CN109461925A - A kind of monocrystalline nickel-cobalt lithium manganate cathode material, presoma and preparation method thereof - Google Patents
A kind of monocrystalline nickel-cobalt lithium manganate cathode material, presoma and preparation method thereof Download PDFInfo
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- CN109461925A CN109461925A CN201810713401.XA CN201810713401A CN109461925A CN 109461925 A CN109461925 A CN 109461925A CN 201810713401 A CN201810713401 A CN 201810713401A CN 109461925 A CN109461925 A CN 109461925A
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- Prior art keywords
- nickel
- cathode material
- lithium manganate
- manganate cathode
- cobalt
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- 239000010406 cathode material Substances 0.000 title claims abstract description 51
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims 1
- 229920002689 polyvinyl acetate Polymers 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 20
- 238000005245 sintering Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000004886 process control Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 7
- 238000005056 compaction Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 230000008646 thermal stress Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- SHLYLUCANOJWJB-UHFFFAOYSA-N [Co].[Ni].[N+](=O)(O)[O-] Chemical compound [Co].[Ni].[N+](=O)(O)[O-] SHLYLUCANOJWJB-UHFFFAOYSA-N 0.000 description 1
- PAMMESUSQVJOMA-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Ni].[Co] PAMMESUSQVJOMA-UHFFFAOYSA-L 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 235000002908 manganese Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- H01M4/485—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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention discloses a kind of monocrystalline nickel-cobalt lithium manganate cathode material, presoma and preparation method thereof, and the positive electrode molecular formula is LiaNixCoyMn1‑x‑yM’zM’’wO2‑δRδ(0.95≤a≤1.25,0≤x≤1,0≤y≤0.5,0≤z≤0.01,0≤w≤0.05,0≤δ≤0.02).This method obtains that a kind of particle is small, pattern is loose, density is smaller, the biggish nickel cobalt manganese hydroxide precursor of specific surface area by the way that dispersing agent is added and controls the content of coprecipitation reaction complexing agent, synthesis pH value, reaction temperature.With this presoma and lithium salts and specific fluxing element additive mixed sintering, the nickel-cobalt lithium manganate cathode material with typical single crystal pattern has been obtained.Present invention process is simple, and process control is easy, without being transformed or adding existing equipment；Resulting presoma easily with lithium salts reaction bonded, reduces sintering temperature, simplifies sintering process, and production efficiency greatly improves.
Description
Technical field
The invention belongs to field of lithium ion battery, just more particularly, to a kind of single-crystal doped polynary nickle cobalt lithium manganate of type
Pole material, presoma and preparation method thereof.
Background technique
Lithium ion battery is green high-capacity amount battery, have voltage is high, energy density is big, good cycle, self discharge are small,
Outstanding advantages of memory-less effect, is widely used in various portable power tools, electronic instrument, mobile phone, notebook electricity
Brain, video camera, weaponry etc., in electric car and all kinds of energy storage fields also large-scale use.
Positive electrode is one of important component of lithium ion battery, and the superiority and inferiority of positive electrode directly determines lithium-ion electric
The performance in pond.Ternary nickle cobalt lithium manganate capacity with higher, excellent circulation and multiplying power performance, in recent years gradually become lithium from
The hot spot of sub- cell positive material research and application.Wherein, application of the ternary material in terms of power battery and high-voltage battery
It is continuously increased.The conventional secondary polycrystalline particle positive electrode powder compacted density of ternary reunion figure is lower, easily produces at high temperature
The problem of raw flatulence, high temperature circulation and high voltage test are performed poor.Therefore, it is necessary to a kind of little particle nickel cobalt manganeses of monocrystalline pattern
Sour lithium material inhibits high temperature to produce gas, improves the compacted density of positive electrode as anode to improve high-temperature behavior.
