CN104134798B - A kind of composite mixed type nickel cobalt positive electrode and preparation method thereof - Google Patents
A kind of composite mixed type nickel cobalt positive electrode and preparation method thereof Download PDFInfo
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- CN104134798B CN104134798B CN201410387874.7A CN201410387874A CN104134798B CN 104134798 B CN104134798 B CN 104134798B CN 201410387874 A CN201410387874 A CN 201410387874A CN 104134798 B CN104134798 B CN 104134798B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 238000012216 screening Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- 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 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 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
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 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 2
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 2
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 230000004941 influx Effects 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 229910013179 LiNixCo1-xO2 Inorganic materials 0.000 description 10
- 229910013171 LiNixCo1−xO2 Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 229910032387 LiCoO2 Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 229940097267 cobaltous chloride Drugs 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 229910003005 LiNiO2 Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 hexafluoro phosphate Chemical compound 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910019549 CoyMzO2 Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910015731 LiNi0.8Co0.05 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910013478 LiNixCoyMzO2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910009454 Y(OH)3 Inorganic materials 0.000 description 1
- 229910017869 a-NaFeO2 Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- ZMFWDTJZHRDHNW-UHFFFAOYSA-N indium;trihydrate Chemical compound O.O.O.[In] ZMFWDTJZHRDHNW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of composite mixed type nickel cobalt positive electrode and preparation method thereof.Described preparation method comprises the following steps: nickel, cobalt salt solution and protosalt mix homogeneously are obtained solution A；High-valency metal saline solution is obtained solution B with chelating agen mix homogeneously；Enveloping agent solution and precipitant solution mix homogeneously are obtained solution C, again solution A, solution B, solution C and oxidant flowing is added in reactor with end liquid and stir, heat, after fully reacting, slurry is carried out solid-liquid separation, washs, obtain nickel cobalt composite material precursor after drying.Calcining under oxygen atmosphere after being mixed homogeneously with lithium salts by presoma, crushing and classification after sintering, screening obtains composite mixed nickel cobalt positive electrode.The technique of the present invention is simpler, and Elemental redistribution is more uniform, it is possible to reach the mixing of atom level, and prepared positive electrode electrical property has obtained comprehensive lifting.
Description
Technical field
The invention belongs to electrode material field, particularly to a kind of composite mixed type nickel cobalt positive electrode and system thereof
Preparation Method.
Background technology
At present, stratiform LiCoO2It is modal positive electrode in practical lithium ion battery, but due to cobalt
Natural resources limited, expensive, its application development is greatly limited.And LiNiO2It is considered
It is to be hopeful most to substitute LiCoO2One of material, its theoretical capacity and LiCoO2Close, and to environment without
Pollute, in terms of price and resource, all occupy advantage, but ratio product is measured in its difficult synthesis, so LiNiO2Also
Not yet obtain large-scale promotion and application.
The comprehensive advantage boring system and nickel based material, replaces Co by part Ni and obtains material LiNixCo1-xO2, its
Have and LiCoO2Similar a-NaFeO2Layer structure, and LiNixCo1-xO2Reversible specific capacity up to
180mAh/g, significantly larger than LiCoO2(about 140mAh/g) and LiMn2O4(about 120mAh/g), if with
LiNixCo1-xO2Compound is positive electrode, and the specific energy of battery will increase substantially.It may be said that
LiNixCo1-xO2Not only possesses LiCoO2Characteristic (be easily-synthesized, stable performance), more have LiNiO concurrently2's
Height ratio capacity, the advantage of low cost, thus be with a wide range of applications.The development and application of such material
Present good growth momentum, and there is preferable combination property, thus become the research of lithium ion battery
One of focus.
