CN112047396A - Method for preparing double-layer nickel-based composite oxide lithium battery anode material by two-step crystallization method - Google Patents
Method for preparing double-layer nickel-based composite oxide lithium battery anode material by two-step crystallization method Download PDFInfo
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- CN112047396A CN112047396A CN202010944969.XA CN202010944969A CN112047396A CN 112047396 A CN112047396 A CN 112047396A CN 202010944969 A CN202010944969 A CN 202010944969A CN 112047396 A CN112047396 A CN 112047396A
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- nickel
- composite
- cobalt
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- 239000010405 anode material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002425 crystallisation Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 104
- 238000002156 mixing Methods 0.000 claims abstract description 67
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910016205 LixNi1-y-zCoy Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 47
- 238000002844 melting Methods 0.000 claims description 26
- 230000008018 melting Effects 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 25
- 239000011572 manganese Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000011265 semifinished product Substances 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 11
- 150000001875 compounds Chemical class 0.000 claims 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 6
- -1 oxide Substances 0.000 claims 6
- 229910021529 ammonia Inorganic materials 0.000 claims 5
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 5
- 150000004679 hydroxides Chemical class 0.000 claims 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 4
- 229910052719 titanium Inorganic materials 0.000 claims 4
- 239000010936 titanium Substances 0.000 claims 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 229910002651 NO3 Inorganic materials 0.000 claims 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 3
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 3
- 229910052782 aluminium Inorganic materials 0.000 claims 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 3
- 150000003891 oxalate salts Chemical class 0.000 claims 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 229910052787 antimony Inorganic materials 0.000 claims 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 2
- 229910052797 bismuth Inorganic materials 0.000 claims 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 2
- 229910052796 boron Inorganic materials 0.000 claims 2
- 229910052792 caesium Inorganic materials 0.000 claims 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 2
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 claims 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 2
- 229910052733 gallium Inorganic materials 0.000 claims 2
- 229910052732 germanium Inorganic materials 0.000 claims 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 2
- 229910052738 indium Inorganic materials 0.000 claims 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims 2
- 150000002602 lanthanoids Chemical class 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- 229910052750 molybdenum Inorganic materials 0.000 claims 2
- 239000011733 molybdenum Substances 0.000 claims 2
- 229910052758 niobium Inorganic materials 0.000 claims 2
- 239000010955 niobium Substances 0.000 claims 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 2
- 235000021317 phosphate Nutrition 0.000 claims 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 2
- 229910052701 rubidium Inorganic materials 0.000 claims 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 229910052712 strontium Inorganic materials 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- 229910052715 tantalum Inorganic materials 0.000 claims 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 2
- 229910052718 tin Inorganic materials 0.000 claims 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 2
- 229910052721 tungsten Inorganic materials 0.000 claims 2
- 239000010937 tungsten Substances 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 229910052727 yttrium Inorganic materials 0.000 claims 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 239000011701 zinc Substances 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- 229920000178 Acrylic resin Polymers 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 claims 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims 1
- UXZUCXCKBOYJDF-UHFFFAOYSA-N [Ti].[Co].[Ni] Chemical compound [Ti].[Co].[Ni] UXZUCXCKBOYJDF-UHFFFAOYSA-N 0.000 claims 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 235000012501 ammonium carbonate Nutrition 0.000 claims 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims 1
- 125000005456 glyceride group Chemical group 0.000 claims 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000011656 manganese carbonate Substances 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910019167 CoC2 Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 229910016719 Ni0.5Co0.5(OH)2 Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910005744 Li1.05Ni0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910017229 Ni0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910015386 Ni0.9Co0.1(OH)2 Inorganic materials 0.000 description 1
- 229910005581 NiC2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a method for preparing a double-layer nickel-based composite oxide lithium battery anode material by a two-step crystallization method, wherein the anode material has the general formula: (1-d) LixNi1‑y‑zCoyM1zO2·dLiaNi1‑b‑cMnbM2cO2Wherein x is more than or equal to 1.0 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.2, a is more than or equal to 1.0 and less than or equal to 1.1, and 0B is more than or equal to 05 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.4, d is more than or equal to 0.01 and less than or equal to 0.5, and M1 and M2 are modification elements and comprise the following steps: s1, mixing the required lithium source, nickel source, cobalt source and M1 source materials according to the molar ratio of the lithium source: a nickel source: a cobalt source: m1 source 1.0-1.2: 0.6-1.0: 0-0.2: 0-0.2 weight percent. The lithium ion battery anode material has the advantages of being large in energy density, good in thermal stability and the like, improving the safety, low-temperature and rate charge and discharge performance of a lithium battery using the anode material, and prolonging the cycle life of the lithium battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a method for preparing a double-layer nickel-based composite oxide lithium battery anode material by a two-step crystallization method.
