CN109455772B - Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material - Google Patents
Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material Download PDFInfo
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- CN109455772B CN109455772B CN201711456555.7A CN201711456555A CN109455772B CN 109455772 B CN109455772 B CN 109455772B CN 201711456555 A CN201711456555 A CN 201711456555A CN 109455772 B CN109455772 B CN 109455772B
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- 239000002243 precursor Substances 0.000 title claims abstract description 75
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 109
- 238000006243 chemical reaction Methods 0.000 claims description 90
- 239000007788 liquid Substances 0.000 claims description 39
- 239000003513 alkali Substances 0.000 claims description 36
- 239000012266 salt solution Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000008139 complexing agent Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 238000012216 screening Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- 239000011572 manganese Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [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 12
- 239000011858 nanopowder Substances 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 229910013716 LiNi Inorganic materials 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 239000002344 surface layer Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- -1 aluminum ions Chemical class 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- NDYMQOUYJJXCKJ-UHFFFAOYSA-N (4-fluorophenyl)-morpholin-4-ylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)N1CCOCC1 NDYMQOUYJJXCKJ-UHFFFAOYSA-N 0.000 claims 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 8
- 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 8
- 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 description 8
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 8
- 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 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 4
- 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 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-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
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910006525 α-NaFeO2 Inorganic materials 0.000 description 1
- 229910006596 α−NaFeO2 Inorganic materials 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
- 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
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
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Abstract
The invention provides a precursor for a lithium ion battery, a positive electrode material and preparation methods of the precursor and the positive electrode material. The precursor is spherical metal hydroxide with a molecular formula of NixCoyMzM1 aM2 d(OH)2+eM is Mn or Al, M1Is an element having an ionic radius greater than 0.76 Å, M2Is an element with an ionic radius of 0.76 Å or less, wherein x is 0.55-0.96, y is 0.02-0.25, z is 0.01-0.25, a is 0.0005-0.005, d is 0.0002-0.005, x + y + z + a + d =1, e is 0-0.06, M1The elements being homogeneously distributed in the bulk phase of the material, M2Elements are uniformly distributed on the surface of the material; the precursor has a novel structure, and the prepared anode material has more excellent capacity, cycle and safety performance. The preparation method is easy to stably control, has low cost and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a modified precursor and a positive electrode material for a lithium ion battery and a preparation method thereof, in particular to a doped and coated spherical metal hydroxide precursor, a positive electrode material prepared from the precursor and a preparation method of the precursor and the positive electrode material, and belongs to the technical field of lithium ion batteries.
Background
The lithium ion battery is the most common secondary battery at present, has the outstanding advantages of high energy density, good cycle performance, small self-discharge, no memory effect and the like, is widely applied to various portable electric tools, mobile phones, notebook computers, tablet computers, video cameras, weaponry and the like, and is also widely used in the fields of electric automobiles and various energy storage.
In recent years, the new energy automobile industry in China develops rapidly. In 2016, the sales volume of new energy vehicles reaches over 50 thousands. The power battery is of great importance as the heart of the electric automobile, and the positive electrode material is used as the core raw material of the power battery, which directly influences the energy density, safety, cycle life and other performances of the power battery. Common lithium ion battery anode materials mainly include ternary materials of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickelate and lithium nickel cobalt manganese. The ternary material has the advantages of high specific capacity, good cycle performance, low raw material cost and the like, but the specific capacity is increased along with the increase of the nickel content, and the cycle performance and the safety performance are correspondingly deteriorated. Therefore, although the ternary material, especially the high-nickel ternary material, has a high specific capacity, there still exist many defects in practical applications, such as safety performance, cycle performance, storage performance, and high-current charge and discharge performance.
At present, the ternary anode material of the lithium ion battery is mainly prepared by preparing a spherical or spheroidal precursor and then mixing and sintering the precursor and a lithium source. For example, chinese patent CN102916177B discloses a nickel-cobalt-manganese hydroxide precursor and a preparation method thereof, in which a nickel-cobalt-manganese mixed salt solution, a sodium hydroxide solution and an ammonia water solution are subjected to a coprecipitation reaction, the pH and the ammonia amount in the reaction process are controlled, and an additive with a particle morphology adjusting function is added to obtain the nickel-cobalt-manganese hydroxide precursor with a spherical structure. Chinese patent CN103400973B discloses a method for preparing lithium nickel cobalt aluminate and its precursor, in which an aluminum salt and a complexing agent are subjected to a complex reaction to form a stable aluminum complex, and then the stable aluminum complex and a nickel cobalt salt solution are simultaneously injected into a reaction kettle for a coprecipitation reaction to prepare a spherical lithium nickel cobalt aluminate precursor, and then the spherical lithium nickel cobalt aluminate precursor is calcined with a lithium source to synthesize the spherical lithium nickel cobalt aluminate material.