Changed the CHARGE DISTRIBUTION of layer structure intraformational bed by dopant ion, improve the covalency of interlayer, have
It is beneficial to improve LiNixCo1-xO2Performance.The introducing of dopant ion, enhances the model of adjacent O-M-O interlayer
De Huali, thus be conducive to keeping stablizing of layer structure.Because LiNixCo1-xO2Send out during degree of depth discharge and recharge
Raw phase transformation, doping radius and Ni3+Close, ion such as Al without electro-chemical activity3+、Mg 2+Can be in charging
During play the effect of support, under conditions of overcharging, layer structure will not be caused because Li continues abjection
Destroy so that layer structure keeps stable.To LiNixCo1-xO2 mixes those electric charges height, ionic radius
High valence ion less, that self polarizability is the highest, can improve the polarization energy of O-M-O layer, thus carry
High LiNixCo1-xO2The stability of interlayer structure.
Work as Al3+Mix LiNixCo1-xO2After, do not provide electronics at charge and discharge process, limit Li ion
Embed and the amount of abjection so that for the Li of abjection+Maintain layer structure, the orderly of hexagonal structure can be improved
Property, reach to strengthen the effect of capacity holding capacity.To LiNixCo1-xO2Those valence states of middle incorporation relatively low from
Son, for making crystal charge conservation, after doping, there is electronic state hole in valence band so that conductivity improves.
Make LiNixCoyMzO2Positive electrode becomes LiNiO2The succedaneum of optimum potentiality.Such as Application No.
201110020708.X, 201210351698.2,200410072071.9 and the invention of 201280017701.5
All disclose positive electrode of nickel cobalt lithia including various element doping and preparation method thereof.
But, LiNi disclosed abovexCoyMzO2The problem that positive electrode still suffers from some.Such as preparation technology
Complexity, and solid phase method doping makes Elemental redistribution uneven；Liquid phase method doping cannot solve high price hydroxide
The thing problem that differential settling velocity that is that cause is excessive because molten long-pending degree is high.Part element doping at a low price is also had to make
Become more serious Ni2+Same Li+Position mixing；Part high valence elements doping can cause the electrical conductivity of material to decline.Cause
This is necessary the chemical property developing a kind of novel nickel cobalt positive electrode to improve material, improves above-mentioned asking
Topic.
Summary of the invention
For overcoming the defect of prior art, an object of the present invention is to provide a kind of composite mixed type nickel cobalt
Method for preparing anode material, by directly by required doped chemical by co-precipitation by the way of mix in material,
Prepared electrical property obtains the composite mixed type nickel cobalt positive electrode of General Promotion.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
A kind of composite mixed type nickel cobalt method for preparing anode material, comprises the following steps:
(1) nickel, cobalt saline solution and protosalt are mixed to obtain solution A, by high-valency metal saline solution
Mix to obtain solution B with chelating agen, obtain solution C by uniform to complexing agent aqueous solution and precipitant aqueous solution；
(2) by step (1) gained solution A, solution B, solution C and oxidant and flow addition the end of with
The reactor of liquid stirs, reacts, after having reacted, slurry is carried out solid-liquid separation, washing, dried
To nickel cobalt composite material precursor；
(3) sintering after being mixed with lithium salts by (2) gained presoma, then crushing and classification, screening can cross 200
The material of eye mesh screen is composite mixed nickel cobalt positive electrode.
According to method of the present invention, the nickel described in step (1), cobalt be the one in its soluble-salt or
Two or more mixing, one or more in the most respective sulfate, nitrate or chlorate
Mixing.
Preferably, described protosalt be Ca, Cu, Mg, Zn salt in one or more
Mixing.
Preferably, described high-valency metal salt is in the salt of Cr, Ga, In, Ti, Al, Y, Ru, Sn
One or more mixing.
Preferably, described chelating agen is EDTA, EDETATE SODIUM, salicylic acid, sulfosalicylic acid, Fructus Citri Limoniae
One or more mixing in acid, sodium citrate and EGTA.
