being dried, obtain the ternary material presoma (Ni of rare-earth-doped modification
aco
1-a-bmn
br
x) (OH)
2, wherein 0<a<1,0<b<1,0<1-a-b<1,0.005<x<0.1;
By the ternary material precursor powder of rare-earth-doped modification and lithium salts powder by a certain percentage ball milling evenly mix, obtain the ternary material LiNi of rare-earth-doped modification through high-temperature calcination
aco
1-a-bmn
br
xo
2;
(3) coated containing the oxide of aluminium, titanium or magnesium and the superpacket coating of carbon on the ternary material surface of rare-earth-doped modification, then calcining at constant temperature, and through the naturally cooling ternary cathode material of lithium ion battery that obtains rare-earth-doped modification.
As preferably, described nickel salts, cobalt salt and manganese salt are respectively one or more in nitrate, sulfate and chlorate; Described nickel salts, cobalt salt and manganese salt is any one in 5:2:3,2:2:1,8:1:1,2:1:2 and 1:1:1 taking the mol ratio of nickel Co-Mn metal respectively; Described rare earth compound is one or more in solubility nitrate, carbonate, sulfate, acetate and the chlorate of rare earth; Described rare earth compound in the summation of rare earth element and described nickel salts, cobalt salt and manganese salt respectively taking the mol ratio of the summation of nickel Co-Mn metal as 0.005～0.1:1; In described mixed ammonium/alkali solutions, the mol ratio of NaOH and ammoniacal liquor is 2:1.
As further preferably, described rare earth compound in the summation of rare earth element and described nickel salts, cobalt salt and manganese salt taking the mol ratio of the summation of nickel Co-Mn metal as 0.005～0.02:1.
As preferably, described lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride and lithium sulfate; Described
lithium saltsin the summation of elemental lithium and the ternary material presoma of rare-earth-doped modification taking the mol ratio of the summation of nickel Co-Mn metal as 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 aluminium, titanium or magnesium is with Al
2o
3, TiO
2or the mass ratio of MgO meter is 1～10:1; Described coating layer and the ternary material of rare-earth-doped modification are with LiNi
aco
1-a-bmn
br
xo
2the mass ratio of meter is 0.001～0.05:1.
As further preferred, described coating layer and the ternary material of rare-earth-doped modification are with LiNi
aco
1-a-bmn
br
xo
2the 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 gas, and calcining heat is 300～800 DEG C, and calcination time is 3～8h.
Compared with prior art, great advantage of the present invention and beneficial effect are as follows:
The present invention adopt simple to operate, hold the rare-earth metal doped element of manageable wet chemical method, each element can mix on atomic level, makes product more even, easily realizes suitability for industrialized production.
(2) adopt rare earth ion to adulterate to material, structure that can stabilizing material, avoids Li in long-term charge and discharge cycles process
+deintercalation destruction that material structure is produced, thereby improve the electric conductivity of positive electrode.
(3) adopt metal oxide effects on surface to be coated, can reduce contacting of active particle and electrolyte, suppress electrolyte produces in cyclic process the HF corrosion to tertiary cathode material, thereby the impedance of lowering battery improves the chemical property of material.
(4) the carbon of coating layer can reduce the charge transfer resistance in material charge and discharge process, improves the surface conductivity of tertiary cathode material, and carbon has loose structure under anoxic hot conditions simultaneously, can be Li
+improve unimpeded passage, effectively improved the high rate performance of tertiary cathode material.
The present invention adopt rear-earth-doped after, adopt metal oxide cheap and easy to get and carbon compound coating, when 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 and preparation method thereof, with metal or rare earth element, ternary material is carried out the coating layer of the oxide, phosphate or the fluoride that contain lithium, aluminium, magnesium, titanium, zirconium at the coated one deck in ternary material surface after doping vario-property, comprehensively improve cycle performance and the high rate performance of material; And the present invention adopt rear-earth-doped after, material surface is carried out to metal oxide and carbon compound coating, more effectively improve cycle performance and doubly forthright.
CN102760884A discloses anode material for lithium-ion batteries that a kind of lithium fast-ionic conductor modifies mutually and preparation method thereof, adopt rare earth element to carry out being coated one deck lithium fast-ionic conductor compound on ternary material surface after doping vario-property to ternary material, and invent therewith, different what be that the present invention adopts is metal oxide cheap and easy to get and carbon compound coating, improves the efficiency for charge-discharge of material when improving cycle performance and high rate performance.
CN102088087A discloses anode material for lithium-ion batteries of a kind of doped with rare-earth elements and preparation method thereof, LiMn2O4 is carried out to doping vario-property with rare earth element, and after modification, cycle performance is greatly improved, but first discharge specific capacity is lower.