Although the above-mentioned patent can prepare a spherical precursor of the cathode material with uniform composition, the precursor is not doped and coated with trace elements, and the existing form of the trace elements and the structure of the material are not designed and controlled, which is not favorable for the performance of the cathode material.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a spherical metal hydroxide precursor, which can improve the capacity, the cycle performance, the safety performance, etc. of the cathode material by improving the material composition design and the process technology.
The invention also provides a preparation method of the metal hydroxide precursor and the anode material, which has the advantages of simple process, easy and stable control of the process, low production cost and suitability for large-scale industrial production.
The technical scheme of the invention is as follows:
the precursor for the lithium ion battery is spherical metal hydroxide, and the chemical molecular formula of the precursor is NixCoyMzM1 aM2 d(OH)2+eM is Mn or Al, M1Is one or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er with the ionic radius larger than 0.76 Å, M2Is one or more of elements Mg, Ti, Nb, Ta, Mo, W, Mn, Fe, Zn and Al with the ionic radius of less than or equal to 0.76 Å, wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, x + y + z + a + d =1, e is more than or equal to 0 and less than1The elements being homogeneously distributed in the bulk phase of the material, M2The elements are uniformly distributed on the surface of the material.
During sintering of this precursor and the Li source, M1The elements can be uniformly distributed in the positive electrode material phase, and the space structure of the material can be effectively supported due to the larger ionic radius of the elements, so that the structural stability of the material is improved, and the insertion and the extraction of lithium ions are facilitated; and M uniformly distributed on the surface of the precursor material2The element can diffuse to the inside of the particles to a certain degree in the sintering process due to small ionic radius, and a certain gradient structure is formed on the surface layer of the anode material, so that the surface activity of the material is stabilized, and a large inert layer cannot be formed to influence the capacity exertion of the material. The invention not only solves the problem of poor cycle performance and safety performance of the anode material, but also avoids forming an inert layer on the surface of the material and reduces the capacity of the final product. The doping element distribution structure of the precursor can realize the requirement of the anode material on high specific capacity, and can simultaneously meet the requirement of the anode material on circulationRing performance and safety performance requirements.
Further, the average particle size of the precursor for the lithium ion battery is 3-19 μm, wherein the average particle size refers to the corresponding particle size when the particle size distribution percentage reaches 50%, and the average particle size can be specifically adjusted according to actual requirements.
The invention also provides a preparation method of the precursor for the lithium ion battery, which comprises the following steps:
(1) preparing a salt solution from nickel salt, cobalt salt and manganese salt; will contain M1The compound of (A) is added into water to prepare M with a certain concentration1Feed liquid; will contain M2The compound of (A) is added into water to prepare M with a certain concentration2Feed liquid; dissolving alkali into an alkali solution with the concentration of 2-10 mol/L; and dissolving a complexing agent into a complexing agent solution with the concentration of 2-13 mol/L.
(2) Mixing the salt solution obtained in the step (1) and M1And (2) feeding the material liquid, the alkali solution and the complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed constant in the process, controlling the reaction pH to be 10.5-12.5, controlling the reaction temperature to be 40-70 ℃, controlling the concentration of the complexing agent in a reaction system to be 1-12 g/L, stopping feeding liquid when the reaction is finished, keeping the temperature of the reaction liquid and the stirring rotation speed unchanged, and continuously stirring for 5-20 min.
(3) Adding M in the step (1) into a reaction kettle according to a certain flow rate2Feed liquid and alkali solution, adjusting the pH of the reaction solution to be 10.5-12.5, and the reaction temperature to be 40-70 ℃, and M2After the feed liquid is added, continuously stirring for 10-60 min to obtain the doped M1Bag M2The hydroxide precursor slurry of (1).
