CN104347853B - Lithium manganate composite positive electrode material, a preparing method thereof and a lithium-ion battery - Google Patents
Lithium manganate composite positive electrode material, a preparing method thereof and a lithium-ion battery Download PDFInfo
- Publication number
- CN104347853B CN104347853B CN201410491048.7A CN201410491048A CN104347853B CN 104347853 B CN104347853 B CN 104347853B CN 201410491048 A CN201410491048 A CN 201410491048A CN 104347853 B CN104347853 B CN 104347853B
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- Prior art keywords
- lithium
- gradient type
- manganese
- oxide
- nickel
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000007774 positive electrode material Substances 0.000 title abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 45
- 239000011572 manganese Substances 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000011065 in-situ storage Methods 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 13
- 238000009768 microwave sintering Methods 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000001694 spray drying Methods 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract 5
- 239000010405 anode material Substances 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 18
- 239000011824 nuclear material Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000000470 constituent Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 230000014759 maintenance of location Effects 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 9
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 8
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000010334 sieve classification Methods 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- SYGXXQPAYVYJIN-UHFFFAOYSA-N C(O)(O)=O.[Mn].[Co].[Ni] Chemical compound C(O)(O)=O.[Mn].[Co].[Ni] SYGXXQPAYVYJIN-UHFFFAOYSA-N 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071264 lithium citrate Drugs 0.000 claims description 4
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 4
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 4
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- KSHLPUIIJIOBOQ-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[Co++].[Ni++] Chemical compound [O--].[O--].[O--].[O--].[Co++].[Ni++] KSHLPUIIJIOBOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 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 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 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
- 239000012266 salt solution 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
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 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 claims 3
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims 2
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims 2
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims 2
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229960001078 lithium Drugs 0.000 claims 1
- 229940031993 lithium benzoate Drugs 0.000 claims 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims 1
- 239000011656 manganese carbonate Substances 0.000 claims 1
- 229940093474 manganese carbonate Drugs 0.000 claims 1
- 235000006748 manganese carbonate Nutrition 0.000 claims 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 15
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000003860 storage Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 235000019504 cigarettes Nutrition 0.000 description 8
- 238000005121 nitriding Methods 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- 229910014143 LiMn2 Inorganic materials 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910011681 LiNi0.7Co0.2Al0.1O2 Inorganic materials 0.000 description 2
- 229910015694 LiNi0.85Co0.1Al0.05O2 Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- -1 lithium alkoxide Chemical class 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 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
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 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
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 239000002270 dispersing agent Substances 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- FTNXDODVXCUJNW-UHFFFAOYSA-N erbium;nitric acid Chemical compound [Er].O[N+]([O-])=O FTNXDODVXCUJNW-UHFFFAOYSA-N 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 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
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- H01M4/362—Composites
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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
- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
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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
- H01M4/52—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
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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
- H01M4/62—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 provides a lithium manganate composite positive electrode material, a preparing method thereof and a lithium-ion battery. The composite positive electrode material is of a core-shell structure. The inner layer of the composite positive electrode material is an in-situ composite of lithium manganate and nickel-rich concentration gradient type nickel cobalt manganese/lithium aluminate LiMn2O4-LiNi1-x-yCox(Al/Mn)yO2, wherein x is more than 0 and less than or equal to 0.25, and y is more than 0 and less than or equal to 0.15; the outer shell of the composite positive electrode material is a metal oxide coated layer. According to the lithium manganate composite positive electrode material and the preparing method thereof, the in-situ composite of lithium manganate and nickel-rich concentration gradient type nickel cobalt manganese/lithium aluminate is obtained after in-site sintering of a manganese source, a nickel-rich concentration gradient type nickel cobalt manganese/lithium aluminate precursor, and a lithium source, then shell-layer metal oxide is cladded by using spray drying, and finally the composite positive electrode material is obtained by combining a microwave sintering process. The composite positive electrode material provided by the invention has relatively high specific capacity, and excellent high temperature cycling and storage performances.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to anode material for lithium-ion batteries and lithium ion battery system
Standby technology, more particularly to a kind of lithium manganate composite anode material and by the positive electrode as positive active material lithium-ion electric
Pond.
Background technology
Lithium ion battery has that voltage is high, energy density is big, cyclicity is good, memory-less effect, self discharge are low many excellent
Point, is widely used in fields such as portable power source, various portable electric appts, high-end number, electric automobiles.Corresponding positive pole material
Expect to play decisive role to the performance of lithium ion battery, all the time, develop electrochemical performance, it is good with high power capacity
The positive electrode of good cycle performance is the study hotspot of lithium ion battery.