Preferably, described chelating agent is ammonia, and preferred concentration is 2-7mol/L, for example, 2.1mol/L,
2.8mol/L, 4mol/L, 6mol/L etc..
Preferably, described precipitant is sodium hydroxide, potassium hydroxide, Lithium hydrate, rubidium hydroxide, hydrogen-oxygen
Change one or more the mixing in caesium, sodium carbonate, potassium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate；
Preferred concentration is 1-10mol/L, for example, 2mol/L, 4mol/L, 6mol/L, 8mol/L etc..
Preferably, the metal ion mol ratio of described nickel salt, cobalt salt, protosalt and high-valency metal salt is
7～9:0.5～2:0.1～1:0.1～1, for example, 72:15:2:5,79:12:6:4,83:18:9:9,88:13:4:8
Deng.
Preferably, in described solution A or solution B, concentration of metal ions summation is respectively 1-10mol/L, example
Such as 1mol/L, 2mol/L, 4mol/L, 8mol/L, preferably 2-6mol/L.
Preferably, the mol ratio of described chelating agen and high-valency metal salt is 1:0.5-5, for example, 1:0.8,1:1.5,
1:2.3,1:3.0,1:3.8,1:4.4 etc., preferably 1:0.5-3.
Preferably, described enveloping agent solution is 1:1-10, preferably 1:2-6 with the volume ratio of precipitant solution.
Preferably, step (2) described oxidant is KClO4、NaClO4、NaClO、H2O2、Na2S2O8、
K2S2O8、(NH4)2S2O8In one or more mixing, preferred concentration is 1-5mol/L.
Preferably, the influx of described oxidant with metal ion total concentration than for 1:0.5-2.5, for example,
1:0.8,1:1.5,1:2.3 etc..
Preferably, solution A is consistent with the flow velocity of solution B, is 1-10ml/min, keeps solution A and molten
In liquid B, metal ion flows into reactor according to certain ratio.
Preferably, the flow velocity of solution C is 1-15ml/min, is used for regulating pH value in reactor so that it is partially
Shifting scope is within ± 0.02..
Preferably, liquid of the described end is the mixed liquor of ammonia and precipitant.
Preferably, in end liquid, ammonia is consistent with precipitant concentration with the chelating agent flowed into the concentration of precipitant.
Preferably, the temperature of liquid of the described end is 40-70 DEG C, for example, 42 DEG C, 46 DEG C, 51 DEG C, 57 DEG C,
62 DEG C, 69 DEG C etc., preferably 45-65 DEG C, more preferably 50 DEG C.
Preferably, described mixing speed is 300-1000r/min.
Preferably, the pH of described reaction system is more than 9, preferably 9.5～11.5, more preferably
11.2±0.02。
Preferably, the time of described reaction is 10-40h.
Preferably, described washing is to wash to the pH value of cleaning mixture to reach 9.5～10.5.
According to method of the present invention, it is sintered in oxygen or air atmosphere carrying out described in step (3).
Preferably, described presoma is 1:1.0-1.1, for example, 1:105,1:1.08 etc. with the mol ratio of lithium salts.
Preferably, the temperature of described sintering is 550 DEG C～850 DEG C；The time of sintering is more than 5h, preferably
For 10h～20h.
An object of the present invention also resides in the composite mixed type nickel cobalt positive pole providing the method for the invention to prepare
Material.The electrical property of the electrode material that the electrode material that the present invention prepares prepares compared with prior art, as 0.1C is put
Capacitance, 1C50 week circulation etc. are greatly improved.
The present invention has the advantage that compared to prior art
1, table 1 is the molten long-pending degree constant table of all doped chemicals related in the present invention.As shown in Table 1,
The molten long-pending degree of metal ion of different valence state is widely different, therefore height to coprecipitation reaction by the way of chelating
Valency element carries out pretreatment so that the sedimentation velocity of element is more nearly.The method of the present invention is directly by required
Doped chemical by co-precipitation by the way of mix in material, technique is simpler, and Elemental redistribution is more
Uniformly, it is possible to reach the mixing of atom level.