(4) Carrying out solid-liquid separation, washing, drying and screening on the hydroxide precursor slurry in the step (3) to obtain a spherical hydroxide precursor material NixCoyMzM1 aM2 d(OH)2+e。
In the preparation method, the preparation method of the salt solution in the step (1) comprises the following steps of mixing nickel salt, cobalt salt and manganese salt according to a molar ratio of x: y: z is dissolved into a mixed salt solution with the concentration of 1-3 mol/L; or mixing nickel salt and cobalt salt according to a molar ratio of x: y is dissolved into a nickel-cobalt salt solution with the concentration of 1-3 mol/L, and an aluminum salt and alkali are mixed according to a certain proportion to prepare an aluminum salt solution with the concentration of 0.1-0.5 mol/L, wherein the molar ratio of aluminum ions and alkali in the aluminum salt and alkali mixed aluminum solution is 1: 5-1: 10.
In the preparation method, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt is one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate; the aluminum salt is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum acetate; said M1The compound of (A) is M1One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol; said M2The compound of (A) is M2One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol; the alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the complexing agent is one or more of salicylic acid, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid.
The positive electrode material for the lithium ion battery provided by the invention has the precursor, and the chemical molecular formula of the precursor is LiNixCoyMzM1 aM2 dO2M is Mn or Al, M1Is one or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er with the ionic radius larger than 0.76 Å, M2The ionic radius is less than or equal to 0.76 Å, wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, and x + y + z + a + d = 1.
The invention also provides a preparation method of the anode material for the lithium ion battery, which comprises the following steps: mixing the precursor with a lithium source, sintering, crushing, and finally screening to obtain the lithium ionPositive electrode material LiNi for sub-batteryxCoyMzM1 aM2 dO2。
In the preparation method, the lithium source is one or more of lithium carbonate, lithium hydroxide and lithium nitrate.
Compared with the prior art, the invention has the following advantages:
(1) the precursor material has a structure that elements with large ionic radius are uniformly distributed in material particles and elements with small ionic radius are uniformly distributed on the surface of the material, so that the structure of the prepared anode material is more stable, the ionic radius of doped elements in a bulk phase is large, the spatial structure of the material can be effectively supported, and the insertion and extraction of lithium ions are facilitated; the ionic radius of the surface doping element is small, the doping element diffuses into the particles in the sintering process, so that a certain gradient structure is formed on the surface layer, the electrode reaction generated on the surface of the particles is weakened, and meanwhile, a larger inert layer cannot be formed to influence the capacity exertion of the material, and the requirements of the anode material on high specific capacity, cycle performance and safety performance are further met.
(2) The preparation method can realize that the elements with large ionic radius are uniformly distributed in the positive electrode material particles, and the elements with small ionic radius form a certain gradient structure on the surface layer of the positive electrode material, thereby solving the problem that the elements with large ionic radius cannot be effectively and uniformly diffused into the positive electrode material in the sintering process by being mixed on the surface of the precursor; in addition, the elements with small ionic radius only act on the surface layer of the cathode material, so that the content of inert elements in the material is reduced, and the capacity of the cathode material is favorably exerted. The whole preparation method has simple process and easily controlled process, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a 2000-fold Scanning Electron Microscope (SEM) image of a precursor prepared in example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a precursor prepared in example 1 of the present invention with a particle cross section of 5000 times.
Fig. 3 is a Scanning Electron Microscope (SEM) image at 3000 times of the positive electrode material produced in example 1 of the present invention.
Fig. 4 is XRD patterns of the cathode material prepared in example 1 of the present invention and comparative example 1.
Fig. 5 is a normal temperature cycle curve diagram of the button cell under the voltage range of 3.0-4.5V for the positive electrode material prepared in example 1 of the invention and comparative example 1.
Fig. 6 is a 45 ℃ high temperature cycling curve diagram of the button cell under the voltage range of 3.0-4.3V for the positive electrode material prepared in example 1 of the invention and comparative example 1.
Detailed Description
The present invention will be understood by the following examples and the accompanying drawings, but the present invention is not limited thereto.
Comparative example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the metal molar ratio of 82: 12: 6 to obtain a mixed salt solution of 2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 6 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 5 mol/L.
Adding 20L of mixed salt solution, aqueous alkali and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 400rpm constant in the process, simultaneously controlling the liquid inlet flow of the mixed salt solution at 400mL/h, the reaction pH at 11.9-12.1, the reaction temperature at 50 ℃, controlling the ammonia concentration in a reaction system at 8-10 g/L, keeping the temperature and the stirring rotation speed of the reaction solution unchanged when the reaction is finished, continuously stirring for 10min, then carrying out solid-liquid separation and washing on the obtained nickel-cobalt-manganese hydroxide slurry, drying the filter cake at 115 ℃ for 5h, and then screening to obtain a spherical hydroxide precursor material Ni0.82Co0.12Mn0.06(OH)2Average particle size D50And 10.2 μm.