Background
In a lithium ion battery, a cathode material is one of the key materials determining the performance of the lithium ion battery. Currently, widely used cathode materials include lithium cobaltate, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganese oxide and the like, which have advantages and disadvantages, and have different application fields.
LiCoO2 has high cost and deficient resources, has potential safety hazard, and can only be applied to the consumer market field, such as portable communication electronic products like mobile phones and computers; the nickel cobalt lithium manganate with application prospect has high energy density, is applied to the traffic fields of new energy automobiles and the like on a large scale, but has poor thermal stability, potential safety hazards, short service life and the like; lithium manganate has the advantage of low cost, but has low energy density, serious capacity loss and poor cycle life in a high-temperature environment, and the factors prevent the lithium manganate from being widely applied; the lithium iron phosphate has good electrochemical performance, stable structure in the charging and discharging process, long cycle life, wider raw material source, lower price and no environmental pollution, but has many disadvantages, such as: the lithium ion battery has low energy density and poor rate discharge performance and low-temperature performance, so the lithium ion battery can only be applied to lithium batteries and energy storage batteries of new energy automobiles such as passenger cars and special vehicles which have low requirements on energy density.
Disclosure of Invention
The invention aims to provide a method for preparing a double-layer nickel-based composite oxide lithium battery positive electrode material by a two-step crystallization method, so as to solve the problem of poor universality of the material proposed in the background technology.
The technical scheme of the invention is as follows: a method for preparing a double-layer nickel-based composite oxide lithium battery anode material by a two-step crystallization method.
Compared with the prior art, the method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method has the following improvements and advantages:
(1) the lithium ion battery anode material has the advantages of high energy density, good thermal stability and the like, improves the safety, low-temperature and rate charge and discharge performance of a lithium battery using the anode material, and prolongs the cycle life of the lithium battery.
(2) The lithium ion battery anode material can be applied to the lithium ion batteries in the fields of manufacturing and consuming digital electronic products such as mobile phones and notebook computers, traffic fields such as electric automobiles, electric bicycles and electric ships, energy storage such as electric tools, communication base stations, wind power generation, solar power stations, power grid peak regulation and valley regulation and the like in a large scale, and has good general applicability.
Drawings
The invention is further explained below with reference to the figures and examples:
FIG. 1 is a graphical representation of the performance range of the present invention;
FIG. 2 is a graphical representation of the properties of materials prepared in examples 1-6 of the present invention.
Detailed Description
The present invention will be described in detail with reference to fig. 1 to 2, and the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides a method for preparing a double-layer nickel-based composite oxide lithium battery anode material by a two-step crystallization method through improvement.