The synthesis of monocrystalline type ternary nickel-cobalt lithium manganate cathode material and preparation and reunion figure more mature at present are secondary
Polycrystalline particle technique is compared, and realizes that difficulty is bigger, is mainly reflected in special appearance used, the synthesis of size presoma and sintered
The two aspects of the doping of auxiliary element in journey.Patent numbers at present about monocrystalline type tertiary cathode material are less, most of
The key content of patent focuses primarily upon sintering processing, sintering temperature, particle in monocrystalline lithium nickel cobalt manganese oxygen chemical combination object preparation process
Be crushed etc., and doping, the research of fluxing element in presoma type used and sintering process are still lacked specifically
It is bright.Application No. is the nickel cobalt manganese hydroxide precursors that the Chinese patent of CN201610739897.9 uses general type, use
Up to 5 sections of sintering process prepares monocrystalline positive electrode, and process flow is complicated, condition is strictly difficult to control, higher cost.Shen
It please number be to be broken for bulky grain presoma for the Chinese patent method for preparing monocrystalline positive electrode of CN201611037434.4
Small fragment, then formed with metallic element additive and lithium source mixed sintering.Large granular spherical presoma is crushed by physics by force
After little particle, multiple indexs such as pattern, density of material different degrees of can be affected, and be unfavorable for final positive electrode
Firing.
The quality of presoma performance indicator directly determines the superiority and inferiority of positive electrode performance, therefore nickel cobalt manganese hydroxide pair
It is most important in the performance of nickel-cobalt-manganternary ternary anode material.Particularity in view of monocrystal material relative to conventional polycrystalline material, has
Necessity prepares a kind of little particle nickel cobalt manganese hydroxide of specific morphology as presoma, obtains monocrystalline by the way that high temperature is once sintered
The primary particle positive electrode of pattern.
Summary of the invention
To achieve the above object, the present invention is intended to provide a kind of nickel-cobalt lithium manganate cathode material presoma, by nickel cobalt
Manganese hydroxide precursor synthesis control and sintering process in specific doped chemical addition, obtain a kind of specific capacity it is higher,
Cycle performance is excellent, and the little particle with typical single crystal pattern adulterates polynary positive pole material.
The present invention also provides the preparation methods of above-mentioned nickel cobalt manganese hydroxide and doped single crystal nickle cobalt lithium manganate.Research and development hair
It is existing, to prepare small particle, large specific surface area, loose, low-density precursor, need guaranteeing between particle in coprecipitation process
Good dispersibility cannot excessively reunite, accumulate.A certain amount of dispersing agent is added in the synthesis process, is able to suppress precipitating and produces
Reunion between object and intensive.Polyethylene glycol HO (CH2CH2O)nH, polyvinyl alcohol (C2H4O)n, polyglycereol (C3H8O3)nEtc. macromoleculars
Polymerize alcohols and be used as non-ionic dispersing agent, with two kinds of hydrophilic groups of hydroxyl and ehter bond without hydrophobic group, good water solubility, not vulnerable to
The influence of acid, alkali.In aqueous solution, polymeric alcohol molecule is in chain long strip type, is easily formed with presoma precipitation particles surface stronger
Hydrogen bond, while its ehter bond also easily with precipitation particles surface generate affinity interaction, so that it is relatively easily adsorbed in particle surface, from
And one layer of polymeric membrane is formed, wrap up forerunner's precipitation particles.On the other hand, the molecular link of polymeric alcohol chain in the reaction can
It protrudes into the system of complexing agent, makes the package protective film generated that there is certain thickness, presentation space steric effect makes between particle
Attraction greatly weaken, to effectively prevent particle growth, inhibit particle agglomeration.
Relative to aggregate polycrystalline material, monocrystalline nickle cobalt lithium manganate oxide generally requires higher temperature during the sintering process
Degree, to realize the single crystallization of particle, keeps the formation of crystal boundary more stable.Add during the sintering process has fluxing property on a small quantity
The lattices intensified element such as the doped chemicals such as Na, Si, Ba, Sr, F, Cl and Al, Mg, La, Ce, can be anti-with the oxidation and sinter of lithium
Answer middle formation low melting point to promote molten compound, reduce the thermal stress of Crystallization, promote crystal boundary mobile, make crystal growth more evenly,
Completely, it is more likely formed monocrystalline.The addition of fluxing doped chemical, can be formed by making it at a lower temperature by primary of single crystallization
Grain increases monocrystal material primary particle size, improves the stability of material.