Lithium manganate having spinel structure belongs to cubic system, and Fd3m space groups, theoretical specific capacity is 148mAh/g, due to three
Dimension tunnel structure, lithium ion can the reversibly deintercalation from spinel crystal lattice, subsiding for structure will not be caused, thus with excellent
High rate performance and stability, be one of more promising lithium ion anode material.Compare the tradition positive electrode such as cobalt acid lithium, manganese
Sour lithium has the advantages that aboundresources, low cost, pollution-free, safety be good, good rate capability, is preferable power battery anode
Material, but its poor cycle performance and electrochemical stability greatly limit its industrialization.In charge and discharge process, especially
It is when depth discharge and recharge, however it remains structural instability, capacity attenuation is fast, the problems such as high temperature cyclic performance difference.Surface modification
Can effectively be modified its chemical property with doping, surface modification can effectively suppress dissolving and the electrolyte decomposition of manganese.Doping can
Effectively suppress the Jahn-Teller effects in charge and discharge process.Surface modification is combined with doping undoubtedly can further improve material
The chemical property of material, can become and be modified one of direction of research to lithium manganate having spinel structure from now on.
Means solution capacity in prior art just frequently with adulterate to spinel lithium manganate other metals and/or cladding declines
Subtract the problem of fast and poor high temperature stability.Such as, Chinese invention patent CN102324515B discloses a kind of lithium manganate having spinel structure
Preparation method and by its prepared LiMn2O4 and battery, first mixes the compound of Li source compound, Mn oxide and doping metals M
In entering dispersant, ball milling is dried, and 500～1200 DEG C of 10～50h of calcining of Jing obtain the LiMn2O4 of doped metallic elements, Ran Houzai
Secondary ball milling mixing is carried out with aluminum phosphate, Jing after 300～900 DEG C are calcined 5～30h, the LiMn2O4 for finally being adulterated and being coated
Positive electrode.According to the method for modifying that the patent is provided, obtained battery first discharge specific capacity under 0.2C multiplying powers is
110mAh/g, first three time discharging efficiency is all higher than 96%, and 50 circulation volumes are the 98.6% of first discharge specific capacity.However,
Although the doped metallic oxide that the patent is provided and method for coating can to a certain extent improve the electrochemistry of LiMn2O4
Can, but uneven problem is adulterated and coated to simple being caused using ball mill mixing method, can further affect be mixed with
Effect.Chinese invention patent CN1238260C provides a kind of lithium ion accumulator positive electrode active material lithium manganate having spinel structure
Preparation method, by lithium carbonate and manganese dioxide micropowder and the metal-oxide mixing and ball milling of needs doping, first 500～600
DEG C 10～15h of pre-burning, then then at 700～950 DEG C of 10～30h of calcining, finally obtains target product, its first discharge specific capacity
112mAh/g, capacitance loss rate is 5% after circulating 50 times.Although the method obtains to a certain extent the modified effect of anticipation
Really, but, employ secondary clacining and not only increase energy consumption, equally can there is a problem of doping it is uneven.
The content of the invention
It is an object of the invention to provide a kind of lithium manganate composite anode material, its preparation method and lithium ion battery, with
Solve the problems, such as lithium manganate having spinel structure capacity attenuation soon and cyclical stability is poor under high temperature.
For achieving the above object, the technical solution adopted in the present invention is：
First, the invention provides a kind of lithium manganate composite anode material, the composite positive pole is nucleocapsid structure, pattern
For spherical or spherical, internal layer is the In-situ reaction thing LiMn of LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate2O4-
LiNi1-x-yCox(Al/Mn)yO2, wherein, 0 ＜ x≤0.25,0 ＜ y≤0.15, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate
LiNi1-x-yCox(Al/Mn)yO2Weight/mass percentage composition for composite positive pole gross mass 0.1～20%；Material shell
For metal-oxide clad, the weight/mass percentage composition of metal-oxide clad for composite positive pole gross mass 0.05～
10%.
Preferably, the structural formula LiNi1-x-yCox(Al/Mn)yO2In, 0 ＜ x≤0.22,0 ＜ y≤0.12, particularly preferably
For, 0 ＜ x≤0.2,0 ＜ y≤0.1；
Preferably, the rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate has nucleocapsid structure, wherein, Ni concentration of element from
Internal granular layer to particle surface is presented decline trend, Ni constituent contents highest in internal granular layer nuclear structure, its weight/mass percentage composition
More than the 60% of total content；Mn concentration of element is presented increasing trend, granule outer layer core-shell structure from internal granular layer to particle surface
Middle Mn constituent contents highest, its weight/mass percentage composition exceedes the 65% of total content；It is further preferred that the internal granular layer core knot
Ni constituent contents exceed the 65% of total content in structure, and Mn constituent contents exceed the 70% of total content in granule outer layer core-shell structure；
It is particularly preferred that Ni constituent contents exceed the 70% of total content, in granule outer layer core-shell structure in the internal granular layer nuclear structure
Mn constituent contents exceed the 75% of total content；
Preferably, the rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate LiNi1-x-yCox(Al/Mn)yO2Quality percentage contain
Measure as the 0.3～15% of composite positive pole gross mass, more preferably 0.5～10%, particularly preferably 1～5%；
Preferably, the weight/mass percentage composition of the metal-oxide clad for composite positive pole gross mass 0.1～
8%, more preferably 0.5～5%, particularly preferably 1～3%.