Mixing the spherical nickel-cobalt-manganese hydroxide material with lithium hydroxide, sintering for 10h at 800 ℃ in an oxygen atmosphere, crushing and screening to obtain the positive material nickel-cobalt-manganese acid lithium for the lithium ion battery, wherein the chemical molecular formula is LiNi0.82Co0.12Mn0.06O2。
Example 1
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the metal molar ratio of 82: 12: 6 to obtain a mixed salt solution with the concentration of 2mol/L, dissolving calcium nitrate into a calcium nitrate solution with the concentration of 0.1mol/L, and dissolving aluminum nitrate into an aluminum nitrate solution with the concentration of 0.5 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 6 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 5 mol/L.
And adding 20L of mixed salt solution, calcium nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed of 500rpm constant in the process, controlling the liquid inlet flow of the mixed salt solution to be 400mL/h, the liquid inlet flow of the calcium nitrate solution to be 16mL/h, controlling the reaction pH to be 11.9-12.1, the reaction temperature to be 50 ℃, controlling the concentration of ammonia in a reaction system to be 8-10 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 10 min.
Adding 160mL of aluminum nitrate solution into a reaction kettle at the flow rate of 160mL/h, adding an alkali solution to adjust the reaction pH to 11.9-12.1 at the reaction temperature of 50 ℃, and continuing stirring for 30min after the aluminum nitrate solution is added to obtain the Ca-doped and Al-coated nickel-cobalt-manganese hydroxide precursor slurry. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake for 5h at 115 ℃, and screening to obtain a spherical hydroxide precursor material Ni0.8167Co0.1195Mn0.0598Ca0.002Al0.002(OH)2.002Average particle size D50And 10.4 μm.
Mixing the precursor with lithium hydroxide, sintering at 800 ℃ for 10h in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.8167Co0.1195Mn0.0598Ca0.002Al0.002O2。
It can be seen from fig. 1 that the precursor material obtained in example 1 is a spherical particle with a regular shape. The internal structure of the spherical particles is oriented radially from inside to outside, and the particles are relatively dense, as shown in fig. 2. The positive electrode material prepared by high-temperature sintering keeps the spherical morphology of the precursor, and no adhesion exists among particles, as shown in figure 3.
From FIG. 4 can be seenThe XRD lines of the products obtained in example 1 and comparative example 1 are sharp, and the comparison of the two curves shows that no other impurity peak exists, which indicates that the crystals of the cathode materials obtained in example 1 and comparative example 1 are both typical alpha-NaFeO2The structure of the positive electrode material is not changed by doping modification of trace elements, but the diffraction peak intensity I of the positive electrode materials obtained in example 1 and comparative example 1(003)/I(104)1.45 and 1.26 respectively, show that the cathode material of the embodiment 1 has higher crystallization degree and more perfect crystal structure.
The positive electrode materials obtained in the embodiment 1 and the comparative example 1 are made into 2032 button cells, and the capacity retention rates after 80 cycles under normal temperature 1C charge-discharge within the voltage range of 3.0-4.5V are respectively 92.7% and 91.0%, as shown in FIG. 5; the capacity retention rates after 80 cycles at 1C @45 ℃ under charge-discharge within the voltage range of 3.0-4.3V were 91.1% and 85.8%, respectively, as shown in FIG. 6. As can be seen from the above test data, the positive electrode material in example 1 has significantly better cycle performance at normal temperature and high temperature than the positive electrode material in comparative example 1.
Example 2
Nickel nitrate and cobalt nitrate are mixed according to a metal molar ratio of 88: 9 to obtain 1mol/L mixed salt solution; mixing aluminum nitrate and sodium hydroxide according to a molar ratio of 1:5 to prepare an aluminum solution with an aluminum ion concentration of 0.3 mol/L; dissolving zirconium nitrate into a zirconium nitrate solution with the concentration of 0.05 mol/L; dissolving cerium nitrate into a cerium nitrate solution with the concentration of 0.05 mol/L; dissolving magnesium sulfate into a magnesium sulfate solution with the concentration of 0.25 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 3 mol/L.