Some preferred embodiments or application examples are listed below to help those skilled in the art to better understand the technical content of the present invention and the technical contribution of the present invention with respect to the prior art:
example 1
(1) Reacting the desired LiOH. H2O、Ni(OH)2、Co(OH)2And Al (OH)3According to a molar ratio of 1.05: 0.8: 0.15: 0.05 weighing and preparing;
(2) and (2) putting the weighed and prepared materials in the step (1) into crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed medium and dispersing agent into the equipment: deionized water and polyethylene glycol, uniformly mixing the materials, crushing the materials to submicron level, and drying the materials;
(3) putting the material prepared in the step (2) into a sintering sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting the sagger for 6 hours at the temperature of 500-600 ℃, then heating the sagger to 890-910 ℃, melting, crystallizing and synthesizing the sagger for 20 hours, cooling the sagger to room temperature, crushing the sagger, sieving the sagger by a 300-mesh sieve, and obtaining a semi-finished product Li1.05Ni0.8Co0.15Al0.05O2(abbreviated as Q1);
(4) reacting the desired LiOH. H2O、NiCO3、MnCO3And CoCO3And (3) waiting for materials according to a molar ratio of 1.06: 0.5: 0.2: 0.3, weighing and preparing;
(5) and (4) putting the weighed and prepared materials in the crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed media and dispersing agents into the equipment: deionized water, ammonia water and polyethylene glycol, uniformly mixing the materials, crushing the materials to submicron grade, and drying to obtain a semi-finished product Q2;
(6) mixing Q1 and Q2 according to a molar ratio of 0.9: 0.1 weighing and preparing;
(7) and (3) putting the materials weighed and prepared in the step (6) into a mixing and drying integrated device, and then adding a certain amount of mixed medium and dispersing agent into the mixing device: deionized water and polyethylene glycol, and uniformly mixing and drying the materials;
(8) and (3) putting the material prepared in the step (7) into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting the sagger for 5 hours at the temperature of 500-600 ℃, then heating the temperature to 900-910 ℃, crystallizing and synthesizing the sagger for 20 hours, then cooling the sagger to room temperature, crushing the sagger, and sieving the sagger by a 300-mesh sieve, wherein the undersize is the double-layer nickel-based composite oxide lithium battery anode material. 0.9Li1.05Ni0.8Co0.15Al0.05O2·0.1Li1.06Ni0.5Mn0.2Co0.3O2。
Example 2
(1) Reacting the desired LiOH. H2O、Ni0.9Mn0.1(OH)2、Co(OH)2And MoO3According to a molar ratio of 1.06: 0.9: 0.09: 0.01 weighing and preparing;
(2) and (2) putting the weighed and prepared materials in the step (1) into crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed medium and dispersing agent into the equipment: ethanol, uniformly mixing the materials, crushing the materials to submicron level, and drying the materials;
(3) putting the material prepared in the step (2) into a sintering sagger, putting the sagger into an oxygen synthetic furnace, decomposing, oxidizing and melting the sagger for 6 hours at the temperature of 580-600 ℃, then heating the sagger to the temperature of 890-910 ℃, melting, crystallizing and synthesizing the sagger for 20 hours, cooling the sagger to room temperature, crushing the sagger, sieving the sagger by a 300-mesh sieve, and obtaining a semi-finished product Li1.06Ni0.81Mn0.09Co0.09Mo0.01O2(abbreviated as Q1);
(4) adding the required Li2CO3、Ni0.5Co0.5(OH)2、MnCO3And TiO2And (3) waiting for materials according to a molar ratio of 0.53: 0.8: 0.19: 0.01 weighing and preparing;
(5) and (4) putting the weighed and prepared materials in the crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed media and dispersing agents into the equipment: deionized water and polyethylene glycol, uniformly mixing the materials, crushing the materials to submicron grade, and drying to obtain a semi-finished product Q2;
(6) mixing Q1 and Q2 according to a molar ratio of 0.95: 0.05 weighing and preparing;
(7) and (3) putting the materials weighed and prepared in the step (6) into a mixing and drying integrated device, and then adding a certain amount of mixed medium and dispersing agent into the mixing device: deionized water, isopropanol and polyethylene glycol, and uniformly mixing and drying the materials;
(8) and (3) putting the material prepared in the step (7) into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting the sagger for 5 hours at the temperature of 480-500 ℃, then heating the temperature to 910-920 ℃, crystallizing and synthesizing the sagger for 20 hours, then cooling the sagger to room temperature, crushing the sagger, and sieving the sagger by a 300-mesh sieve, wherein the undersize is the double-layer nickel-based composite oxide lithium battery anode material. 0.95Li1.06Ni0.81Mn0.09Co0.09Mo0.01O2·0.05Li1.06Ni0.4Co 0.4Mn0.19Ti0.01O2。
Example 3
(1) Reacting the desired LiOH. H2O、NiC2O4·2H2O、CoC2O4·2H2O and MgCO3According to a molar ratio of 1.06: 0.83: 0.15: 0.02 weighing and preparing;