Secondly, the invention provides a kind of preparation method of lithium manganate composite anode material, specifically includes following steps：
(1) LiMn2O4 will be obtained after the calcining in situ of manganese source, rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma and lithium source
With the In-situ reaction thing of rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate；
(2) washing is carried out to above-mentioned complex with the salpeter solution of 0.05～0.25mol/L and obtains inner nuclear material；
(3) inner nuclear material is added and be obtained in metal salt solution suspension, it is spray-dried, microwave sintering, broken
Sieve, be classified after obtain nucleocapsid structure lithium manganate composite anode material.
Used as the preferred of the inventive method, manganese source described in step (1) is electrolytic manganese dioxide, mangano-manganic oxide, carbonic acid
One kind or at least two combination in manganese.
As the preferred of the inventive method, rich nickel concentration gradient type nickel cobalt manganese described in step (1)/lithium aluminate presoma bag
Include a kind in carbonic acid nickel cobalt manganese/aluminum presoma, hydroxide nickel cobalt manganese/aluminum presoma and cobalt nickel oxide manganses/aluminum or at least two
Combination；
Preferably, the rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate presoma has nucleocapsid structure, wherein, Ni elements
Concentration is presented decline trend, Ni constituent contents highest in internal granular layer nuclear structure, its quality hundred from internal granular layer to particle surface
Content is divided to exceed the 60% of total content；Mn concentration of element is presented increasing trend, granule outer shell from internal granular layer to particle surface
Mn constituent contents highest in nuclear structure, its weight/mass percentage composition exceedes the 65% of total content；
It is further preferred that Ni constituent contents exceed the 65% of total content in the internal granular layer nuclear structure, granule outer layer
Mn constituent contents exceed the 70% of total content in core-shell structure；
It is particularly preferred that Ni constituent contents exceed the 70% of total content in the internal granular layer nuclear structure, granule outer shell
Mn constituent contents exceed the 75% of total content in nuclear structure.
Used as the preferred of the inventive method, lithium source described in step (1) is lithium chloride, lithium bromide, lithium phosphate, biphosphate
Lithium, the lithium of phosphoric acid hydrogen two, lithium sulfate, lithium carbonate, Lithium hydrate, Quilonorm (SKB), lithium nitrate, lithium oxalate, lithium formate, tert-butyl alcohol lithium, benzene
1 kind or at least 2 kinds of combination in lithium formate and Lithium Citrate de；
More preferably lithium carbonate, Lithium hydrate, Quilonorm (SKB), lithium nitrate, lithium oxalate, lithium formate, Lithium Citrate de, tertiary fourth
1 kind or at least 2 kinds of combination in lithium alkoxide；
1 kind or at least 2 kinds particularly preferably in lithium carbonate, Lithium hydrate, Quilonorm (SKB), lithium oxalate, Lithium Citrate de
Combination.
As the preferred of the inventive method, in step (1), need manganese source, rich nickel concentration gradient type nickel cobalt before calcination
Manganese/lithium aluminate presoma, lithium source weigh dispensing according to certain proportioning, then carry out ball milling or three-dimensional hybrid；
Preferably, the ball milling includes any one in planetary type ball-milling, blue type ball mill or high-energy ball milling, during ball milling
Between be 1～20h, more preferably more preferably 2～15h, 3～10h；
Preferably, the three-dimensional hybrid adopts three-dimensional mixer, and incorporation time is 1～25h, more preferably 2～
20h, more preferably 3～15h.
Used as the preferred of the inventive method, the calcination process described in step (1) is carried out in Muffle furnace, and calcining heat is
650～1050 DEG C, then 2～40h of calcination time naturally cools to room temperature, it is size-reduced, sieve after obtain LiMn2O4 and rich nickel is dense
The In-situ reaction thing of degree gradient type nickel cobalt manganese/lithium aluminate；
Preferably, the calcining heat is minimum 650 DEG C, more preferably 700～1000 DEG C, and particularly preferably 750
～950 DEG C；
Preferably, the programming rate during calcining be 1～15 DEG C/min, more preferably 3～12 DEG C/min, especially
Preferably 5～10 DEG C/min；
Preferably, the calcination time at least 2h, particularly preferably more preferably 4～30h, 6～25h；
Preferably, the calcining is carried out in an oxidizing atmosphere, at least particularly preferably in air and oxygen atmosphere
Plant is carried out under atmosphere；
Preferably, the flow of the oxidizing atmosphere is 1～300ml/min, more preferably 5～250ml/min, special
You Xuanwei not 10～200ml/min.
Used as the preferred of the inventive method, step (2) is specifically included：By LiMn2O4 and rich nickel concentration gradient type nickel cobalt manganese/
The In-situ reaction thing of lithium aluminate is added into described dilute nitric acid solution, agitated to mix to obtain suspension, by the suspension from
Heart separation, washing, drying, sieve classification excessively obtain inner nuclear material；
Preferably, the concentration of the dilute nitric acid solution is at least 0.05mol/L, more preferably 0.08～0.2mol/
L, particularly preferably 0.1～0.15mol/L；
Preferably, solvent for use is deionized water in the washing process, or deionized water and ethanol, propanol, the third three
Any one in alcohol and acetone or more than one combination；
Preferably, the drying be microwave drying, the baking temperature be 80～250 DEG C, more preferably 90～200
DEG C, particularly preferably 100～150 DEG C.
