CN116632218A - 锂离子电池用单晶富锂锰正极材料及其制备方法 - Google Patents
锂离子电池用单晶富锂锰正极材料及其制备方法 Download PDFInfo
- Publication number
- CN116632218A CN116632218A CN202310873929.4A CN202310873929A CN116632218A CN 116632218 A CN116632218 A CN 116632218A CN 202310873929 A CN202310873929 A CN 202310873929A CN 116632218 A CN116632218 A CN 116632218A
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- Prior art keywords
- lithium
- nickel cobalt
- positive electrode
- electrode material
- rich
- Prior art date
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- Pending
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 25
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 13
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 5
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 11
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 11
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 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 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 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 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 2
- 150000007965 phenolic acids Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin 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
- 239000000463 material Substances 0.000 abstract description 32
- 230000008569 process Effects 0.000 abstract description 6
- 150000002736 metal compounds Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 3
- 239000011164 primary particle Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 21
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 14
- 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 14
- 230000014759 maintenance of location Effects 0.000 description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GFBBLVIVJHUGIF-UHFFFAOYSA-N [Mn].[Ni].[Co].[Ni] Chemical compound [Mn].[Ni].[Co].[Ni] GFBBLVIVJHUGIF-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000009768 microwave sintering Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 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
- H01M4/36—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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/36—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
-
- 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
- H01M4/58—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种锂离子电池用单晶富锂锰正极材料及其制备方法,用通式Li1+ xNi0.13Co0.13Mn0.54MyO2表示,其具体方法是:分别称取镍钴锰的化合物、锂盐、助熔剂、添加剂Ⅰ混合均匀后,在马弗炉中进行高温煅烧,冷却后水洗、烘干、筛分,再与添加剂Ⅱ混合进行二次烧结,制备单晶富锂锰正极材料。该方法材料合成过程中加入助熔剂促使一次颗粒长大,金属离子和阴离子双掺杂稳定富锂材料晶体结构稳定性,C源和金属化合物双包覆形成O空位,抑制表面气体释放,激活四面体位置的Li,提高材料的首次库伦效率、容量和循环稳定性。
Description
技术领域
本发明涉及一种锂离子电池用正极材料,尤其涉及一种具有单晶形貌的富锂锰正极材料。
背景技术
随着新能源汽车的高速发展,对动力电池性能的需求不断提升,近年来,新能源汽车对续航里程的要求越来越高,对锂离子电池的能量密度、循环性能和安全性能也有更高的挑战。富锂锰正极材料(Li1+wNixCoyMnzO2)凭借高比容量(~250 mAh g-1)、高工作电压(~3.6 V)及低成本等优势,有望成为下一代商用高比能锂电池的正极材料。
富锂锰正极材料具有首次不可逆容量损失大、循环性能差等缺点。富锂锰正极材料在首次充放电过程,Li和O在高电压下不可逆脱出导致首周不可逆容量损失大和首次库伦效率低;晶格氧的不可逆损失会导致过渡金属迁移、结构重排和表界面副反应等情况的发生,加剧高压下与电解液发生副反应,进而导致循环性能变差。常见的富锂锰正极材料是由纳米一次小颗粒团聚成的二次颗粒,但二次颗粒机械强度较低、易破裂,循环过程中二次离子内部会出现晶间裂纹,导致二次粒子破裂,使循环稳定性降低。单晶材料具有机械强度高、比表面积小等特点,由单晶材料制成极片的压实密度高、辊压时不易破碎;由于单晶材料内部不存在晶界界面,多次充放电循环后不发生晶界破碎;单晶材料的比表面积小,与电解液接触面积小,副反应小。
申请号为CN202310132212.4将锂源、镍源、钴源、锰源、络合剂配成溶液后进行喷雾干燥,后对其进行微波烧结,后与表面活性剂进行修饰得到修饰单晶富锂锰正极材料。申请号为CN202310437175.8将前驱体、50%含锂化合物和熔盐混合后进行煅烧、洗涤、烘干后,与剩余50%含锂化合物进行二次煅烧制备得到单晶富锂锰基正极材料。申请号为CN202210991039.9是在富锂锰前驱体合成时加入含溶胀材料来制备掺杂锡的富锂锰前驱体,后烧结得到富锂锰单晶正极材料。申请号为CN201910642068.2通过调控复合导电剂溶液的Zeta电位与类单晶富锂锰基正极材料混合,后超声分散、烘干、烧结得到复合导电剂包覆类单晶正极材料。本专利是在富锂锰材料合成过程中加入助熔剂促使一次颗粒长大,金属离子和阴离子双掺杂稳定富锂材料晶体结构稳定性,C源和金属化合物双包覆形成O空位,抑制表面气体释放,激活四面体位置的Li,提高材料的首次库伦效率、容量和循环稳定性。
发明内容
针对现有技术中存在的问题,本发明提供一种具有首次库伦效率高、容量高、循环性能好、振实密度高的锂离子电池用单晶富锂锰正极材料及其制备方法。本发明的富锂锰正极材料一方面通过掺杂具有d0排布的过渡金属离子稳定富锂材料的O,掺杂阴离子增强晶格氧框架稳定性,C源和金属化合物双包覆可在颗粒表面形成O空位,抑制表面气体释放,激活四面体位置的Li,减少颗粒与电解液的接触,降低颗粒与电解液的副反应,从而提高材料的首次库伦效率、容量和循环稳定性,另一方面通过制备单晶形貌抑制循环过程中颗粒破碎,提高振实密度和电化学性能。
为解决上述技术问题,本发明采用以下技术方案:
一种锂离子电池用单晶富锂锰正极材料,用通式LixNi0.13Co0.13Mn0.54MyO2表示,M选自Mo、V、W、Nb、Ti、Ta、Hf、Zr、F、S、Br、Mg、Ce、Al、Sr、C的至少三种元素,且M必须包含d0排布的过渡金属离子、阴离子和C元素,1.1≤x≤1.3,0≤y≤0.02,其形貌为单晶,平均粒径D50为0.1-5μm。
本发明所述的锂离子电池用单晶富锂锰正极材料的制备方法,步骤在于:分别称取镍钴锰化合物、锂盐、助熔剂、添加剂Ⅰ混合均匀后,在马弗炉中进行高温煅烧,冷却后水洗、烘干、筛分,再与添加剂Ⅱ混合后进行二次烧结,制得锂二次电池用单晶富锂锰正极材料,其中锂盐选自碳酸锂、单水氢氧化锂、碳酸氢锂、草酸锂、硝酸锂或乙酸锂中的至少一种。
进一步,所述镍钴锰化合物为镍钴锰氢氧化物、镍钴锰碳酸盐、镍钴锰氧化物,平均粒径D50为1-5μm,镍钴锰氧化物是由镍钴锰氢氧化物或镍钴锰碳酸盐高温300-700℃预烧1-10h后得到的;
进一步,所述助熔剂为氯化钾、氯化钠、硫酸锂、氯化锂、硫酸钠、硼酸、碳酸锂中的至少一种,助熔剂添加量与镍钴锰化合物的摩尔比为(0.5-50):1,锂源与镍钴锰化合物的摩尔比为(1.15-1.40):1;所用锂盐均为电池级,且平均粒径D50为3-15μm;
进一步,所述添加剂I为含有d0排布的过渡金属离子的氧化物或氢氧化物,以及和含有阴离子F、S或Br的化合物中的至少一种组成的混合物,其中含有d0排布的过渡金属离子为Mo、V、W、Nb、Ti、Ta、Hf、Zr中的至少一种;添加剂I的平均粒径D50为10-100nm。
进一步,所述添加剂Ⅱ为含有蔗糖、葡萄糖、淀粉、酚酸树脂、油酸、纤维素或有机高分子聚合物中的至少一种,以及和含有Zr、Al、W、Mg、Ti、Ce、Sr的氧化物或氢氧化物的至少一种组成的混合物。进一步,所述高温煅烧为两段烧结,先经过450-600℃烧结1-6h,后750-950℃烧结10-30h。
进一步,所述水洗温度为10-40℃,水洗时间为1-60min,水洗倍数为5-100倍水。烘干温度为60-120℃,时间1-5h。
进一步,所述二次烧结的温度为400-700℃,烧结时间为0.5-10h,烧结气氛为惰性气体,如Ar、N2。
本发明的有益效果:助熔剂有利于材料高温过程中一次颗粒的生长,使材料在较低的烧结温度时生成较好的单晶形貌和晶体结构,提升材料的压实密度和循环性能,水洗去除助熔剂的影响;具有d0排布的过渡金属离子掺杂稳定富锂材料的O,阴离子掺杂增强晶格氧框架稳定性,C源和金属化合物双包覆可在颗粒表面形成O空位,抑制表面气体释放,激活四面体位置的Li,减少颗粒与电解液的接触,降低颗粒与电解液的副反应,从而提高材料的首次库伦效率、容量和循环稳定性。通过微观结构调控,减少晶格氧释放,实现富理层状氧化物正极材料的精确设计和可控制备。
附图说明
图1为实施例1中得到的高镍正极材料的扫描电镜图;
图2为实施例1中得到的高镍正极材料的X射线衍射图;
图3为实施例1中得到的高镍正极材料在0.5 C条件下的循环保护率图。
具体实施方式
下面结合具体实施例,对本发明做进一步说明。应理解,以下实施例仅用于说明本发明而非用于限制本发明的范围,该领域的技术熟练人员可以根据上述发明的内容作出一些非本质的改进和调整。
实施例1
本实施例锂离子电池用单晶富锂锰正极材料的制备方法如下:
取D50为2.5μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用由碳酸锂,碳酸锂与镍钴锰氢氧化物前驱体的摩尔比为1.35:1的方式进行调配,添加剂为20 nm的纳米氧化锆和氟化锂的混合物,锆元素与镍钴锰氢氧化物的摩尔比为0.002:1、氟元素与镍钴锰氢氧化物的摩尔比为0.003:1,助熔剂为氯化锂,助熔剂量与镍钴锰氢氧化物的摩尔比为4:1,用球磨机混合均匀后,在马弗炉中先低温550℃焙烧4h,后在860℃焙烧20小时,冷却后加水溶解水洗,水洗温度为30℃,水洗时间为30min,水洗倍数为50倍水,烘干温度为80℃,时间3h。烘干后过200目筛网,再与葡萄糖和氧化锆混合均匀,葡萄糖与锂镍钴锰氧化物的摩尔比为0.001:1,氧化锆与锂镍钴锰氧化物的摩尔比为0.001:1,后在管式炉Ar气氛中700℃烧结0.5h后,得到单晶Li1.26Ni0.13Co0.13Mn0.54Zr0.003F0.003C0.001O2。
Li1.26Ni0.13Co0.13Mn0.54Zr0.003F0.003C0.001O2的扫描电镜图见图1所示。图2为Li1.26Ni0.13Co0.13Mn0.54Zr0.003F0.003C0.001O2的X射线衍射图,图3为得到的Li1.26Ni0.13Co0.13Mn0.54Zr0.003F0.003C0.001O2组装的扣式CR2025在0.5C/0.5C循环性能图。0.1 C条件下,所得材料的放电比容量为298 mAh/g,首次库伦效率为82%,0.5C/0.5C循环100圈容量保持率为91 %,具有较好的循环性能。