Technical scheme is as follows:
Nickel-cobalt lithium manganate cathode material presoma provided by the invention is nickel cobalt manganese hydroxide, and chemical molecular formula is
NixCoyMn1-x-y(OH)2, wherein 0≤x≤1,0≤y≤0.5；The D of the nickel-cobalt lithium manganate cathode material presoma50It is 2~7
μm, specific surface area is 7~30m2/ g, apparent density AD are 0.5~1.0g/cm3, tap density TD is 1.0~2.0 g/cm3。
The preparation method of above-mentioned nickel-cobalt lithium manganate cathode material presoma provided by the invention, comprising the following steps:
(1) nickel salt, cobalt salt, manganese salt are dissolved into the mixing salt solution that concentration is 1~3mol/L by certain mol proportion, by precipitating reagent
It is dissolved into the precipitant solution that concentration is 2~15mol/L, it is molten that complexing agent is dissolved into the complexing agent that concentration is 1~15mol/L
Liquid；Dispersing agent is dissolved into the dispersing aid solution that concentration is 1~200g/L；
(2) above-mentioned mixing salt solution, precipitant solution, enveloping agent solution, dispersant solution are passed through in reaction kettle, in inertia
In, reaction temperature controls between 40~80 DEG C, and complexing agent concentration is 1~15mol/L, and pH value is between 10.0~13.0, instead
It should obtain the spherical nickel cobalt manganese hydroxide of short texture；
(3) it will be dried at the resulting nickel cobalt manganese hydroxide washing of step (2), 105 ~ 130 DEG C, obtain nickle cobalt lithium manganate anode material
Material precursor.
In above-mentioned preparation method, salt-mixture described in step (1) is sulfate, chlorate, nitrate, one in acetate
It plants or in which several；The precipitating reagent is the one or two of NaOH, KOH；The complexing agent is ammonium hydroxide, ethylenediamine tetrem
The one or more of acid disodium, ammonium nitrate, ammonium chloride, ammonium sulfate；The dispersing agent is polyethylene glycol PEG, polyvinyl alcohol
One or more of PVA, polyglycereol.
In above-mentioned preparation method, inert gas described in step (2) includes the one or two of nitrogen, argon gas.
In above-mentioned preparation method, lye described in step (3) is that NaOH, KOH are one such or two kinds.
Nickel-cobalt lithium manganate cathode material provided by the invention is obtained by above-mentioned forerunner's precursor reactant, and chemical molecular formula is
LiaNixCoyMn1-x-yM’zM’’wO2-δRδ, wherein 0.95≤a≤1.25,0≤x≤1,0≤y≤0.5,0≤z≤0.01,0≤w
≤ 0.05,0≤δ≤0.02；M ' is one or more of elements of Al, Mg, La, Ce, Y, Hf, and M ' ' is Al, Si, Sr, Ba, Na, Ca
One or more of elements, one or more of elements of R Cl, F.
The present invention also provides the preparation methods of above-mentioned nickel-cobalt lithium manganate cathode material, comprising the following steps: by above-mentioned nickel
Cobalt manganic acid lithium positive electrode material precursor and lithium salts and the additive mix containing element-specific, in oxygen or air atmosphere
In, it is sintered 4~20h at 700~1200 DEG C, after broken, screening, obtains the monocrystalline nickel-cobalt lithium manganate cathode material.
In method described above, the additive containing element-specific be M ', the oxide of M ' ' element, hydroxide,
The one or more of carbonate, oxalates, nitrate, chloride, fluoride.
In above-mentioned preparation method, the lithium salts is one kind of lithium carbonate, lithium chloride, lithium hydroxide, lithium fluoride, lithium nitrate
Or it is several.