Used as the preferred of the inventive method, the slaine described in step (3) is cerous nitrate, nickel nitrate, zirconium nitrate, nitric acid
Erbium, nitric acid molybdenum, aluminum nitrate, magnesium nitrate, butyl titanate, ammonium metavanadate, tetraethyl orthosilicate, Lanthanum (III) nitrate, nitric acid stannum, copper nitrate, nitre
One kind or at least two combination in sour zinc, Yttrium trinitrate and chromic nitrate；
Preferably, described spray drying adopts centrifugal spray dryer, air flow type spray drying machine or press spray
One kind in drying machine, particularly preferably using centrifugal spray dryer；
Preferably, microwave sintering temperature be 250～750 DEG C, more preferably 300～700 DEG C, particularly preferably 350
～600 DEG C；
Preferably, the microwave sintering time is 1～40h, particularly preferably more preferably 3～35h, 5～25h.
Again, the present invention also provides a kind of lithium ion battery, and the positive active material of the battery is including provided by the present invention
A kind of manganate cathode material for lithium and above-mentioned steps described in preparation method in the lithium manganate composite anode material that is related to；
As the preferred of the inventive method, the perfume (or spice) of above-mentioned lithium ion battery in the preparation process of anode pole piece to discard
Product of the tobacco filters in ammonia after nitrogen treatment is used as carbon source；
Preferably, carbon source preparation method is, will collect the discarded cigarette filter for coming in ammonia atmosphere in 750～
1～5h of nitrogen treatment is carried out between 950 DEG C, programming rate is maintained at 1～15 DEG C/min, obtains and has sub-hole and microcellular structure
Nitrogenous material with carbon element as carbon source；
Preferably, above-mentioned nitriding temperature is preferably 800～900 DEG C, and the nitrogen treatment time is preferably 1.5～4h, especially excellent
Elect 2～3h as；
Preferably, programming rate is at least 1 DEG C/min, more preferably 3～10 DEG C/min, and particularly preferably 4～6
DEG C/min.
The manganate cathode material for lithium that the present invention is provided is the lithium manganate composite anode material prepared by any of the above-described scheme, by
Lithium ion battery prepared by lithium manganate composite anode material first discharge specific capacity in 0.5C multiplying powers is more than 110mAh/
G, first three time discharging efficiency is all higher than 98%, and capability retention is more than 97.5% after circulating 100 times；Hold after circulating 50 times when 55 DEG C
Amount conservation rate is more than 98.2%.
The lithium manganate composite anode material described in arbitrary above-mentioned technical proposal and lithium ion battery that the present invention is provided has
Specific capacity is high, and capacity attenuation is few, the outstanding advantages such as high temperature circulation good stability.Compared with prior art, beneficial effect of the invention
It is really：
(1) present invention is using the rich ni-type nickel cobalt manganese/aluminum presoma with Concentraton gradient, Li source compound and manganese source chemical combination
The method of thing in-situ sintering completes the doping in situ of rich nickel concentration gradient type nickel cobalt manganese/lithium aluminate, improves specific capacity.
(2) the slaine wiring solution-forming of cladding will be needed, using being spray-dried and the technique that combines of microwave sintering is in manganese
Sour lithium composite positive pole surface realizes the uniform cladding of metal-oxide, solves manganate cathode material for lithium high temperature circulation
Difference, the outstanding problem such as specific capacity is low, decay is fast.
(3) carry out carrying out acidifying washing to lithium manganate composite anode material material before metallic element Surface coating, reduce
The pH value of material surface, is conducive to improve the dispersibility and stability of slurry when slurry is prepared, and then improves battery
High temperature circulation stability.
(4) lithium ion battery with lithium manganate composite anode material as positive electrode active materials that the present invention is provided, in positive pole
Using the nitrogenous material with carbon element of the sub-hole after discarded cigarette filter nitridation and microcellular structure as carbon in the preparation process of pole piece
Source, also realizes recycling for garbage, with very while higher specific capacity and good multiplying power property is obtained
Good practical application and business promotion is worth.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment.Those skilled in the art will manage
Solution, following examples are only the preferred embodiments of the present invention, in order to more fully understand the present invention, thus should not be regarded as limiting this
The scope of invention.For a person skilled in the art, the present invention can have various modifications and variations, all essences in the present invention
Within god and principle, any modification, equivalent or improvement for being made etc. should be included within the scope of the present invention.