实施例2
本实施例锂离子电池用单晶富锂锰正极材料的制备方法如下:
取D50为3μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用由单水氢氧化锂,单水氢氧化锂与镍钴锰氢氧化物前驱体的摩尔比为1.34:1的方式进行调配,添加剂为50 nm的纳米氧化钛和氯化锂的混合物,钛元素与镍钴锰氢氧化物的摩尔比为0.002:1,氯元素与镍钴锰氢氧化物的摩尔比为0.001:1,助熔剂为氯化钠,助熔剂量与镍钴锰氢氧化物的摩尔比为6:1,用球磨机混合均匀后,在马弗炉中先低温550℃焙烧3h,后在900 ℃焙烧12小时,冷却后加水溶解水洗,水洗温度为30℃,水洗时间为30min,水洗倍数为20倍水,烘干温度为100℃,时间1h。烘干后过200目筛网,再与酚醛树脂和氧化铝混合均匀,酚醛树脂与锂镍钴锰氧化物的摩尔比为0.002:1,铝元素与锂镍钴锰氧化物的摩尔比为0.001:1,后在管式炉N2气氛中550℃烧结3h后,得到单晶Li1.20Ni0.13Co0.13Mn0.54Ti0.002Cl0.001Al0.002C0.002O2。0.1 C条件下,所得材料的放电比容量为286 mAh/g,首次库伦效率为84%,0.5C/0.5C循环80圈容量保持率为92 %。
实施例3
本实施例锂离子电池用单晶富锂锰正极材料的制备方法如下:
将2.5μm的Ni0.13Co0.13Mn0.54(OH)2前驱体在马弗炉中500℃焙烧3h得到镍钴锰Ni0.13Co0.13Mn0.54O2,锂盐采用碳酸锂,碳酸锂与镍钴锰氧化物前驱体的摩尔比为1.4:1的方式进行调配,添加剂为50 nm的纳米氧化钒和硫化钠的混合物,钒元素与镍钴锰氧化物的摩尔比为0.002:1,硫元素与镍钴锰氧化物的摩尔比为0.003:1,助熔剂为氯化钾,助熔剂量与镍钴锰氧化物的摩尔比为5:1,用球磨机混合均匀后,在马弗炉中先低温720℃焙烧0.5h,后在920 ℃焙烧12小时,冷却后加水溶解水洗,水洗温度为40℃,水洗时间为10min,水洗倍数为60倍水,烘干温度为80℃,时间5h。烘干后过200目筛网,再与油酸、氧化锆混合均匀,油酸与锂镍钴锰氧化物的摩尔比为0.004:1,氧化锆与锂镍钴锰氧化物的摩尔比为0.002:1,后在管式炉Ar气氛中600℃烧结5h后,得到单晶Li1.18Ni0.13Co0.13Mn0.54V0.002S0.003Zr0.002C0.004O2。0.1 C条件下,所得材料的放电比容量为284 mAh/g,首次库伦效率为79%,0.5C/0.5C循环80圈容量保持率为90 %。
实施例4
本实施例锂离子电池用单晶富锂锰正极材料的制备方法如下:
将4.5μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用醋酸锂,醋酸锂与镍钴锰氢氧化物前驱体的摩尔比为1.4:1的方式进行调配,添加剂为100 nm的纳米氧化钨和溴化钠,钨元素与镍钴锰氢氧化物的摩尔比为0.002:1,溴元素与镍钴锰氢氧化物的摩尔比为0.002:1,助熔剂为硫酸锂,助熔剂量与镍钴锰氢氧化物的摩尔比为3:1,用球磨机混合均匀后,在马弗炉中先低温580℃焙烧2h,后在840 ℃焙烧20小时,冷却后加水溶解水洗,水洗温度为20℃,水洗时间为50min,水洗倍数为40倍水,烘干温度为70℃,时间3h。烘干后过200目筛网,再与纤维素、氧化镁混合均匀,纤维素与锂镍钴锰氧化物的摩尔比为0.002:1,镁元素与锂镍钴锰氧化物的摩尔比为0.001:1,后在管式炉Ar气氛中700℃烧结5h后,得到单晶Li1.2 5Ni0.13Co0.13Mn0.54W0.002Br0.002Mg0.001C0.002O2。0.1 C条件下,所得材料的放电比容量为289mAh/g,首次库伦效率为78%,0.5C/0.5C循环80圈容量保持率为89 %。
实施例5
本实施例锂离子电池用单晶富锂锰正极材料的制备方法如下:
将1μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用单水氢氧化锂,单水氢氧化锂与镍钴锰氢氧化物前驱体的摩尔比为1.25:1的方式进行调配,添加剂为30 nm的纳米氧化钽和氟化锂的混合物,钽元素与镍钴锰氢氧化物的摩尔比为0.002:1,氟元素与镍钴锰氢氧化物的摩尔比为0.002:1,助熔剂为硫酸钠,助熔剂量与镍钴锰氢氧化物的摩尔比为8,用球磨机混合均匀后,在马弗炉中先低温450℃焙烧5h,后在750 ℃焙烧30小时,冷却后加水溶解水洗,水洗温度为20℃,水洗时间为20min,水洗倍数为10倍水,烘干温度为60℃,时间3h。烘干后过200目筛网,再与酚醛树脂和氧化钨混合均匀,酚醛树脂与锂镍钴锰氧化物的摩尔比为0.002:1,钨元素与锂镍钴锰氧化物的摩尔比为0.002:1,后在管式炉Ar气氛中650℃烧结5h后,得到单晶Li1.19Ni0.13Co0.13Mn0.54Ta0.002F0.002W0.002C0.002O2。0.1 C条件下,所得材料的放电比容量为290 mAh/g,首次库伦效率为82%,0.5C/0.5C循环50圈容量保持率为95%。
对比例1
将3μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用碳酸锂,锂盐与镍钴锰氢氧化物的摩尔比为1.3:1的方式进行调配,用球磨机混合均匀后,在马弗炉中先低温450℃焙烧2h,后在1050 ℃焙烧15小时,后过200目筛网,得到单晶形貌Li1.22Ni0.13Co0.13Mn0.54O2。0.1 C条件下,所得材料的放电比容量为203 mAh/g,首次库伦效率为68%,0.5C/0.5C循环80圈容量保持率为85 %。
对比例2
将2μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用单水氢氧化锂,锂盐与镍钴锰氢氧化物的摩尔比为1.35:1的方式进行调配,用球磨机混合均匀后,在马弗炉中先低温550℃焙烧4h,后在860 ℃焙烧20小时,后过200目筛网,得到多晶形貌Li1.25Ni0.13Co0.13Mn0.54O2。0.1 C条件下,所得材料的放电比容量为240 mAh/g,首次库伦效率为63%,0.5C/0.5C循环80圈容量保持率为88 %。
对比例3
将3μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用单水氢氧化锂,锂盐与镍钴锰氢氧化物的摩尔比为1.25:1的方式进行调配,添加剂为氧化锆,锆元素与镍钴锰氢氧化物的摩尔比为0.002:1,用球磨机混合均匀后,在马弗炉中先低温550℃焙烧4h,后在860 ℃焙烧20小时,后过200目筛网,与氧化镁混合均匀,镁元素与锂镍钴锰氧化物的摩尔比为0.002:1,后再马弗炉中600℃煅烧5h,得到多晶形貌Li1.25Ni0.13Co0.13Mn0.54Zr0.002Mg0.002O2。0.1 C条件下,所得材料的放电比容量为238 mAh/g,首次库伦效率为65%,0.5C/0.5C循环80圈容量保持率为92 %。
对比例4
将3μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用单水氢氧化锂,锂盐与镍钴锰氢氧化物的摩尔比为1.35:1的方式进行调配,助熔剂为硫酸锂,助熔剂量与镍钴锰氢氧化物的摩尔比为3:1,用球磨机混合均匀后,在马弗炉中先低温550℃焙烧4h,后在850 ℃焙烧20小时,冷却后加水溶解水洗,水洗温度为20℃,水洗时间为50min,水洗倍数为40倍水,烘干温度为70℃,时间3h,水洗烘干后过200目筛网,添加剂为氧化锆和葡萄糖,锆元素与锂镍钴锰氧化物的摩尔比为0.002:1,葡萄糖与锂镍钴锰氧化物的摩尔比为0.001:1,后在Ar气氛中600℃煅烧5h,得到单晶形貌Li1.20Ni0.13Co0.13Mn0.54Zr0.002C0.001O2。0.1 C条件下,所得材料的放电比容量为253 mAh/g,首次库伦效率为78%,0.5C/0.5C循环80圈容量保持率为86 %。
对比例5
将2μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用单水氢氧化锂,锂盐与镍钴锰氢氧化物的摩尔比为1.40:1的方式进行调配,添加剂为氧化锆和氟化锂,锆元素与镍钴锰氢氧化物的摩尔比为0.002:1,氟元素与镍钴锰氢氧化物的摩尔比为0.001:1,助熔剂为氯化钠,助熔剂量与镍钴锰氢氧化物的摩尔比为5:1,用球磨机混合均匀后,在马弗炉中先低温650℃焙烧4h,后在880 ℃焙烧18小时,冷却后加水溶解水洗,水洗温度为20℃,水洗时间为50min,水洗倍数为20倍水,烘干温度为70℃,时间3h,水洗烘干后过200目筛网,得到单晶形貌Li1.25Ni0.13Co0.13Mn0.54Zr0.002F0.001O2。0.1 C条件下,所得材料的放电比容量为236 mAh/g,首次库伦效率为69%,0.5C/0.5C循环80圈容量保持率为89 %。