CN201310397441 discloses a kind of method of modifying of tertiary cathode material, adopts Rare Earth Lanthanum to be coated modification to ternary material, has just carried out single coated modification; And the present invention is that employing is rear-earth-doped, oxide is coated composite modified.
CN103280572A has announced a kind of lithium ion cell positive ternary material and preparation method, adopts lutetium element ternary material to carry out doping vario-property, has just carried out single doping vario-property; And the present invention is that employing is rear-earth-doped, oxide is coated composite modified.
Brief description of the drawings
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.
Embodiment
For the present invention being had to darker understanding; below in conjunction with in embodiment, technical scheme being clearly and completely described; but embodiments of the invention are only used to explain the present invention; and unrestricted the present invention; the every other case study on implementation that those skilled in the art obtain under the prerequisite of not making creative work, all belongs to protection scope of the present invention.
Embodiment 1:
Ni:Mn:Co:La=1:1:1:0.005 preparing metal total concentration is 2mol/L in molar ratio nickel nitrate, manganese nitrate, cobalt nitrate, lanthanum nitrate mixed aqueous solution; The NaOH that preparation total concentration is 10mol/L and the mixed solution of ammoniacal liquor, wherein the mol ratio of NaOH and ammoniacal liquor is 2:1.
Above-mentioned two kinds of solution are joined to reactor with certain speed simultaneously, control reaction pH value be 12, reaction temperature is 50 DEG C, reaction 6h after ageing 8h, after filtration, washing, dry after obtain lanthanum adulterate nickel-cobalt-manganese ternary material presoma.
By the nickel-cobalt-manganese ternary material presoma of above-mentioned lanthanum doping with lithium carbonate according to Li:(Ni+Mn+Co) after the ratio of=1.01:1 mixes, at 1000 DEG C of high-temperature calcination 8h, cooling, pulverize, sieving obtains the nickle cobalt lithium manganate ternary material that lanthanum adulterates.
The nickle cobalt lithium manganate ternary material that above-mentioned lanthanum is adulterated is by 100% mass parts, with the Al of 0.2% mass parts
2o
3to carry out surface recombination coated with the C of 1% mass parts, and after oven dry, in 700 DEG C, argon gas atmosphere, constant temperature is processed 8h, obtains the tertiary cathode material of aluminium oxide and carbon compound coating.
The electrochemical property test of material adopts blue electric battery test system to test at 25 DEG C, and test voltage scope is 2.7V～4.3V; High rate performance test condition: 0.1C discharges and recharges once, and 0.2C discharges and recharges once, and 0.2C charging 1C discharges once; Cycle performance test condition: discharge and recharge with 1C multiplying power, circulate 50 weeks, investigate capability retention.The specific discharge capacity of material under 0.1C multiplying power is 195.0mAh/g, and under 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 better.1C charges and discharge 50 weeks capability retentions of circulation and is greater than 98%, and cycle performance is better.
Embodiment 2:
Ni:Mn:Co:Pr=5:3:2:0.01 preparing metal total concentration is 1mol/L in molar ratio nickel nitrate, manganese nitrate, cobalt nitrate, praseodymium nitrate mixed aqueous solution; The NaOH that preparation total concentration is 10mol/L and the mixed solution of ammoniacal liquor, wherein the mol ratio of NaOH and ammoniacal liquor is 2:1.
Above-mentioned two kinds of solution are joined to reactor with certain speed simultaneously, control reaction pH value be 12, reaction temperature is 45 DEG C, reaction 6h after ageing 8h, after filtration, washing, dry after obtain praseodymium adulterate nickel-cobalt-manganese ternary material presoma.
By the nickel-cobalt-manganese ternary material presoma of above-mentioned praseodymium doping with lithium carbonate according to Li:(Ni+Mn+Co) after the ratio of=1.02:1 mixes, at 1000 DEG C of high-temperature calcination 8h, cooling, pulverize, sieving obtains the nickle cobalt lithium manganate ternary material that praseodymium adulterates.
The nickle cobalt lithium manganate ternary material that above-mentioned praseodymium is adulterated is by 100% mass parts, carrying out surface recombination with the MgO of 0.1% mass parts and the C of 1% mass parts is coated, after oven dry, in 800 DEG C, argon gas atmosphere, constant temperature is processed 7h, obtains the tertiary cathode material of magnesium oxide and carbon compound coating.
Embodiment 3:
Ni:Mn:Co:Ce=4:4:2:0.001 preparing metal total concentration is 2mol/L in molar ratio nickel nitrate, manganese nitrate, cobalt nitrate, cerous nitrate mixed aqueous solution; The NaOH that preparation total concentration is 10mol/L and the mixed solution of ammoniacal liquor, wherein the mol ratio of NaOH and ammoniacal liquor is 2:1.