Embodiment 1
Design is LiMn2O4-LiNi0.65Co0.25Mn0.15O2, wherein, rich nickel concentration gradient type nickle cobalt lithium manganate
LiNi0.65Co0.25Mn0.15O2Weight/mass percentage composition for composite positive pole gross mass 15%.By electrolytic manganese dioxide, richness
Nickel concentration gradient type carbonic acid nickel cobalt manganese presoma and Lithium hydrate weigh dispensing according to aforementioned proportion, are mixed using three-dimensional mixer
1h, then calcines 8h in Muffle furnace in 850 DEG C, and programming rate is 1 DEG C/min, and whole calcination process is 300ml/ in flow
Carry out in the oxygen atmosphere of min, naturally cool to room temperature, it is size-reduced, sieve after obtain LiMn2O4 and rich nickel concentration gradient type nickel
The In-situ reaction thing of cobalt manganic acid lithium, is added to the complex stirring in the dilute nitric acid solution of 0.05mol/L and mixes to obtain suspension,
It is centrifuged, washs, 80 DEG C of microwave drying, sieve classifications excessively obtains inner nuclear material.The inner nuclear material is added into aluminum nitrate, magnesium nitrate
With prepared suspension in the mixed solution of zirconium nitrate so that aluminium oxide, magnesium oxide and zirconic gross mass in final clad
For the 3% of composite positive pole gross mass, then Jing centrifugal spray dryers are spray-dried, and are burnt in 750 DEG C of microwaves
Knot 1h, the final lithium manganate composite anode material for obtaining nucleocapsid structure.
With above-mentioned composite as positive active material, with product of the discarded cigarette filter in ammonia after nitrogen treatment
Thing makes lithium ion battery as carbon source (the nitrogen treatment time is 5h, and 750 DEG C of nitriding temperature, heating rate is 10 DEG C/min)
Find by test, in 0.5C multiplying powers, first discharge specific capacity is 112mAh/g, and first three time discharging efficiency is all higher than 98%, follows
Capability retention is 98.1% after ring 100 times；Capability retention is 98.5% after circulating 50 times when 55 DEG C.
Embodiment 2
Design is LiMn2O4-LiNi0.7Co0.2Al0.1O2, wherein, rich nickel concentration gradient type nickel cobalt aluminic acid
LiNi0.7Co0.2Al0.1O2Weight/mass percentage composition for composite positive pole gross mass 10%.By electrolytic manganese dioxide, rich nickel
Concentraton gradient type nickel cobalt aluminum hydroxide presoma and Lithium hydrate weigh dispensing according to aforementioned proportion, are mixed using three-dimensional mixer
10h, then calcines 15h in Muffle furnace in 800 DEG C, and programming rate is 5 DEG C/min, and whole calcination process is 100ml/ in flow
Carry out in the oxygen atmosphere of min, naturally cool to room temperature, it is size-reduced, sieve after obtain LiMn2O4 and rich nickel concentration gradient type nickel
The In-situ reaction thing of cobalt lithium aluminate, is added to the complex stirring in the dilute nitric acid solution of 0.2mol/L and mixes to obtain suspension,
It is centrifuged, washs, 250 DEG C of microwave drying, sieve classifications excessively obtains inner nuclear material.The inner nuclear material is added into chromic nitrate, inclined vanadium
Suspension is obtained in the mixed solution of sour ammonium and nitric acid stannum so that chromium oxide, vanadium oxide and stannum oxide is total in final clad
Quality is the 8% of composite positive pole gross mass, and then Jing centrifugal spray dryers are spray-dried, and micro- in 650 DEG C
Ripple sinters 10h, the final lithium manganate composite anode material for obtaining nucleocapsid structure.
With above-mentioned composite as positive active material, with product of the discarded cigarette filter in ammonia after nitrogen treatment
Thing as carbon source (the nitrogen treatment time be 2h, 900 DEG C of nitriding temperature, heating rate be 5 DEG C/min), make lithium ion battery after
Jing tests find that first discharge specific capacity is 116mAh/g in 0.5C multiplying powers, and first three time discharging efficiency is all higher than 98%, circulation
Capability retention is 98.5% after 100 times；Capability retention is 98.6% after circulating 50 times when 55 DEG C.
Embodiment 3
Design is LiMn2O4-LiNi0.8Co0.15Al0.05O2, wherein, rich nickel concentration gradient type nickel cobalt aluminic acid
LiNi0.8Co0.15Al0.05O2Weight/mass percentage composition for composite positive pole gross mass 5%.By electrolytic manganese dioxide, rich nickel
Concentraton gradient type nickel cobalt aluminum hydroxide presoma and Lithium hydrate weigh dispensing according to aforementioned proportion, with deionized water and anhydrous second
The mixture of alcohol is solvent ball milling 8h in high energy ball mill, then calcines 20h in 750 DEG C in Muffle furnace, and programming rate is
10 DEG C/min, whole calcination process is carried out in flow is for the oxygen atmosphere of 150ml/min, naturally cools to room temperature, size-reduced,
The In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickel cobalt lithium aluminate is obtained after sieving, the complex is added to
Stirring in the dilute nitric acid solution of 0.25mol/L mixes to obtain suspension, is centrifuged, washs, 200 DEG C of microwave drying, crossing and sieve
Level obtains inner nuclear material.Suspension is obtained in the mixed solution that the inner nuclear material is added tetraethyl orthosilicate and butyl titanate so that
The gross mass of silicon oxide and titanium oxide is the 5% of composite positive pole gross mass in final clad, then Jing atomizers
Drying machine is spray-dried, and in 500 DEG C of microwave sintering 15h, the final lithium manganate composite anode material for obtaining nucleocapsid structure.