(2) and (2) putting the weighed and prepared materials in the step (1) into crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed medium and dispersing agent into the equipment: deionized water, ammonia water and polyethylene glycol, uniformly mixing the materials, crushing the materials to submicron level, and drying the materials;
(3) putting the material prepared in the step (2) into a sintering sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting the sagger for 6 hours at the temperature of 550-560 ℃, then heating the sagger to the temperature of 850-860 ℃ for melting, crystallizing and synthesizing the sagger for 20 hours, then cooling the sagger to room temperature, crushing the sagger, sieving the sagger by a 300-mesh sieve, wherein the undersize is a semi-finished product Li1.06Ni0.83Co0.15Mg0.02O2(abbreviated as Q1);
(4) adding the required Li2CO3、Ni0.5Co0.5CO3、MnO2And Nb2O5According to the molar ratio of materialsIs 0.54: 0.84: 0.15: 0.005 is weighed and prepared;
(5) and (4) putting the weighed and prepared materials in the crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed media and dispersing agents into the equipment: deionized water, polyethylene glycol, oxalic acid and ammonium bicarbonate, uniformly mixing the materials, crushing the materials to submicron grade, and drying to obtain a semi-finished product Q2;
(6) mixing Q1 and Q2 according to a molar ratio of 0.9: 0.1 weighing and preparing;
(7) and (3) putting the materials weighed and prepared in the step (6) into a mixing and drying integrated device, and then adding a certain amount of mixed medium and dispersing agent into the mixing device: ethanol, mixing the two materials uniformly, and drying;
(8) and (3) putting the material prepared in the step (7) into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting for 6 hours at the temperature of 400-500 ℃, then heating the temperature to 860-880 ℃, crystallizing and synthesizing for 20 hours, then cooling to room temperature, crushing, sieving by a 300-mesh sieve, and taking the sieved material as the double-layer nickel-based composite oxide lithium battery anode material. 0.9Li1.06Ni0.83Co0.15Mg0.02O2·0.1Li1.08Ni0.42Co0.42Mn0.15Nb0.01O2。
Example 4
(1) Reacting the desired LiOH. H2O、Ni0.9Mn0.1(OH)2、CoC2O4·2H2O and MoO3According to a molar ratio of 1.07: 0.90: 0.09: 0.01 weighing and preparing;
(2) and (2) putting the weighed and prepared materials in the step (1) into crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed medium and dispersing agent into the equipment: deionized water and polyvinyl alcohol, uniformly mixing the materials, crushing the materials to submicron level, and drying the materials;
(3) putting the material prepared in the step (2) into a sintering sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting the sagger for 6 hours at the temperature of 500-520 ℃, then heating the sagger to the temperature of 800-810 ℃, melting, crystallizing and synthesizing the sagger for 20 hours, cooling the sagger to room temperature, crushing the sagger, sieving the sagger with a 300-mesh sieve, and screening the underflowIs a semi-finished product Li1.07Ni0.81Mn0.09Co0.09Mo0.01O2(abbreviated as Q1);
(4) adding the required Li2CO3、Ni0.4Co0.4Mn0.2(OH)2、MnCO3And Al (OH)3And (3) waiting for materials according to a molar ratio of 0.54: 0.8: 0.19: 0.01 weighing and preparing;
(5) and (4) putting the weighed and prepared materials in the crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed media and dispersing agents into the equipment: deionized water and polyethylene glycol, uniformly mixing the materials, crushing the materials to submicron grade, and drying to obtain a semi-finished product Q2;
(6) mixing Q1 and Q2 according to a molar ratio of 0.93: 0.07 weighing and preparing;
(7) and (3) putting the materials weighed and prepared in the step (6) into a mixing and drying integrated device, and then adding a certain amount of mixed medium and dispersing agent into the mixing device: deionized water, and uniformly mixing and drying the materials;
(8) and (3) putting the material prepared in the step (7) into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting for 6 hours at the temperature of 450-480 ℃, then heating the temperature to 870-880 ℃, crystallizing and synthesizing for 20 hours, then cooling to room temperature, crushing, and sieving by a 300-mesh sieve, wherein the sieved material is the double-layer nickel-based composite oxide lithium battery anode material. 0.93Li1.07Ni0.81Mn0.09Co0.09Mo0.01O2·0.07Li1.08Ni0.32C o0.32Mn0.35Al0.01O2。
Example 5
(1) Reacting the desired LiOH. H2O、Ni0.95Co0.05(OH)2、CoC2O4·2H2O and SrCO3According to a molar ratio of 1.07: 0.85: 0.14: 0.01 weighing and preparing;
(2) and (2) putting the weighed and prepared materials in the step (1) into crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed medium and dispersing agent into the equipment: deionized water, polyethylene glycol and urea, uniformly mixing the materials, crushing the materials to submicron level, and drying the materials;