2, carry out composite mixed by the metal ion of high-valence state and lower valency, not only improve material crystal structure
Stability, improve again the electrical conductivity of material so that the electrical property of material has obtained comprehensive lifting.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the nickel aluminum positive electrode powder obtained in embodiment 1；
Fig. 2 is the button cell cyclic curve figure of the positive electrode obtained in embodiment 1-4 and comparative example 1.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art it will be clearly understood that
Described embodiment is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Embodiment 1
(1) 8:1:0.5:0.5 weighs Nickel dichloride., cobaltous chloride, magnesium chloride and aluminum chloride crystal in molar ratio, will
After Nickel dichloride., cobaltous chloride and magnesium chloride are dissolved in water, mix homogeneously obtains solution A, and its concentration of metal ions is
2.0mol/L；By aluminum chloride with chelator acid citrate sodium according to 1:1 ratio mix homogeneously soluble in water, obtain solution
B；By 7mol/L ammonia and 2mol/L sodium hydroxide solution according to the volume ratio mix homogeneously of 1:4, obtain solution
C。
(2) by the NaClO of solution A, solution B and solution C Yu 2mol/L4And it is anti-to flow addition seriality
Answer in still, reactor fills with pH value be 11.0, temperature be the end liquid of 50 DEG C.Controlled anti-by solution C
Answer the pH value of system 11.0 ± 0.02, react 30h.After precipitated product washing, pH value is below 10.0, stops
Only wash and slurry is dried, obtaining the composite mixed presoma of nickel cobalt.
(3) by dried presoma and Lithium hydrate according to the ratio of 1:1.05 in oxygen atmosphere 850 DEG C
Sintering 20 hours, it is nickel aluminum compositely doped material that crushing and classification crosses the material of 200 mesh sieves.Molecular formula is
LiNi0.8Co0.1Mg0.05Al0.05O2。
Embodiment 2
(1) 7:2:0.1:0.9 weighs nickel sulfate, cobaltous sulfate, zinc sulfate and aluminum sulfate crystal in molar ratio, will
After nickel sulfate, cobaltous sulfate and zinc sulfate are dissolved in water, mix homogeneously obtains solution A, and its concentration of metal ions is
2.0mol/L；By calcium sulfate with chelating agen salicylic acid according to 1:3 ratio mix homogeneously soluble in water, obtain solution B；
By 2mol/L ammonia and 4mol/L sodium hydroxide solution according to the volume ratio mix homogeneously of 1:3, obtain solution C.
(2) by the NaClO of solution A, solution B and solution C Yu 5mol/L4And it is anti-to flow addition seriality
Answer in still, reactor fills with pH value be 9.5, temperature be the end liquid of 70 DEG C.Reaction is controlled by solution C
The pH value of system, 10.6 ± 0.02, reacts 30h.After precipitated product washing, pH value is below 10.0, stops
Only wash and slurry is dried, obtaining the composite mixed presoma of nickel cobalt.
(3) by dried presoma and lithium carbonate according to ratio 750 DEG C of burnings in oxygen atmosphere of 1:1.04
Tying 10 hours, it is nickel aluminum compositely doped material that crushing and classification crosses the material of 200 mesh sieves.Molecular formula is
LiNi0.7Co0.2Zn0.01Al0.09O2。
Embodiment 3
(1) 8:0.5:1:0.5 weighs Nickel dichloride., cobaltous chloride, calcium chloride and Chlorizate chromium crystal in molar ratio, will
After Nickel dichloride., cobaltous chloride and calcium chloride are dissolved in water, mix homogeneously obtains solution A, and its concentration of metal ions is
2.0mol/L；By Chlorizate chromium with chelating agen EDTA according to 1:1 ratio mix homogeneously soluble in water, obtain solution B；
By 4mol/L ammonia and 6mol/L sodium hydroxide solution according to the volume ratio mix homogeneously of 1:2, obtain solution C.