Compared with prior art, the present invention has an advantage that
(1) persursor material of the invention has the characteristics that partial size is small, pattern is loose, density is smaller, specific surface area is larger, uses
The presoma of this special construction easily with lithium salts reaction bonded, can reduce sintering temperature, simplify sintering process, make monocrystalline nickel cobalt
The production efficiency of manganate cathode material for lithium greatly improves.
(2) specific aggregation alcohol is added as dispersion in preparation method of the invention during nickel cobalt manganese coprecipitation reaction
Agent, it is original not changing by adjusting the content, reaction temperature, the pH value of reaction mother liquor of complexing agent in coprecipitation reaction simultaneously
Under conditions of equipment, make obtained little particle presoma that there is loose apparent form, biggish specific surface area, lesser pine
Dress and tap density can form monocrystalline nickel-cobalt lithium manganate cathode material more easily in conjunction with lithium salts during the sintering process.
(3) it is multiple to form low melting point lithium to preparation method of the invention by adding specific fluxing element during the sintering process
Oxide is closed, the thermal stress of crystal growth is reduced, is conducive to the formation of monocrystalline；Sintering temperature is reduced simultaneously, is shortened anti-
Between seasonable, without excessively high sintering temperature and multiple repeated calcination, the primary particle with typical single crystal pattern can be obtained just
Pole material drastically reduces corresponding process costs.
Detailed description of the invention
Fig. 1 is nickel cobalt manganese hydroxide precursor Ni in the embodiment of the present invention 10.5Co0.2Mn0.3(OH)2Scanning electron it is aobvious
Micro mirror (SEM) figure.
Fig. 2 is nickel-cobalt lithium manganate cathode material LiNi in the embodiment of the present invention 10.5Co0.2Mn0.3Sr0.005Mg0.001O2.006's
Scanning electron microscope (SEM) figure.
Fig. 3 is nickel cobalt manganese hydroxide precursor Ni in the embodiment of the present invention 20.63Co0.17Mn0.2(OH)2Scanning electricity
Sub- microscope (SEM) figure.
Fig. 4 is nickel-cobalt lithium manganate cathode material in the embodiment of the present invention 2
LiNi0.63Co0.17Mn0.2Al0.004Ba0.001O2.001Cl0.012Scanning electron microscope (SEM) figure.
Fig. 5 is nickel cobalt manganese hydroxide precursor Ni in the embodiment of the present invention 30.82Co0.09Mn0.09(OH)2Scanning electron
Microscope (SEM) figure.
Fig. 6 is nickel-cobalt lithium manganate cathode material in the embodiment of the present invention 3
LiNi0.82Co0.09Mn0.09Si0.003Ca0.001O2.006F0.002Scanning electron microscope (SEM) figure.
Fig. 7 is nickel cobalt manganese hydroxide precursor Ni in comparative example 1 of the present invention0.5Co0.2Mn0.3(OH)2Scanning electron it is aobvious
Micro mirror (SEM) figure.
Fig. 8 is nickel-cobalt lithium manganate cathode material LiNi in comparative example 1 of the present invention0.5Co0.2Mn0.3O2Scanning electron microscopy
Mirror (SEM) figure.
Fig. 9 is nickel-cobalt lithium manganate cathode material LiNi in comparative example 2 of the present invention0.5Co0.2Mn0.3O2Scanning electron microscopy
Mirror (SEM) figure.
Figure 10 is nickel-cobalt lithium manganate cathode material LiNi in comparative example 3 of the present invention0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006
Scanning electron microscope (SEM) figure.
Figure 11 is embodiment 1 and material button cell cycle performance figure in comparative example 1, comparative example 2, comparative example 3.
Specific embodiment
The production of button cell:
Firstly, by the compound nickel-cobalt-manganese multi positive active material of non-aqueous electrolyte secondary battery, acetylene black and gathering inclined difluoro
Ethylene (PVDF) is mixed according to mass ratio 95%:2.5%:2.5%, coated on aluminium foil and drying and processing is carried out, uses 100MPa
Pressure punch forming be diameter 12mm, thick 120 μm of anode pole piece, then anode pole piece is put into 120 in vacuum drying box
DEG C drying 12h.