(3) putting the material prepared in the step (2) into a sintering sagger, putting the sagger into an oxygen synthetic furnace, decomposing, oxidizing and melting the sagger for 6 hours at the temperature of 480-510 ℃, then heating the sagger to the temperature of 820-830 ℃, melting, crystallizing and synthesizing the sagger for 20 hours, cooling the sagger to room temperature, crushing the sagger, sieving the sagger by a 300-mesh sieve, and obtaining a semi-finished product Li1.07Ni0.81Co0.18Sr0.01O2(abbreviated as Q1);
(4) adding the required Li2CO3、Ni0.5Co0.5(OH)2、MnC2O4·2H2O and ZrO2And (3) waiting for materials according to a molar ratio of 0.54: 0.7: 0.295: 0.005 is weighed and prepared;
(5) and (4) putting the weighed and prepared materials in the crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed media and dispersing agents into the equipment: deionized water, urea and polyethylene glycol, uniformly mixing the materials, crushing the materials to submicron grade, and drying to obtain a semi-finished product Q2;
(6) mixing Q1 and Q2 according to a molar ratio of 0.92: 0.08 weight percent and preparation;
(7) and (3) putting the materials weighed and prepared in the step (6) into a mixing and drying integrated device, and then adding a certain amount of mixed medium and dispersing agent into the mixing device: deionized water and polyethylene glycol, and uniformly mixing and drying the materials;
(8) and (3) putting the material prepared in the step (7) into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting for 6 hours at the temperature of 470-490 ℃, then heating the temperature to 830-840 ℃, crystallizing and synthesizing for 20 hours, then cooling to room temperature, crushing, sieving by a 300-mesh sieve, and taking the sieved material as the double-layer nickel-based composite oxide lithium battery anode material. 0.92Li1.07Ni0.81Co0.18Sr0.01O2·0.08Li1.08Ni0.35Co0.35M n0.295Al0.005O2。
Example 6
(1) Reacting the desired LiOH. H2O、Ni0.9Co0.1(OH)2、MnC2O4·2H2O and MgCO3According to a molar ratio of 1.08: 0.90: 0.095: 0.005 is weighed and prepared;
(2) and (2) putting the weighed and prepared materials in the step (1) into crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed medium and dispersing agent into the equipment: deionized water, citric acid and polyoxyethyleneamine, uniformly mixing the materials, crushing the materials to submicron level, and drying the materials;
(3) putting the material prepared in the step (2) into a sintering sagger, putting the sagger into an oxygen synthetic furnace, decomposing, oxidizing and melting the sagger for 6 hours at the temperature of 540-550 ℃, then heating the sagger to the temperature of 820-830 ℃, melting, crystallizing and synthesizing the sagger for 20 hours, cooling the sagger to room temperature, crushing the sagger, sieving the sagger by a 300-mesh sieve, and obtaining a semi-finished product Li1.08Ni0.81Co0.09Mn0.095Mg0.005O2(abbreviated as Q1);
(4) adding the required Li2CO3、NiCO3、CoCO3、MnCO3And Nb2O5The molar ratio of the materials is 0.52: 0.4: 0.29: 0.3: 0.005 is weighed and prepared;
(5) and (4) putting the weighed and prepared materials in the crushing, mixing and drying integrated equipment, and then adding a certain amount of mixed media and dispersing agents into the equipment: uniformly mixing deionized water, oxalic acid, polyethylene glycol and ammonia water, crushing the materials to submicron grade, and drying to obtain a semi-finished product Q2;
(6) mixing Q1 and Q2 according to a molar ratio of 0.94: 0.06 weighing and preparing;
(7) and (3) putting the materials weighed and prepared in the step (6) into a mixing and drying integrated device, and then adding a certain amount of mixed medium and dispersing agent into the mixing device: deionized water and polyethylene glycol, and uniformly mixing and drying the materials;
(8) and (3) putting the material prepared in the step (7) into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting for 6 hours at the temperature of 460-480 ℃, then heating the temperature to 840-850 ℃, crystallizing and synthesizing for 20 hours, then cooling to room temperature, crushing, and sieving by a 300-mesh sieve, wherein the sieved material is the double-layer nickel-based composite oxide lithium battery anode material. 0.94Li1.08Ni0.81Co0.09Mn0.095Mg0.005O2·0.06Li1.04Ni0.4C o0.29Mn0.3Nb0.01O2。
The working principle of the invention is as follows: the operator mixes the required lithium source, nickel source, cobalt source and M1 source materials according to the mol ratio of the lithium source: a nickel source: a cobalt source: m1 source 1.0-1.2: 0.6-1.0: 0-0.2: 0-0.2 weighing and preparing the materials to be prepared, then putting the weighed materials into crushing, mixing and drying integrated equipment, adding a certain amount of mixing medium and dispersing agent into the equipment, uniformly mixing the materials, crushing the materials to submicron level, drying the materials, putting the products into a sagger by an operator after drying, putting the sagger into an oxygen synthesis furnace for decomposition, oxidation and melting, wherein the temperature of the decomposition, oxidation