对比例6
将3μm的Ni0.13Co0.13Mn0.54(OH)2前驱体,锂盐采用单水氢氧化锂,锂盐与镍钴锰氢氧化物的摩尔比为1.25:1的方式进行调配,添加剂为氟化锂,氟元素与镍钴锰氢氧化物的摩尔比为0.002:1,助熔剂为氯化钾,助熔剂量与镍钴锰氢氧化物的摩尔比为8:1,用球磨机混合均匀后,在马弗炉中先低温550℃焙烧4h,后在900 ℃焙烧20小时,冷却后加水溶解水洗,水洗温度为20℃,水洗时间为30min,水洗倍数为10倍水,烘干温度为80℃,时间2h,后过200目筛网,与氧化镁混合均匀,镁元素与锂镍钴锰氧化物的摩尔比为0.002:1,后再马弗炉中600℃煅烧5h,得到单晶形貌Li1.25Ni0.13Co0.13Mn0.54F0.002Mg0.002O2。0.1 C条件下,所得材料的放电比容量为248 mAh/g,首次库伦效率为66%,0.5C/0.5C循环80圈容量保持率为90 %。
上述测试结果如表1所示。
表1 测试结果
以上显示和描述了本发明的基本原理和主要特征以及本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (10)
1.一种锂离子电池用单晶富锂锰正极材料,其特征在于,所述单晶正极材料用通式LixNi0.13Co0.13Mn0.54MyO2表示,M选自Mo、V、W、Nb、Ti、Ta、Hf、Zr、F、S、Br、Mg、Ce、Al、Sr、C的至少三种元素,且M必须包含d0排布的过渡金属离子、阴离子和C元素,1.1≤x≤1.3,0≤y≤0.02,其形貌为单晶,平均粒径D50为0.1-5μm。
2.根据权利要求1所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:分别称取镍钴锰化合物、锂盐、助熔剂、添加剂Ⅰ混合均匀后,在马弗炉中进行高温煅烧,冷却后水洗、烘干、筛分,再与添加剂Ⅱ混合后进行二次烧结,制得锂二次电池用单晶富锂锰正极材料。
3.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述镍钴锰化合物为镍钴锰氢氧化物、镍钴锰碳酸盐、镍钴锰氧化物,平均粒径D50为1-5μm,其中镍钴锰氧化物是由镍钴锰氢氧化物或镍钴锰碳酸盐高温300-700℃预烧1-10h后得到的。
4.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述锂盐选自碳酸锂、单水氢氧化锂、碳酸氢锂、草酸锂、硝酸锂或乙酸锂中的至少一种,所用锂盐均为电池级,且平均粒径D50为3-15μm。
5.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述助熔剂为氯化钾、氯化钠、硫酸锂、氯化锂、硫酸钠、硼酸中的至少一种。
6.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述助熔剂与镍钴锰化合物的摩尔比为(0.5-50):1,锂盐与镍钴锰化合物的摩尔比为(1.15-1.40):1。
7.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述添加剂I为含有d0排布的过渡金属离子的氧化物或氢氧化物,以及和含有阴离子F、S或Br的化合物中的至少一种组成的混合物,其中含有d0排布的过渡金属离子为Mo、V、W、Nb、Ti、Ta、Hf、Zr中的至少一种;添加剂I的平均粒径D50为10-100nm;
添加剂Ⅱ为含有蔗糖、葡萄糖、淀粉、酚酸树脂、油酸、纤维素或有机高分子聚合物中的至少一种,以及和含有Zr、Al、W、Mg、Ti、Ce、Sr的氧化物或氢氧化物的至少一种组成的混合物。
8.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述高温煅烧为两段烧结,先经过450-600℃烧结1-6h,后750-950℃烧结10-30h。
9.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述水洗温度为10-40℃,水洗时间为1-60min,水洗倍数为5-100倍水,烘干温度为60-120℃,时间1-5h。
10.根据权利要求2所述的锂离子电池用单晶富锂锰正极材料的制备方法,其特征在于:所述二次烧结的温度为400-700℃,烧结时间为0.5-10h,烧结气氛为惰性气体。
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