Cathode is 17mm using diameter, with a thickness of the Li sheet metal of 1mm；The polyethylene porous that diaphragm uses with a thickness of 25 μm
Film；Electrolyte uses the LiPF6 of 1mol/L, the equivalent mixed liquor of ethylene carbonate (EC) and diethyl carbonate (DEC).
Anode pole piece, diaphragm, cathode pole piece and electrolyte are respectively less than to the Ar gas gloves of 5ppm in water content and oxygen content
2025 type button cells are assembled into case, using battery at this time as unactivated battery.
The performance evaluation of button cell about production is such as given a definition:
2h is placed after production button cell, after open-circuit voltage is stablized, the mode that the current density to anode is 0.1C, which charges to, is cut
Only voltage 4.3V, then constant-voltage charge 30min, are then discharged to blanking voltage 3.0V with same current density；By same side
Formula carries out 1 time again, using battery at this time as active cell.
Cycle performance test is as follows: use active cell, with the current density of 1C 3.0~4.5V voltage range,
At a temperature of 45 DEG C, the high temperature capacity retention ratio of 80 investigation materials is recycled.
Embodiment 1
Prepare the nickel cobalt mn sulphate mixed solution (molar ratio Ni:Co:Mn=50:20:30) of 1.5mol/L, the NaOH of 3mol/L
Above-mentioned several solns are passed through instead by solution, the ammonium hydroxide of 3mol/L, the PEG1000 aqueous dispersant of 10g/L in manner of cocurrent flow
It answers in kettle, keeping reaction temperature is 50 DEG C, pH value in reaction 12.0, under nitrogen protection atmosphere, washed, 120 DEG C of drying, mistakes
Sieve, obtains the little particle nickel cobalt manganese hydroxide precursor Ni of loose pattern0.5Co0.2Mn0.3(OH)2.As shown in Figure 1, the nickel cobalt
Manganese hydroxide is in the intensive stacked of small plate, and density is low, large specific surface area；Test result D50It is 5.5 μm, DmaxFor 14.47 μ
M, specific surface area 12.92m2/ g, apparent density AD are 0.86g/cm3, tap density TD is 1.65 g/cm3。
By gained nickel-cobalt lithium manganate cathode material presoma, lithium carbonate, strontium carbonate, magnesia, according to Li/ (Ni+Co+
Mn)/Sr/Mg=1.03:1:0.005:0.001 ratio, 950 DEG C of roasting 14h in high-speed mixer and mixing, air atmosphere are natural
It cools, after broken, sieving, obtains monocrystalline type doping nickel-cobalt lithium manganate cathode material
LiNi0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006.As shown in Fig. 2, the nickel-cobalt lithium manganate cathode material is the single crystal grain of standard
Pattern, it is mutually indepedent between particle, second particle is not constituted, specific surface area is small, and density is high；Test the nickle cobalt lithium manganate anode material
Expect D50For 6.90mm, specific surface area 0.48m2/ g, tap density TD are 2.54g/cm3, 3.88 g/cm of pole piece compaction density3。
Under 4.3V voltage, the discharge capacity for the first time (0.2C) of positive electrode is 165.3mAh/g.