(2) by the NaClO of solution A, solution B and solution C Yu 1mol/L4And it is anti-to flow addition seriality
Answer in still, reactor fills with pH value be 10.0, temperature be the end liquid of 40 DEG C.Controlled anti-by solution C
Answer the pH value of system 10.4 ± 0.02, react 30h.After precipitated product washing, pH value is below 10.0,
Stop washing and slurry is dried, obtaining the composite mixed presoma of nickel cobalt.
(3) by dried presoma and Lithium hydrate according to the ratio of 1:1.03 in oxygen atmosphere 800 DEG C
Sintering 15 hours, it is nickel aluminum compositely doped material that crushing and classification crosses the material of 200 mesh sieves.Molecular formula is
LiNi0.8Co0.05Ca0.1Cr0.05O2。
Embodiment 4
With embodiment 1, only protosalt and high-valency metal salt dopping thing are changed to Zn and In respectively corresponding
Nitrate, obtains LiNi0.8Co0.1Zn0.05In0.05O2。
Table 1 is the molten long-pending degree constant table of all doped chemicals related in the present invention.As shown in Table 2, no
Widely different with the molten long-pending degree of the metal ion of valence state, high valence elements to coprecipitation reaction by the way of chelating
Carry out pretreatment, the sedimentation velocity of element can be made to be more nearly, thus the comprehensive of prepared material can be improved
Energy.
Table 1
| Sequence number | Molecular formula | Ksp | pKsp |
| 1 | Mg(OH)2 | 1.8×10-11 | 10.74 |
| 2 | Ca(OH)2 | 5.5×10-6 | 5.26 |
| 3 | Cu(OH)2 | 4.8×10-20 | 19.32 |
| 4 | Zn(OH)2 | 2.09×10-16 | 15.68 |
| 5 | Co(OH)2 | 2.00×10-16 | 15.7 |
| 6 | Ni(OH)2 | 2.0×10-15 | 14.7 |
| 7 | Cr(OH)3 | 6.3×10-31 | 30.2 |
| 8 | Ga(OH)3 | 7.0×10-36 | 35.15 |
| 9 | In(OH)3 | 1.3×10-37 | 36.9 |
| 10 | Ti(OH)3 | 1.0×10-40 | 40 |
| 11 | Al(OH)3 | 4.57×10-33 | 32.34 |
| 12 | Y(OH)3 | 8.0×10-23 | 22.1 |
| 13 | Ru(OH)3 | 1.0×10-36 | 36 |
| 14 | Sn(OH)4 | 1.0×10-56 | 56 |
Comparative example 1
(1) conventional control crystallization process synthesis Ni is used0.85Co0.15(OH)2Presoma.
(2) by nickel cobalt presoma, ZnO powder and Lithium hydrate 1:0.06:1.04 ball milling 4h in molar ratio,
Mix homogeneously.
(3) under oxygen atmosphere 850 DEG C sinter 20 hours, then natural cooling, crushing and classification crosses 200 mesh
Sieve obtains nickel aluminum ternary material LiNi0.8Co0.14Zn0.6O2。
Battery makes:
Above example 1～4 and comparative example 1 prepare positive electrode in a conventional way respectively at the ratio of 90:5:5
Example is applied on aluminium foil after being sufficiently stirred for organic solvent N-methyl-2-pyrrole network alkanone (NMP), is placed in 120 DEG C
Vacuum oven is dried 8h and obtains pole piece.In Braun inert atmosphere glove box, it is negative with metal lithium sheet
Pole, 1mol/L-lithium hexafluoro phosphate (LiPF6)+ethylene carbonate (EC)+dimethyl carbonate (DMC)+
Diethyl carbonate (MEC) (volume ratio 1:1:1) is electrolyte, and porous polypropylene film is barrier film, makes 2032
Button cell.Its electrical property result such as table 2 below.