Adding 20L of mixed salt solution, aluminum solution, zirconium nitrate solution, cerium nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed at 600rpm constant in the process, simultaneously controlling the liquid inlet flow of the mixed salt solution at 400mL/h, the liquid inlet flow of the aluminum solution at 41mL/h, the liquid inlet flow of the zirconium nitrate solution at 12.5mL/h, the liquid inlet flow of the cerium nitrate solution at 12.5mL/h, the reaction pH at 12.2-12.4, the reaction temperature at 55 ℃, controlling the concentration of ammonia in a reaction system at 9-11 g/L, and when the reaction is finished, keeping the temperature and the stirring rotation speed of the reaction solution unchanged, and continuing stirring for 15 min.
Adding 125mL of magnesium sulfate solution into a reaction kettle at a flow rate of 80mL/h, adding an alkali solution to adjust the reaction pH to 12.2-12.4 at the reaction temperature of 55 ℃, and continuously stirring for 20min after the magnesium sulfate solution is added to obtain the Zr and Ce doped and Mg coated nickel-cobalt-aluminum hydroxide precursor slurry. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake at 120 ℃ for 5h, and then screening to obtain a spherical hydroxide precursor material Ni0.8762Co0.0896Al0.0297Zr0.0015Ce0.0015Mg0.0015(OH)2.036Average particle size D50It was 8.6 μm.
Mixing the precursor with lithium hydroxide, sintering for 8h at 750 ℃ in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.8762Co0.0896Al0.0297Zr0.0015Ce0.0015Mg0.0015O2。
Example 3
Nickel sulfate, cobalt chloride and manganese chloride are mixed according to a metal molar ratio of 60: 20: 20 to obtain 2.5mol/L mixed salt solution; dissolving lanthanum nitrate into a lanthanum nitrate solution with the concentration of 0.1 mol/L; adding TiO into the mixture2The nanometer powder is prepared into TiO with the concentration of 0.2mol/L2Suspending liquid; dissolving sodium hydroxide into an alkali solution with the concentration of 10 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 12 mol/L.
And adding 20L of mixed salt solution, lanthanum nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 650rpm constant in the process, controlling the liquid inlet flow of the mixed salt solution at 200mL/h, the liquid inlet flow of the lanthanum nitrate solution at 10mL/h, controlling the reaction pH at 11.2-11.4, the reaction temperature at 60 ℃, controlling the concentration of ammonia in a reaction system at 6-8 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 5 min.
150ml of TiO2Adding the suspension into the reaction kettle at the flow rate of 75mL/h, and simultaneously adding an alkali solution to adjust the pH of the reaction to 11.2-11.4, the reaction temperature is 60 ℃, and TiO2And continuing stirring for 30min after the suspension is added to obtain the La-doped and Ti-coated nickel-cobalt-manganese hydroxide precursor slurry. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake for 3h at 130 ℃, and screening to obtain a spherical hydroxide precursor material Ni0.5984Co0.1995Mn0.1995La0.002Ti0.0006(OH)2.003Average particle size D50It was 14.8 μm.
Mixing the precursor with lithium carbonate, sintering at 870 ℃ for 13h in air atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.5984Co0.1995Mn0.1995La0.002Ti0.0006O2。
Example 4
Nickel acetate, cobalt acetate and manganese acetate are mixed according to a metal molar ratio of 65: 20: 15 to obtain 1.5mol/L mixed salt solution; dissolving cerium acetate into a cerium acetate solution with the concentration of 0.05 mol/L; dissolving ammonium tungstate into an ammonium tungstate solution with the concentration of 0.2 mol/L; dissolving niobium oxalate into niobium oxalate solution with the concentration of 0.2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 8 mol/L; dissolving ammonia water into a complexing agent solution with the concentration of 8 mol/L.
And adding 20L of mixed salt solution, a cerium acetate solution, an alkali solution and a complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 700rpm constant in the process, controlling the liquid inlet flow rate of the mixed salt solution at 200mL/h, the liquid inlet flow rate of the cerium acetate solution at 20mL/h, the reaction pH at 11.4-11.6, the reaction temperature at 65 ℃, controlling the concentration of ammonia in a reaction system at 5-7 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 10 min.