Embodiment 2
Prepare the nickel cobalt nitric acid hydrochlorate mixed solution (molar ratio Ni:Co:Mn=63:17:20) of 1.8mol/L, the NaOH of 5mol/L
Above-mentioned several solns are passed through instead by solution, the ammonium hydroxide of 5mol/L, the polyvinyl alcohol aqueous dispersant of 5g/L in manner of cocurrent flow
It answers in kettle, setting reaction temperature is 55 DEG C, pH value 12.5, is precipitated in the case where argon gas protects atmosphere, washed, 115 DEG C of drying, mistakes
Sieve, obtains the little particle nickel-cobalt lithium manganate cathode material presoma Ni of loose pattern0.63Co0.17Mn0.2(OH)2；As shown in figure 3,
The nickel cobalt manganese hydroxide is in the intensive stacked of small plate, and similar to 1 pattern of embodiment, granularity is smaller；Test the nickel cobalt manganese hydrogen
The D of oxide50It is 4.26 μm, DmaxIt is 12.19 μm, specific surface area 18.75m2/ g, apparent density AD are 0.82g/cm3, vibration
Real density TD is 1.63 g/cm3。
By gained nickel cobalt manganese hydroxide precursor, lithium nitrate, aluminium chloride, barium carbonate, according to Li/ (Ni+Co+Mn)/Al/
The ratio of Ba=1.04:1:0.004:0.001,900 DEG C of roasting 14h in high-speed mixer and mixing, air atmosphere, natural cooling drop
Temperature obtains monocrystalline type doping nickel-cobalt lithium manganate cathode material after broken, sieving
LiNi0.63Co0.17Mn0.2Al0.004Ba0.001O2.001Cl0.012.As shown in figure 4, the nickel-cobalt lithium manganate cathode material is the list of standard
Brilliant granule-morphology, similar to 1 pattern of embodiment, granularity is smaller；Test nickel-cobalt lithium manganate cathode material D50For 5.2mm, compare table
Area is 0.52m2/ g, tap density TD are 2.43g/cm3, pole piece compaction density 3.82g/cm3.Under 4.3V voltage, positive electrode
Discharge capacity for the first time (0.2C) be 176.8mAh/g.
Embodiment 3
The nickel cobalt mn sulphate mixed solution (molar ratio Ni:Co:Mn=82:9:9) of preparation 2mol/L, the NaOH solution of 8mol/L,
Above-mentioned several solns are passed through reaction kettle by the ammonium hydroxide of 8mol/L, the polyglycereol aqueous dispersant of 20g/L in manner of cocurrent flow
In, setting reaction temperature is 60 DEG C, pH value 12.8, sink to forming sediment in nitrogen protection atmosphere, washed, 115 DEG C of drying, sieving,
Obtain the little particle nickel-cobalt lithium manganate cathode material presoma Ni of loose pattern0.82Co0.09Mn0.09(OH)2.As shown in figure 5, should
Nickel cobalt manganese hydroxide is in the intensive stacked of fritter, and particle is smaller, D similar to 1 pattern of embodiment50It is 3.98 μm, DmaxFor
9.93 μm, specific surface area 21.28m2/ g, apparent density AD are 0.80g/cm3, tap density TD is 1.51 g/cm3。
By gained nickel cobalt manganese hydroxide precursor, lithium hydroxide, silica, calcirm-fluoride, according to Li/ (Ni+Co+
Mn)/Si/Ca/=1.05:1:0.003:0.001 ratio, 800 DEG C of roasting 10h in high-speed mixer and mixing, oxygen atmosphere, from
It so cools, after broken, sieving, obtains monocrystalline type doping nickel-cobalt lithium manganate cathode material
LiNi0.82Co0.09Mn0.09Si0.003Ca0.001O2.006F0.002.As shown in fig. 6, the nickel-cobalt lithium manganate cathode material is the list of standard
Brilliant granule-morphology, mutual adhesion between particle are similar to 1 pattern of embodiment；Test nickel-cobalt lithium manganate cathode material D50For
4.40mm, specific surface area 0.62m2/ g, tap density TD are 2.36g/cm3, 3.75 g/cm of pole piece compaction density3.4.3V electric
Pressure, the discharge capacity for the first time (0.2C) of positive electrode are 201.6mAh/g.