With above-mentioned composite as positive active material, with product of the discarded cigarette filter in ammonia after nitrogen treatment
Thing as carbon source (the nitrogen treatment time be 1h, 950 DEG C of nitriding temperature, heating rate be 1 DEG C/min), make lithium ion battery after
Jing tests find that first discharge specific capacity is 115mAh/g in 0.5C multiplying powers, and first three time discharging efficiency is all higher than 98%, circulation
Capability retention is 98.7% after 100 times；Capability retention is 98.5% after circulating 50 times when 55 DEG C.
Embodiment 4
Design is LiMn2O4-LiNi0.85Co0.1Mn0.05O2, wherein, rich nickel concentration gradient type nickel cobalt mangaic acid
LiNi0.85Co0.1Mn0.05O2Weight/mass percentage composition for composite positive pole gross mass 1%.By manganese nitrate, rich nickel concentration ladder
Degree type carbonic acid nickel cobalt manganese presoma and lithium carbonate, lithium nitrate weigh dispensing according to aforementioned proportion, with deionized water and dehydrated alcohol
Mixture be solvent ball milling 15h in high energy ball mill, then in Muffle furnace in 1050 DEG C calcine 2h, 3 DEG C of programming rate/
Min, whole calcination process is carried out in flow is for the oxygen atmosphere of 50ml/min, naturally cools to room temperature, it is size-reduced, sieve after
The In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickle cobalt lithium manganate is obtained, the complex is added to into 0.05mol/L's
Stirring in dilute nitric acid solution mixes to obtain suspension, is centrifuged, washs, 120 DEG C of microwave drying, crossing sieve classifications and obtain kernel material
Material.The inner nuclear material is added and be obtained in ammonium metavanadate solution suspension so that silicon oxide and titanium oxide in final clad
Gross mass is the 0.3% of composite positive pole gross mass, and then Jing centrifugal spray dryers are spray-dried, and in 250
DEG C microwave sintering 20h, the final lithium manganate composite anode material for obtaining nucleocapsid structure.
With above-mentioned composite as positive active material, with product of the discarded cigarette filter in ammonia after nitrogen treatment
Thing as carbon source (the nitrogen treatment time be 3h, 800 DEG C of nitriding temperature, heating rate be 6 DEG C/min), make lithium ion battery after
Jing tests find that first discharge specific capacity is 111.5mAh/g in 0.5C multiplying powers, and first three time discharging efficiency is all higher than 98%, follows
Capability retention is 98% after ring 100 times；Capability retention is 98.3% after circulating 50 times when 55 DEG C.
Embodiment 5
Design is LiMn2O4-LiNi0.85Co0.1Al0.05O2, wherein, rich nickel concentration gradient type nickel cobalt aluminic acid
LiNi0.85Co0.1Al0.05O2Weight/mass percentage composition for composite positive pole gross mass 3%.Mangano-manganic oxide, rich nickel is dense
Degree gradient type carbonic acid nickel cobalt aluminum presoma and Lithium hydrate, Quilonorm (SKB) weigh dispensing according to aforementioned proportion, using three-dimensional mixer
Mixing 15h, then calcines 6h, 6 DEG C/min of programming rate in Muffle furnace in 900 DEG C, and whole calcination process is in flow
Carry out in the air atmosphere of 120ml/min, naturally cool to room temperature, it is size-reduced, sieve after obtain LiMn2O4 and rich nickel concentration ladder
The In-situ reaction thing of degree type nickel cobalt lithium aluminate, is added to the complex stirring in the dilute nitric acid solution of 0.1mol/L and mixes and must hang
Turbid liquid, is centrifuged, washs, 150 DEG C of microwave drying, crossing sieve classifications and obtain inner nuclear material.By the inner nuclear material add Lanthanum (III) nitrate,
Suspension is obtained in the mixed solution of cerous nitrate and nitric acid molybdenum so that lanthana, cerium oxide and molybdenum oxide in final clad
Gross mass is the 2% of composite positive pole gross mass, and then Jing centrifugal spray dryers are spray-dried, and in 550 DEG C
Microwave sintering 12h, the final lithium manganate composite anode material for obtaining nucleocapsid structure.
With above-mentioned composite as positive active material, with product of the discarded cigarette filter in ammonia after nitrogen treatment
Thing as carbon source (the nitrogen treatment time be 2h, 880 DEG C of nitriding temperature, heating rate be 5 DEG C/min), make lithium ion battery after
Jing tests find that first discharge specific capacity is 114.2mAh/g in 0.5C multiplying powers, and first three time discharging efficiency is all higher than 98%, follows
Capability retention is 98.3% after ring 100 times；Capability retention is 98.5% after circulating 50 times when 55 DEG C.