Table 2
As can be seen from the above table, compared with existing mg-doped nickel cobalt binary material, the present invention is used to prepare
Positive electrode, is adulterated by the metal composite of different valence state, improves the combination property of material.
Applicant states, the present invention illustrates detailed process equipment and the technique of the present invention by above-described embodiment
Flow process, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention
Have to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field should
This understands, any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (31)
1. a composite mixed type nickel cobalt method for preparing anode material, comprises the following steps:
(1) nickel, cobalt saline solution and protosalt are mixed to obtain solution A, by high-valency metal saline solution
Mix to obtain solution B with chelating agen, obtain solution C by uniform to complexing agent aqueous solution and precipitant aqueous solution；
(2) by step (1) gained solution A, solution B, solution C and oxidant and flow addition the end of with
The reactor of liquid stirs, reacts, after having reacted, slurry is carried out solid-liquid separation, washing, dried
To nickel cobalt composite material precursor；
(3) sintering after being mixed with lithium salts by (2) gained presoma, then crushing and classification, screening can cross 200
The material of eye mesh screen is composite mixed nickel cobalt positive electrode；
Described chelating agent is ammonia, and its concentration is 2-7mol/L；
The metal ion mol ratio of step (1) described nickel salt, cobalt salt, protosalt and high-valency metal salt is
7～9:0.5～2:0.1～1:0.1～1；
In end liquid, ammonia is consistent with precipitant concentration with the chelating agent flowed into the concentration of precipitant；
The flow velocity of step (2) described solution A and solution B is 1-10ml/min.
Preparation method the most according to claim 1, it is characterised in that nickel described in step (1),
Cobalt salt is one or more the mixing in its soluble-salt.
Preparation method the most according to claim 2, it is characterised in that nickel described in step (1),
Cobalt salt is one or more the mixing in respective sulfate, nitrate or chlorate.
Preparation method the most according to claim 1, it is characterised in that described protosalt is
One or more mixing in the salt of Ca, Cu, Mg, Zn.
Preparation method the most according to claim 1, it is characterised in that described high-valency metal salt is
One or more mixing in the salt of Cr, Ga, In, Ti, Al, Y, Ru, Sn.
Preparation method the most according to claim 1, it is characterised in that described chelating agen be EDTA,
One in EDETATE SODIUM, salicylic acid, sulfosalicylic acid, citric acid, sodium citrate and EGTA or
Two or more mixing.
Preparation method the most according to claim 1, it is characterised in that described precipitant be sodium hydroxide,
Potassium hydroxide, Lithium hydrate, rubidium hydroxide, Cesium hydrate., sodium carbonate, potassium carbonate, lithium carbonate, carbonic acid
One or more mixing in rubidium, cesium carbonate.
Preparation method the most according to claim 1, it is characterised in that described precipitant concentration is 1-10
mol/L。
Preparation method the most according to claim 1, it is characterised in that step (1) described solution A
Or the concentration of metal ions summation in solution B is respectively 1-10mol/L.
Preparation method the most according to claim 1, it is characterised in that step (1) described chelating agen
It is 1:0.5-5 with the mol ratio of high-valency metal salt.
11. preparation methoies according to claim 10, it is characterised in that step (1) described chelating
The mol ratio of agent and high-valency metal salt is 1:0.5-3.
12. preparation method according to claim 1, it is characterised in that step (1) described chelating agent
Solution is 1:1-10 with the volume ratio of precipitant solution.
13. preparation methoies according to claim 1, it is characterised in that step (2) described oxidant
For KClO4、NaClO4、NaClO、H2O2、Na2S2O8、K2S2O8、(NH4)2S2O8In one or
Two or more mixing.
14. preparation method according to claim 1, it is characterised in that step (2) described oxidant
Concentration is 1-5mol/L.