Comparative example 1
Prepare the nickel cobalt mn sulphate mixed solution (molar ratio Ni:Co:Mn=50:20:30) of 1.5mol/L, the NaOH of 2mol/L
Above-mentioned several solns are passed through in reaction kettle by solution, the ammonium hydroxide of 1mol/L in manner of cocurrent flow, and keeping reaction temperature is 50 DEG C,
PH value in reaction 11.0 sinks to forming sediment in nitrogen protection atmosphere, washed, 120 DEG C of drying, sieving, before obtaining nickel cobalt manganese hydroxide
Drive body Ni0.5Co0.2Mn0.3(OH)2.As shown in fig. 7, the nickel cobalt manganese hydroxide particles are smaller, pattern is fine and close, and density is larger；It surveys
Test result D50It is 3.91 μm, DmaxIt is 10.94 μm, specific surface area 6.55m2/ g, apparent density AD are 1.20g/cm3, vibration density
Degree TD is 2.09 g/cm3。
By lithium carbonate and obtained nickel cobalt manganese hydroxide precursor Ni0.5Co0.2Mn0.3(OH)2According to Li/ (Ni+Co+
Mn)=1.03:1 ratio, 950 DEG C of roasting 14h in high-speed mixer and mixing, air atmosphere, natural cooling cooling, through broken, mistake
After sieve, LiNi is obtained0.5Co0.2Mn0.3Finished product.As shown in figure 8, the nickel-cobalt lithium manganate cathode material is polycrystalline little particle pattern, D50
For 4.5mm, specific surface area 0.76m2/ g, tap density TD are 2.26g/cm3, 3.10 g/cm of pole piece compaction density3.4.3V electric
Pressure, the discharge capacity for the first time (0.2C) of positive electrode are 164.5mAh/g.
Comparative example 2
Use nickel cobalt manganese hydroxide precursor Ni same as Example 10.5Co0.2Mn0.3(OH)2, by lithium carbonate and its according to
Li/ (Ni+Co+Mn)=1.03:1 ratio, 950 DEG C of roasting 14h in high-speed mixer and mixing, air atmosphere, natural cooling drop
Temperature obtains LiNi after broken, sieving0.5Co0.2Mn0.3O2Finished product.As shown in figure 9, the nickel-cobalt lithium manganate cathode material is class
Single crystal grain pattern tests nickel-cobalt lithium manganate cathode material D50For 6.5mm, specific surface area 0.56m2/ g, tap density TD
For 2.31g/cm3；3.27 g/cm of pole piece compaction density3.Under 4.3V voltage, the discharge capacity for the first time (0.2C) of positive electrode is
164.7mAh/g。
Comparative example 3
Use nickel cobalt manganese hydroxide precursor Ni identical with comparative example 10.5Co0.2Mn0.3(OH)2, by lithium carbonate and its according to
Li/ (Ni+Co+Mn)/Sr/Mg=1.03:1:0.005:0.001 ratio, 950 DEG C in high-speed mixer and mixing, air atmosphere
14h is roasted, natural cooling cooling obtains LiNi after broken, sieving0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006Finished product.Such as figure
Shown in 5, which is polycrystalline little particle pattern, D50For 5.7mm, specific surface area 0.73m2/ g, jolt ramming
Density T D is 1.88g/cm3, 3.35 g/cm of pole piece compaction density3.Under 4.3V voltage, the discharge capacity for the first time of positive electrode
(0.2C) is 165.1mAh/g.
It can be seen that polymeric alcohol dispersing agent by comparing embodiment 1 and 1,2,3 presoma of comparative example and positive electrode Electronic Speculum pattern
Addition play a significant role to multiple indexs such as presoma pattern, density and specific surface area, and it is specific fluxing in sintering process
The addition of effect doped chemical then plays an important role the formation of monocrystalline nickel-cobalt lithium manganate cathode material.
Monocrystalline nickel-cobalt lithium manganate cathode material embodiment 1 compares the comparative example 1,2,3 of on-monocrystalline pattern, and granule strength is more
By force, there is higher pole piece compaction density.As can be seen that using the loose shape for thering is dispersing agent to synthesize from the circulation comparison of Figure 11
Looks presoma and specific obtained monocrystalline nickel-cobalt lithium manganate cathode material is sintered with fluxing action doped chemical has most
Excellent cycle performance, capacity retention ratio is 98% or so after recycling within 80 weeks.It is not added with doped chemical under the same terms and does not disperse
1,2,3 cycle life of comparative example that sample is added in agent is significantly lower than embodiment 1, and downward trend is obvious.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, and it is any
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by those familiar with the art, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection scope of claims
It is quasi-.