Adding 108mL of ammonium tungstate solution and 92mL of niobium oxalate solution into a reaction kettle respectively according to the flow rates of 27mL/h and 23mL/h, adding an alkali solution to adjust the reaction pH to be 11.4-11.6 at the reaction temperature of 65 ℃, and continuing stirring for 15min after the ammonium tungstate solution and the niobium oxalate solution are added to obtain the Ce-doped W, Nb-coated nickel-cobalt-manganese hydroxide precursor slurry. Then theCarrying out solid-liquid separation and washing on the obtained hydroxide slurry, drying a filter cake for 4h at 120 ℃, and screening to obtain a spherical hydroxide precursor material Ni0.647Co0.1991Mn0.1493Ce0.0033W0.0007Nb0.0006(OH)2.01Average particle size D50It was 8.7 μm.
Mixing the precursor with lithium hydroxide, sintering at 840 ℃ for 10h in air atmosphere, crushing and screening to obtain the spherical anode material LiNi for the lithium ion battery0.647Co0.1991Mn0.1493Ce0.0033W0.0007Nb0.0006O2。
Example 5
Nickel sulfate and cobalt chloride are mixed according to a metal molar ratio of 92: 4 to obtain 2mol/L mixed salt solution; mixing aluminum nitrate and potassium hydroxide according to a molar ratio of 1:8 to prepare an aluminum solution with an aluminum ion concentration of 0.4 mol/L; dissolving strontium nitrate into a strontium nitrate solution with the concentration of 0.05 mol/L; dissolving ammonium paramolybdate into an ammonium paramolybdate solution with the molybdenum concentration of 0.3 mol/L; dissolving sodium hydroxide and lithium hydroxide into an alkali solution with the concentration of 5mol/L according to the molar ratio of 20: 1; sulfosalicylic acid and ammonium chloride are respectively dissolved into a solution with the concentration of 2mol/L to be jointly used as a complexing agent solution.
Adding 20L of mixed salt solution, strontium nitrate solution, alkali solution and complexing agent solution into a reaction kettle in a co-current manner for reaction, keeping the stirring rotation speed at 600rpm constant in the process, controlling the liquid inlet flow of the mixed salt solution at 200mL/h, the liquid inlet flow of the aluminum solution at 42mL/h, the liquid inlet flow of the strontium nitrate solution at 10mL/h, controlling the reaction pH at 12.2-12.4, the reaction temperature at 55 ℃, controlling the concentration of ammonia in a reaction system at 3-5 g/L, and continuously stirring for 15min when the reaction is finished and the temperature and the stirring rotation speed of the reaction solution are kept unchanged.
Adding 300mL of ammonium paramolybdate solution into a reaction kettle at the flow rate of 50mL/h, adding an alkali solution to adjust the reaction pH to 12.2-12.4 at the reaction temperature of 55 ℃, and continuing stirring for 20min after the ammonium paramolybdate solution is added to obtain the Sr-doped and Mo-coated nickel-cobalt-aluminum hydroxide precursor slurry. Then the obtained hydroxide slurry is mixedCarrying out solid-liquid separation and washing, drying a filter cake at 120 ℃ for 4h, and screening to obtain a spherical hydroxide precursor Ni0.9166Co0.0399Al0.0402Sr0.0012Mo0.0022(OH)2.045Average particle size D50It was 7.5 μm.
Mixing the precursor with lithium hydroxide, sintering for 6h at 720 ℃ in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.9166Co0.0399Al0.0402Sr0.0012Mo0.0022O2。
Example 6
Nickel nitrate, cobalt nitrate and manganese nitrate are mixed according to a metal molar ratio of 95: 2: 3 to obtain a mixed salt solution of 1.0 mol/L; dissolving yttrium nitrate into yttrium nitrate solution with the concentration of 0.07 mol/L; dissolving lanthanum chloride into a lanthanum chloride solution with the concentration of 0.07 mol/L; dissolving aluminum nitrate into an aluminum nitrate solution with the concentration of 0.2 mol/L; dissolving zinc sulfate into a zinc sulfate solution with the concentration of 0.2 mol/L; dissolving sodium hydroxide into an alkali solution with the concentration of 4 mol/L; dissolving ammonium sulfate into a complexing agent solution with the concentration of 2 mol/L.