and melting is 300-600 ℃ and the time is 3-10h, after the completion, the operator raises the temperature to 610-950 ℃ so as to melt, crystallize and synthesize the materials for 3-30h, then airing the products for 10-24h, cooling the products to room temperature, then crushing the products and sieving the products by a 300-mesh sieve, and the undersize products are semi-finished products LixNi1-y-zCoyM1zO2Hereinafter referred to as Q1; the operator mixes the required lithium source, nickel source, manganese source and M2 source materials according to the mol ratio of the lithium source: a nickel source: a manganese source: m2 source 1.0-1.1: 0.1-0.95: 0.05-0.5: weighing and preparing 0-0.4, then putting the weighed and prepared materials into crushing, mixing and drying integrated equipment, adding a certain amount of mixed medium and dispersant into the equipment, uniformly mixing the materials, crushing the materials to submicron level, and drying to obtain a semi-finished product Q2; the operator then Q1 and Q2 were mixed in a molar ratio Q1: q2 ═ 0.5-0.99: weighing and preparing 0.01-0.5, putting the prepared materials into a mixing and drying integrated device, adding a certain amount of mixing medium and dispersant into the mixing device, uniformly mixing and drying the materials, then putting the product prepared in S6 into a sagger, putting the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting for 2-10h at the temperature of 600 ℃ plus materials of 300 plus materials, then heating the temperature to 950 ℃ plus materials of 610 plus materials, melting and crystallizing for synthesis for 3-30h, then airing the product for 10-24h, naturally cooling to room temperature, finally crushing the product and sieving through a 300 mesh sieve, wherein the undersize product is the double-layer nickel-based composite oxide lithium battery anode material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for preparing a double-layer nickel-based composite oxide lithium battery anode material by a two-step crystallization method is characterized by comprising the following steps of: the composition general formula of the anode material is as follows: (1-d) LixNi1-y-zCoyM1zO2·dLiaNi1-b-cMnbM2cO2Wherein x is more than or equal to 1.0 and less than or equal to 1.2, y is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.2, a is more than or equal to 1.0 and less than or equal to 1.1, b is more than or equal to 0.05 and less than or equal to 0.5, c is more than or equal to 0 and less than or equal to 0.4, d is more than or equal to 0.01 and less than or equal to 0:
s1, mixing the required lithium source, nickel source, cobalt source and M1 source materials according to the molar ratio of the lithium source: a nickel source: a cobalt source: m1 source 1.0-1.2: 0.6-1.0: 0-0.2: 0-0.2 weight percent;
s2, the materials weighed and prepared in the step S1 are loaded into crushing, mixing and drying integrated equipment, a certain amount of mixed medium and dispersing agent are added into the equipment, and the materials are uniformly mixed, crushed to submicron level and dried;
s3, putting the product in the S2 into a sagger, putting the sagger into an oxygen synthesis furnace for decomposition, oxidation and melting at the temperature of 300-600 ℃ for 3-10h, raising the temperature to 610-950 ℃ by an operator after the decomposition, oxidation and melting are finished, so that the material is melted, crystallized and synthesized for 3-30h, airing the product for 10-24h, cooling to room temperature, crushing the product, sieving by a 300-mesh sieve, and obtaining a semi-finished product Li as a undersize productxNi1-y-zCoyM1zO2Hereinafter referred to as Q1;
s4, mixing the required lithium source, nickel source, manganese source and M2 source materials according to the molar ratio of the lithium source: a nickel source: a manganese source: m2 source 1.0-1.1: 0.1-0.95: 0.05-0.5: 0-0.4 weight percent;
s5, the materials weighed and prepared in the step S4 are loaded into crushing, mixing and drying integrated equipment, a certain amount of mixed medium and dispersing agent are added into the equipment, the materials are uniformly mixed, crushed to submicron level and dried, and a semi-finished product Q2 is obtained;
s6, mixing Q1 in S3 and Q2 in S5 according to a molar ratio of Q1: q2 ═ 0.5-0.99: weighing 0.01-0.5, preparing, putting the prepared materials into a mixing and drying integrated device, adding a certain amount of mixing medium and dispersant into the mixing device, uniformly mixing the materials and drying;
s7, placing the product prepared in the step S6 into a sagger, placing the sagger into an oxygen synthesis furnace, decomposing, oxidizing and melting the sagger for 2-10h at the temperature of 300-600 ℃, then heating the temperature to 610-950 ℃, melting, crystallizing and synthesizing the sagger for 3-30h, airing the product for 10-24h, naturally cooling the product to room temperature, finally crushing the product and sieving the crushed product by a 300-mesh sieve, wherein the sieved product is the double-layer nickel-based composite oxide lithium battery anode material.
2. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the lithium source is Li2CO3、LiOH·H2O、LiOH、CH3COOLi、Li2C2O4、C6H5Li3O7·4H2One or more of O.
3. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the nickel source is at least one of oxalate, acetate, ammonia coordination compound, carbonyl coordination compound, hydroxide, oxide, carbonate, carbide and nitrate containing nickel, or one or more of composite hydroxide, composite carbonate, oxide, composite oxalate and composite acetate containing nickel, cobalt and manganese, nickel, cobalt and aluminum, nickel, cobalt and titanium and nickel and titanium elements.
4. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the cobalt source is at least one of oxalate, acetate, ammonia coordination compound, carbonyl coordination compound, hydroxide, oxide, carbonate, carbide and nitrate containing cobalt, or one or more of composite hydroxide, composite carbonate, oxide, composite oxalate and composite acetate of nickel-cobalt-manganese, nickel-cobalt, cobalt-manganese, nickel-cobalt-aluminum, nickel-cobalt-titanium and cobalt-titanium elements.
5. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the M1 source is one or more of hydroxides, carbonates, oxides, fluorides, phosphates, acetates, oxalates, ammonia coordination compounds and carbonyl coordination compounds of manganese, aluminum, titanium, antimony, magnesium, bismuth, gallium, tin, tungsten, germanium, tantalum, vanadium, strontium, cesium, indium, zinc, niobium, yttrium, molybdenum, rubidium, zirconium, silicon, boron and lanthanide elements, or one or more of composite hydroxides, composite carbonates or composite oxides containing the above elements.
6. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the manganese source is one or more of oxalate, acetate, ammonia coordination compound, carbonyl coordination compound, hydroxide, oxide, carbonate, carbide and nitrate containing manganese, or composite hydroxide, composite carbonate, oxide, composite oxalate and composite acetate containing nickel, cobalt and manganese, nickel and manganese and cobalt and manganese elements.
7. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the M2 source is one or more of hydroxides, carbonates, oxides, fluorides, phosphates, acetates, oxalates, ammonia coordination compounds and carbonyl coordination compounds of cobalt, aluminum, titanium, antimony, magnesium, bismuth, gallium, tin, tungsten, germanium, tantalum, vanadium, strontium, cesium, indium, zinc, niobium, yttrium, molybdenum, rubidium, zirconium, silicon, boron and lanthanide elements, or composite hydroxides, composite carbonates or composite oxides containing the above elements, or composite hydroxides, composite carbonates, composite oxides, composite oxalates and composite acetates of lithium cobalt manganese, lithium cobalt, lithium manganese, cobalt aluminum and cobalt titanium elements.
8. The method for preparing the double-layer nickel-based composite oxide lithium battery anode material by the two-step crystallization method according to claim 1, characterized in that: the dispersing agent is one or more of ethanol, isopropanol, deionized water, oxalic acid, acetic acid, citric acid, ethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene amine, urea, liquid ammonia, ammonium bicarbonate, ammonium carbonate, polyvinyl alcohol, polyacrylamide, acrylic resin, alkylolamide, stearic acid, fatty glyceride and other compounds in water solution.
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