Claims (9)
1. a kind of preparation method of nickel-cobalt lithium manganate cathode material presoma, which comprises the following steps:
(1) nickel salt, cobalt salt, manganese salt are dissolved into the mixing salt solution that concentration is 1~3mol/L by certain mol proportion, by precipitating reagent
It is dissolved into the precipitant solution that concentration is 2~15mol/L, it is molten that complexing agent is dissolved into the complexing agent that concentration is 1~15mol/L
Liquid；Dispersing agent is dissolved into the dispersing aid solution that concentration is 1~200g/L；
(2) above-mentioned mixing salt solution, precipitant solution, enveloping agent solution, dispersant solution are passed through in reaction kettle, in inertia
In, reaction temperature controls between 40~80 DEG C, and complexing agent concentration is 1~15mol/L, and pH value is between 10.0~13.0, instead
It should obtain the spherical nickel cobalt manganese hydroxide of short texture；
(3) it will be dried at the resulting nickel cobalt manganese hydroxide washing of step (2), 105 ~ 130 DEG C, obtain nickle cobalt lithium manganate anode material
Material precursor；
Above-mentioned nickel-cobalt lithium manganate cathode material presoma chemical molecular formula is NixCoyMn1-x-y(OH)2, wherein 0≤x≤1,0≤y
≤0.5；The D of the nickel-cobalt lithium manganate cathode material presoma50It is 2~7 μm, specific surface area is 7~30m2/ g, apparent density AD
For 0.5~1.0g/cm3, tap density TD is 1.0~2.0 g/cm3。
2. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to claim 1, which is characterized in that step
(1) salt-mixture described in is one of sulfate, chlorate, nitrate, acetate or in which several；The precipitating reagent is
The one or two of NaOH, KOH；The complexing agent is ammonium hydroxide, disodium ethylene diamine tetraacetate, ammonium nitrate, ammonium chloride, ammonium sulfate
One or more.
3. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to claim 1, which is characterized in that step
(1) dispersing agent described in is one or more of polyethylene glycol PEG, PVAC polyvinylalcohol, polyglycereol.
4. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to claim 1, which is characterized in that step
(2) inert gas described in includes the one or two of nitrogen, argon gas.
5. the preparation method of nickel-cobalt lithium manganate cathode material presoma according to claim 1, which is characterized in that step
(3) lye described in is NaOH, KOH one such or two kinds.
6. a kind of nickel-cobalt lithium manganate cathode material, it is characterised in that before nickel-cobalt lithium manganate cathode material described in claim 1
It drives precursor reactant to obtain, chemical molecular formula LiaNixCoyMn1-x-yM’zM’’wO2-δRδ, wherein 0.95≤a≤1.25,0≤x≤
1,0≤y≤0.5,0≤z≤0.01,0≤w≤0.05,0≤δ≤0.02；M ' is the one or more of Al, Mg, La, Ce, Y, Hf
Element, M ' ' are one or more of elements of Al, Si, Sr, Ba, Na, Ca, one or more of elements of R Cl, F.
7. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 6, which is characterized in that including following step
It is rapid: by additive mix of the above-mentioned nickel-cobalt lithium manganate cathode material presoma with lithium salts and containing element-specific, in oxygen
Or in air atmosphere, it is sintered 4~20h at 700~1200 DEG C, after broken, screening, obtains the monocrystalline nickle cobalt lithium manganate
Polynary positive pole material.
8. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 6, which is characterized in that described containing specific
The additive of element is M ', the oxide of M ' ' element, hydroxide, carbonate, oxalates, nitrate, chloride, fluoride
One or more.
9. the preparation method of nickel-cobalt lithium manganate cathode material according to claim 6, which is characterized in that the lithium salts is
The one or more of lithium carbonate, lithium chloride, lithium hydroxide, lithium fluoride, lithium nitrate.
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| CN113764658B (en) * | 2021-08-31 | 2024-04-16 | 中南大学 | Anion-cation co-doped high-nickel monocrystal ternary cathode material, and preparation method and application thereof |
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