Adding 20L of mixed salt solution, yttrium nitrate solution, lanthanum chloride solution, alkali solution and complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed at 500rpm constant in the process, simultaneously controlling the liquid inlet flow of the mixed salt solution at 300mL/h, the liquid inlet flow of the yttrium nitrate solution at 10mL/h, the liquid inlet flow of the lanthanum chloride solution at 10mL/h, the reaction pH at 12.3-12.5, the reaction temperature at 50 ℃, controlling the concentration of ammonia in a reaction system at 10-12 g/L, and when the reaction is finished, keeping the temperature of the reaction solution and the stirring rotation speed unchanged, and continuing stirring for 20 min.
Adding 250mL of aluminum nitrate solution and 250mL of zinc sulfate solution into a reaction kettle respectively according to the flow rate of 50mL/h, simultaneously adding aqueous alkali to adjust the reaction pH to be 12.3-12.5, controlling the reaction temperature to be 50 ℃, and continuously stirring for 30min after the aluminum nitrate solution and the zinc sulfate solution are added to obtain Y, La-doped nickel-cobalt-manganese hydroxide precursor slurry containing Al and Zn. Then carrying out solid-liquid separation and washing on the obtained hydroxide slurry, and drying a filter cake at 120 ℃ for 4Sieving after h to obtain a spherical hydroxide precursor Ni0.9411Co0.0198Mn0.0297Y0.0023La0.0023Al0.0024Zn0.0024(OH)2.007Average particle size D50And 9.3 μm.
Mixing the precursor with lithium hydroxide, sintering for 8h at 720 ℃ in an oxygen atmosphere, crushing and screening to obtain the spherical positive electrode material LiNi for the lithium ion battery0.9411Co0.0198Mn0.0297Y0.0023La0.0023Al0.0024Zn0.0024O2。
Finally, it is to be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: it is to be understood that modifications may be made to the technical solutions described in the foregoing embodiments, or some or all of the technical features may be equivalently replaced, and the modifications or the replacements may not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A modified precursor for a lithium ion battery is characterized in that: the precursor is spherical metal hydroxide, and the chemical molecular formula is NixCoyMzM1 aM2 d(OH)2+eM is Mn or Al, M1Is an ionic radius greater than
One or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er, M2The ionic radius is less than or equal toOne or more of elements Mg, Ti, Nb, Ta, Mo, W, Mn, Fe, Zn and Al, wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, and x +y + z + a + d is 1, and e is more than or equal to 0 and less than or equal to 0.06; m in the precursor1The elements being homogeneously distributed in the bulk phase of the material, M2The elements are uniformly distributed on the surface of the material.
2. The precursor for a lithium ion battery according to claim 1, wherein the average particle size of the precursor for a lithium ion battery is 3 to 19 μm.
3. A positive electrode material for a lithium ion battery, which comprises the precursor of any one of claims 1 to 2, wherein the molecular formula of the positive electrode material is LiNixCoyMzM1 aM2 dO2M is Mn or Al, M1Is an ionic radius greater than
One or more of Ca, Sr, Ba, Zr, Y, La, Ce, Sm and Er, M2The ionic radius is less than or equal to
Wherein x is more than or equal to 0.55 and less than or equal to 0.96, y is more than or equal to 0.02 and less than or equal to 0.25, z is more than or equal to 0.01 and less than or equal to 0.25, a is more than or equal to 0.0005 and less than or equal to 0.005, d is more than or equal to 0.0002 and less than or equal to 0.005, and x + y + z + a + d is equal to 1; m in the positive electrode material2The elements form a certain gradient structure on the surface layer of the anode material particles, and the content of the elements is gradually reduced from outside to inside.