Embodiment 6
Design is LiMn2O4-LiNi0.8Co0.1Mn0.1O2, wherein, rich nickel concentration gradient type nickel cobalt mangaic acid
LiNi0.8Co0.1Mn0.1O2Weight/mass percentage composition for composite positive pole gross mass 2%.Electrolytic manganese dioxide, rich nickel is dense
Degree gradient type carbonic acid nickel cobalt manganese presoma and Lithium hydrate weigh dispensing according to aforementioned proportion, using three-dimensional mixer mixing 12h,
Then 4h, 5 DEG C/min of programming rate are calcined in 1000 DEG C in Muffle furnace, whole calcination process is in flow for 150ml/min's
Carry out in air atmosphere, naturally cool to room temperature, it is size-reduced, sieve after obtain LiMn2O4 and rich nickel concentration gradient type nickel cobalt mangaic acid
The In-situ reaction thing of lithium, is added to the complex stirring in the dilute nitric acid solution of 0.05mol/L and mixes to obtain suspension, Jing centrifugations
Separate, wash, 200 DEG C of microwave drying, sieve classifications excessively obtain inner nuclear material.The inner nuclear material is added into the mixed of aluminum nitrate and magnesium nitrate
Close and be obtained in solution suspension so that the gross mass of aluminium oxide and magnesium oxide is composite positive pole gross mass in final clad
1%, then Jing centrifugal spray dryers be spray-dried, it is final to obtain nucleocapsid knot and in 450 DEG C of microwave sintering 16h
The lithium manganate composite anode material of structure.
With above-mentioned composite as positive active material, with product of the discarded cigarette filter in ammonia after nitrogen treatment
Thing makes lithium ion battery as carbon source (the nitrogen treatment time is 1.5h, and 900 DEG C of nitriding temperature, heating rate is 3 DEG C/min)
Find by test, in 0.5C multiplying powers, first discharge specific capacity is 116.3mAh/g, and first three time discharging efficiency is all higher than 98%,
Capability retention is 98.4% after circulating 100 times；Capability retention is 98.6% after circulating 50 times when 55 DEG C.
Claims (10)
1. a kind of lithium manganate composite anode material, it is characterised in that the composite positive pole is nucleocapsid structure, pattern is spherical
Or it is spherical, internal layer is the In-situ reaction thing LiMn of LiMn2O4 and rich nickel concentration gradient type nickle cobalt lithium manganate2O4-LiNi1-x- yCoxMnyO2, wherein 0 ＜ x≤0.25,0 ＜ y≤0.15, rich nickel concentration gradient type nickle cobalt lithium manganate LiNi1-x-yCoxMnyO2Matter
Amount percentage composition is the 0.1～20% of composite positive pole gross mass；Material shell is metal-oxide clad, described
Metal-oxide is aluminium oxide, magnesium oxide and zirconium oxide, and the weight/mass percentage composition of metal-oxide clad is anode composite material
The 0.05～10% of material gross mass；
The rich nickel concentration gradient type nickle cobalt lithium manganate has nucleocapsid structure, wherein, Ni concentration of element is from internal granular layer to granule
Surface is presented decline trend, and Ni constituent contents highest in internal granular layer nuclear structure, its weight/mass percentage composition exceedes total content
60%；Mn concentration of element is presented increasing trend from internal granular layer to particle surface, and Mn constituent contents are most in granule outer layer shell structure
Height, its weight/mass percentage composition exceedes the 65% of total content.
2. a kind of a kind of preparation method of lithium manganate composite anode material as claimed in claim 1, comprises the following steps：
(1) LiMn2O4 and rich nickel will be obtained after the calcining in situ of manganese source, rich nickel concentration gradient type precursor of nickel-cobalt-lithium-manganese-oxide and lithium source
The In-situ reaction thing of Concentraton gradient type nickle cobalt lithium manganate；
(2) washing is carried out to above-mentioned complex with the salpeter solution of 0.05～0.25mol/L and obtains inner nuclear material；
(3) inner nuclear material is added and be obtained in metal salt solution suspension, spray-dried, microwave sintering, it is broken sieve,
The lithium manganate composite anode material of nucleocapsid structure is obtained after classification.
3. preparation method according to claim 2, it is characterised in that manganese source described in step (1) be electrolytic manganese dioxide,
One kind or at least two combination in mangano-manganic oxide, manganese carbonate.
4. preparation method according to claim 2, it is characterised in that rich nickel concentration gradient type nickel cobalt described in step (1)
Manganate precursor for lithium is including a kind in carbonic acid nickel cobalt manganese presoma, hydroxide nickel cobalt manganese presoma and cobalt nickel oxide manganses or at least
Two kinds of combination；
The rich nickel concentration gradient type precursor of nickel-cobalt-lithium-manganese-oxide has nucleocapsid structure, wherein, Ni concentration of element is from internal granular layer
Decline trend is presented to particle surface, Ni constituent contents highest in internal granular layer nuclear structure, its weight/mass percentage composition exceedes and always contains
The 60% of amount；Mn concentration of element is presented increasing trend from internal granular layer to particle surface, and Mn elements contain in granule outer layer shell structure
Amount highest, its weight/mass percentage composition exceedes the 65% of total content.