Above-mentioned two kinds of solution are joined to reactor with certain speed simultaneously, control reaction pH value be 12, reaction temperature is 50 DEG C, reaction 6h after ageing 8h, after filtration, washing, dry after obtain cerium adulterate nickel-cobalt-manganese ternary material presoma.
By the nickel-cobalt-manganese ternary material presoma of above-mentioned cerium doping with lithium carbonate according to Li:(Ni+Mn+Co) after the ratio of=1.01:1 mixes, at 1000 DEG C of high-temperature calcination 8h, cooling, pulverize, sieving obtains the nickle cobalt lithium manganate ternary material that cerium adulterates.
The nickle cobalt lithium manganate ternary material that above-mentioned cerium is adulterated is by 100% mass parts, with the TiO of 0.5% mass parts
2to carry out surface recombination coated with the C of 0.5% mass parts, and after oven dry, in 700 DEG C, argon gas atmosphere, constant temperature is processed 8h, obtains the tertiary cathode material of titanium oxide and carbon compound coating.
Claims (10)
1. a ternary cathode material of lithium ion battery for rare-earth-doped modification, is characterized in that, chemical general formula is: LiNi
aco
1-a-bmn
br
xo
2/ 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 of aluminium, titanium or magnesium and the superpacket coating of carbon.
2. the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 1, is characterized in that, described superpacket coating and LiNi
aco
1-a-bmn
br
xo
2mass ratio be 0.001～0.05:1; In described superpacket coating, the mass ratio of carbon and metal oxide is 1～10:1.
3. the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 1, is characterized in that, described superpacket coating and LiNi
aco
1-a-bmn
br
xo
2mass ratio be 0.005～0.03:1.
4. a preparation method for the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 1, is characterized in that, comprises 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 mixed with mixing salt solution, NaOH and ammonia solvent are mixed with 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, through filtering, wash and being dried, obtain the ternary material presoma (Ni of rare-earth-doped modification
aco
1-a-bmn
br
x) (OH)
2, wherein 0<a<1,0<b<1,0<1-a-b<1,0.005<x<0.1;
By the ternary material precursor powder of rare-earth-doped modification and lithium salts powder by a certain percentage ball milling evenly mix, obtain the ternary material LiNi of rare-earth-doped modification through high-temperature calcination
aco
1-a-bmn
br
xo
2;
(3) coated containing the oxide of aluminium, titanium or magnesium and the superpacket coating of carbon on the ternary material surface of rare-earth-doped modification, then calcining at constant temperature, and through the naturally cooling ternary cathode material of lithium ion battery that obtains rare-earth-doped modification.
5. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 4, is characterized in that, described nickel salts, cobalt salt and manganese salt are respectively one or more in nitrate, sulfate and chlorate; Described nickel salts, cobalt salt and manganese salt is any one in 5:2:3,2:2:1,8:1:1,2:1:2 and 1:1:1 taking the mol ratio of nickel Co-Mn metal respectively; Described rare earth compound is one or more in solubility nitrate, carbonate, sulfate, acetate and the chlorate of rare earth; Described rare earth compound in the summation of rare earth element and described nickel salts, cobalt salt and manganese salt respectively taking the mol ratio of the summation of nickel Co-Mn metal as 0.005～0.1:1; In described mixed ammonium/alkali solutions, the mol ratio of NaOH and ammoniacal liquor is 2:1.
6. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 5, it is characterized in that, described rare earth compound in the summation of rare earth element and described nickel salts, cobalt salt and manganese salt taking the mol ratio of the summation of nickel Co-Mn metal as 0.005～0.02:1.
7. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 4, is characterized in that, described lithium salts is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium chloride and lithium sulfate; Described lithium salts in the summation of elemental lithium and the ternary material presoma of rare-earth-doped modification taking the mol ratio of the summation of nickel Co-Mn metal as 1.01～1.10:1.
8. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 4, is characterized in that, one or more in sucrose, glucose, starch and polyethylene glycol of described carbon source; The oxide of described carbon and aluminium, titanium or magnesium is with Al
2o
3, TiO
2or the mass ratio of MgO meter is 1～10:1; Described coating layer and the ternary material of rare-earth-doped modification are with LiNi
aco
1-a-bmn
br
xo
2the mass ratio of meter is 0.001～0.05:1.
9. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 4, is characterized in that, described coating layer and the ternary material of rare-earth-doped modification are with LiNi
aco
1-a-bmn
br
xo
2the mass ratio of meter is 0.005～0.03:1.
10. the preparation method of the ternary cathode material of lithium ion battery of rare-earth-doped modification as claimed in claim 4, is characterized in that, 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 gas, and calcining heat is 300～800 DEG C, and calcination time is 3～8h.
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