4. The method for preparing a precursor for a lithium ion battery according to any one of claims 1 to 2, comprising the steps of:
(1) preparing a salt solution from nickel salt, cobalt salt and manganese salt; will contain M1The compound of (A) is added into water to prepare M with a certain concentration1Feed liquid; will contain M2The compound of (A) is added into water to prepare M with a certain concentration2Feed liquid; dissolving alkali into an alkali solution with the concentration of 2-10 mol/L; dissolving a complexing agent into a complexing agent solution with the concentration of 2-13 mol/L；
(2) Mixing the salt solution obtained in the step (1) and M1Feeding the material liquid, the alkali solution and the complexing agent solution into a reaction kettle in a parallel flow manner for reaction, keeping the stirring rotation speed constant in the process, controlling the reaction pH to be 10.5-12.5, controlling the reaction temperature to be 40-70 ℃, controlling the concentration of the complexing agent in a reaction system to be 1-12 g/L, stopping feeding liquid when the reaction is finished, keeping the temperature of the reaction liquid and the stirring rotation speed unchanged, and continuously stirring for 5-20 min;
(3) adding M in the step (1) into a reaction kettle according to a certain flow rate2Feed liquid and alkali solution, adjusting the pH of the reaction solution to be 10.5-12.5, and the reaction temperature to be 40-70 ℃, and M2After the feed liquid is added, continuously stirring for 10-60 min to obtain the doped M1Bag M2The hydroxide precursor slurry of (1);
(4) carrying out solid-liquid separation, washing, drying and screening on the hydroxide precursor slurry in the step (3) to obtain a spherical hydroxide precursor material NixCoyMzM1 aM2 d(OH)2+e。
5. The method for preparing a positive electrode material for a lithium ion battery according to claim 3, comprising the steps of: mixing the precursor of any one of claims 1 to 2 with a lithium source, sintering, crushing, and finally screening to obtain the positive electrode material LiNi for the lithium ion batteryxCoyMzM1 aM2 dO2。
6. The method for preparing a precursor for a lithium ion battery according to claim 4, wherein the salt solution in the step (1) is prepared by mixing a nickel salt, a cobalt salt and a manganese salt in a molar ratio of x: y: z is dissolved into a mixed salt solution with the concentration of 1-3 mol/L; or mixing nickel salt and cobalt salt according to a molar ratio of x: y is dissolved into a nickel-cobalt salt solution with the concentration of 1-3 mol/L, and aluminum salt and alkali are mixed according to a certain proportion to prepare an aluminum salt solution with the concentration of 0.1-0.5 mol/L.
7. The method for preparing the precursor for the lithium ion battery according to claim 6, wherein the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt is one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate; the aluminum salt is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum acetate; the alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide; the complexing agent is one or more of salicylic acid, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid.
8. The method according to claim 4, wherein M is selected from the group consisting of1The compound of (A) is M1One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol; said M2The compound of (A) is M2One or more of soluble salt, oxide nano powder, hydroxide nano powder, oxyhydroxide nano powder and sol.
9. The method according to claim 5, wherein the lithium source is one or more of lithium carbonate and lithium hydroxide.
10. The method for preparing the precursor for the lithium ion battery according to claim 6, wherein the molar ratio of the aluminum ions to the alkali in the aluminum salt solution prepared by mixing the aluminum salt and the alkali is 1:5 to 1: 10.
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| EP3793011B1 (en) * | 2019-03-29 | 2024-04-24 | JX Metals Corporation | Oxide-based positive electrode active material for all-solid-state lithium ion batteries, method for producing precursor of oxide-based positive electrode active material for all-solid-state lithium ion batteries, method for producing oxide-based positive electrode active material for all-solid-state lithium ion batteries, and all-solid-state lithium ion battery |
| CN110085827A (en) * | 2019-04-23 | 2019-08-02 | 中国电力科学研究院有限公司 | A kind of lithium-rich manganese-based anode material and its preparation method and application |
| CN112447962A (en) * | 2019-08-27 | 2021-03-05 | 荆门市格林美新材料有限公司 | Precursor for doped lithium ion battery, positive electrode material and preparation methods of precursor and positive electrode material |
| WO2021039239A1 (en) * | 2019-08-30 | 2021-03-04 | パナソニック株式会社 | Positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery |
| CN110571427B (en) * | 2019-09-09 | 2021-01-05 | 中伟新材料股份有限公司 | Ternary cathode material, preparation method thereof and lithium battery |
| CN110808367B (en) * | 2019-11-19 | 2020-10-30 | 浙江帕瓦新能源股份有限公司 | Ternary precursor and preparation method thereof |
| CN112357972A (en) * | 2020-09-30 | 2021-02-12 | 宜宾光原锂电材料有限公司 | Low-nickel cobalt-free precursor, cathode material and preparation method thereof |
| CN113745497B (en) * | 2021-08-06 | 2022-07-12 | 华南理工大学 | Gradient doping and surface modification method for single crystal high nickel lithium ion battery anode material |
| CN113651374B (en) * | 2021-10-20 | 2021-12-21 | 浙江帕瓦新能源股份有限公司 | Preparation method of ferrozirconium-doped nickel-cobalt-manganese ternary precursor |
| CN115020698B (en) * | 2022-07-28 | 2023-05-09 | 广东邦普循环科技有限公司 | Modified lithium cobalt oxide positive electrode material, preparation method thereof and lithium ion battery |
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