15. preparation methoies according to claim 1, it is characterised in that step (2) described oxidant
Influx with metal ion total concentration than for 1:0.5-2.5.
16. preparation method according to claim 1, it is characterised in that step (2) described solution C
Flow velocity be 1-15ml/min.
17. preparation methoies according to claim 1, it is characterised in that step (2) described end liquid is
Ammonia and the mixed liquor of precipitant.
18. preparation methoies according to claim 1, it is characterised in that the temperature of liquid of the described end is
40-70℃。
19. preparation methoies according to claim 18, it is characterised in that the temperature of liquid of the described end is
45-65℃。
20. preparation method according to claim 19, it is characterised in that the temperature of liquid of the described end is
50℃。
21. preparation methoies according to claim 1, it is characterised in that step (2) described stirring speed
Degree is 300-1000r/min.
22. preparation methoies according to claim 1, it is characterised in that step (2) described reactant
The pH of system is more than 9.
23. preparation methoies according to claim 22, it is characterised in that step (2) described reaction
The pH of system is 9.5～11.5.
24. preparation methoies according to claim 23, it is characterised in that step (2) described reaction
The pH of system is 11.2 ± 0.02.
25. preparation methoies according to claim 1, it is characterised in that step (2) described reaction
Time is 10-40h.
26. preparation methoies according to claim 1, it is characterised in that step (2) described washing is
Washing reaches 9.5～10.5 to the pH value of cleaning mixture.
27. preparation methoies according to claim 1, it is characterised in that step is sintered in described in (3)
Oxygen or air atmosphere are carried out.
28. preparation method according to claim 1, it is characterised in that step (3) described presoma
It is 1:1.0-1.1 with the mol ratio of lithium salts.
29. preparation methoies according to claim 1, it is characterised in that the temperature of described sintering is
550 DEG C～850 DEG C；The time of sintering is more than 5h.
30. preparation method according to claim 29, it is characterised in that the time of described sintering is
10h～20h.
The composite mixed type nickel cobalt positive electrode that preparation method described in 31. any one of claim 1-30 prepares.
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| CN104934595B (en) * | 2015-05-08 | 2017-08-08 | 广州锂宝新材料有限公司 | Prepare the nickel cobalt aluminium precursor material being distributed with aluminium element gradient and the method for positive electrode |
| CN105206827A (en) * | 2015-08-31 | 2015-12-30 | 宁波金和锂电材料有限公司 | Nickel, cobalt and aluminum hydroxide and preparation method thereof and cathode material for lithium ion cell |
| CN106058244A (en) * | 2016-06-30 | 2016-10-26 | 广东省稀有金属研究所 | Preparation method and device of nickel-cobalt-aluminum anode material precursor |
| CN109768275B (en) * | 2019-01-03 | 2021-04-27 | 湖南中伟新能源科技有限公司 | Preparation method of titanium-doped lithium ion positive electrode material precursor |
| CN110776018B (en) * | 2019-10-29 | 2022-02-01 | 湖南中伟新能源科技有限公司 | Cobalt oxyhydroxide, preparation method thereof, lithium cobaltate, electrode and lithium ion battery |
| CN113839017A (en) * | 2021-08-23 | 2021-12-24 | 上海大学 | Water-based zinc ion battery positive electrode material with silver ear shape and preparation method thereof |
| CN113845154B (en) * | 2021-09-17 | 2023-10-13 | 天津市捷威动力工业有限公司 | Positive electrode solid solution material precursor, and preparation method and application thereof |
| CN114426313A (en) * | 2022-01-07 | 2022-05-03 | 云南大学 | High-energy-density ternary cathode material and preparation method and application thereof |
| CN116177616A (en) * | 2022-11-25 | 2023-05-30 | 浙江海创锂电科技有限公司 | NC high-nickel precursor with nano-flake spherical structure for NCA positive electrode material and preparation method thereof |
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