5. preparation method according to claim 2, it is characterised in that lithium source described in step (1) is lithium chloride, bromination
Lithium, lithium phosphate, lithium dihydrogen phosphate, the lithium of phosphoric acid hydrogen two, lithium sulfate, lithium carbonate, Lithium hydrate, Quilonorm (SKB), lithium nitrate, lithium oxalate,
1 kind or at least 2 kinds of combination in lithium formate, tert-butyl alcohol lithium, lithium benzoate and Lithium Citrate de.
6. preparation method according to claim 2, it is characterised in that in step (1), need manganese source, richness before calcination
Nickel concentration gradient type precursor of nickel-cobalt-lithium-manganese-oxide, lithium source weigh dispensing according to certain proportioning, then carry out ball milling or three-dimensional mixed
Close.
7. preparation method according to claim 2, it is characterised in that the calcination process described in step (1) is in Muffle furnace
In carry out, calcining heat is 650～1050 DEG C, and then 2～40h of calcination time naturally cools to room temperature, it is size-reduced, sieve after
Obtain the In-situ reaction thing of LiMn2O4 and rich nickel concentration gradient type nickle cobalt lithium manganate.
8. preparation method according to claim 2, it is characterised in that step (2) is specifically included：LiMn2O4 and rich nickel is dense
The In-situ reaction thing of degree gradient type nickle cobalt lithium manganate is added into described salpeter solution, agitated to mix to obtain suspension, by institute
State suspension centrifugation, washing, drying, cross sieve classification obtain inner nuclear material.
9. the preparation method described in any one in claim 2～8, it is characterised in that the gold described in step (3)
Category salt is aluminum nitrate, magnesium nitrate and zirconium nitrate；
It is described to be spray-dried using in centrifugal spray dryer, air flow type spray drying machine or pressure spray dryer
Kind；
Microwave sintering temperature is 250～750 DEG C；The microwave sintering time is 1～40h.
10. the lithium ion battery that prepared by lithium manganate composite anode material according to claim 1, it is characterised in that by institute
State the first discharge specific capacity in 0.5C multiplying powers of the lithium ion battery prepared by lithium manganate composite anode material and be more than 110mAh/g,
First three time discharging efficiency is all higher than 98%, and capability retention is more than 97.5% after circulating 100 times；Capacity after circulating 50 times when 55 DEG C
Conservation rate is more than 98.2%.
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| CN116154174A (en) * | 2023-04-12 | 2023-05-23 | 河南电池研究院有限公司 | Multiphase composite layered manganese-based positive electrode material and preparation method thereof |
| CN116544489B (en) * | 2023-07-06 | 2023-09-19 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948101A (en) * | 2010-09-09 | 2011-01-19 | 浙江瑞邦科技有限公司 | Method for preparing anode material lithium iron phosphate material of lithium battery |
| CN102709546A (en) * | 2012-06-12 | 2012-10-03 | 浙江南都电源动力股份有限公司 | Method for producing high voltage anode material LiNi 0.5 Mn 1.5O4 of lithium ion battery |
| CN103050683A (en) * | 2012-12-28 | 2013-04-17 | 深圳市贝特瑞新能源材料股份有限公司 | Polyphase manganese base solid solution composite cathode material and preparation method thereof |
| CN104037407A (en) * | 2014-05-22 | 2014-09-10 | 北大先行科技产业有限公司 | Lithium cobalt oxide compound material coated with lithium super-Ion conductor and preparation method thereof |
| CN104037411A (en) * | 2014-05-18 | 2014-09-10 | 深圳赛骄阳能源科技有限公司 | Multielement doped lithium phosphate anode material and preparation method |
-
2014
- 2014-09-24 CN CN201410491048.7A patent/CN104347853B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948101A (en) * | 2010-09-09 | 2011-01-19 | 浙江瑞邦科技有限公司 | Method for preparing anode material lithium iron phosphate material of lithium battery |
| CN102709546A (en) * | 2012-06-12 | 2012-10-03 | 浙江南都电源动力股份有限公司 | Method for producing high voltage anode material LiNi 0.5 Mn 1.5O4 of lithium ion battery |
| CN103050683A (en) * | 2012-12-28 | 2013-04-17 | 深圳市贝特瑞新能源材料股份有限公司 | Polyphase manganese base solid solution composite cathode material and preparation method thereof |
| CN104037411A (en) * | 2014-05-18 | 2014-09-10 | 深圳赛骄阳能源科技有限公司 | Multielement doped lithium phosphate anode material and preparation method |
| CN104037407A (en) * | 2014-05-22 | 2014-09-10 | 北大先行科技产业有限公司 | Lithium cobalt oxide compound material coated with lithium super-Ion conductor and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4098626A1 (en) * | 2021-06-02 | 2022-12-07 | Samsung SDI Co., Ltd. | Composite cathode active material, method of preparing the same, cathode including the same, and lithium secondary battery including cathode |
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