CN109461925B - Single crystal nickel cobalt lithium manganate positive electrode material, precursor and preparation method thereof - Google Patents
Single crystal nickel cobalt lithium manganate positive electrode material, precursor and preparation method thereof Download PDFInfo
- Publication number
- CN109461925B CN109461925B CN201810713401.XA CN201810713401A CN109461925B CN 109461925 B CN109461925 B CN 109461925B CN 201810713401 A CN201810713401 A CN 201810713401A CN 109461925 B CN109461925 B CN 109461925B
- Authority
- CN
- China
- Prior art keywords
- equal
- lithium
- positive electrode
- electrode material
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 51
- 239000002243 precursor Substances 0.000 title claims abstract description 50
- 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 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013078 crystal Substances 0.000 title abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 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 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 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 21
- 239000000243 solution Substances 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 10
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [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
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 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
- 229910052749 magnesium Inorganic materials 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
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 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
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 229910052727 yttrium 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 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 description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910003618 NixCoyMn1-x-y(OH)2 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
- 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 39
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 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 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000007873 sieving Methods 0.000 description 9
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 8
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method 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
- 229910013716 LiNi Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910012653 LiNi0.5Co0.2Mn0.3 Inorganic materials 0.000 description 3
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 3
- 229910006025 NiCoMn Inorganic materials 0.000 description 3
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000001376 precipitating effect Effects 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
- 239000002033 PVDF binder Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- WJNPTRISSCIBDB-UHFFFAOYSA-N cobalt(2+) nickel(2+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Co+2].[Ni+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WJNPTRISSCIBDB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000010413 mother solution 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
- 239000008188 pellet Substances 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
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 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
Images
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 invention discloses a monocrystal nickel cobalt lithium manganate positive electrode material, a precursor and a preparation method thereof, wherein the molecular formula of the positive electrode material is LiaNixCoyMn1‑x‑yM’zM’’wO2‑δRδ(a is more than or equal to 0.95 and less than or equal to 1.25, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.01, w is more than or equal to 0 and less than or equal to 0.05, and delta is more than or equal to 0 and less than or equal to 0.02). According to the method, a nickel-cobalt-manganese hydroxide precursor with small particles, loose appearance, small density and large specific surface area is obtained by adding a dispersing agent and controlling the content of a coprecipitation reaction complexing agent, the synthesis pH value and the reaction temperature. The precursor, lithium salt and a specific fluxing element additive are mixed and sintered to obtain the nickel cobalt lithium manganate anode material with a typical single crystal morphology. The invention has simple process and easy process control, and does not need to reform or add the original equipment; the obtained precursor is easy to react and combine with lithium salt, the sintering temperature is reduced, the sintering process is simplified, and the production efficiency is greatly improved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a single crystal doped multi-component nickel cobalt lithium manganate positive electrode material, a precursor and a preparation method thereof.
Background
The lithium ion battery is a green high-energy battery, has the outstanding advantages of high voltage, large energy density, good cycle performance, small self-discharge, no memory effect and the like, is widely applied to various portable electric tools, electronic instruments, mobile phones, notebook computers, video cameras, weaponry and the like, and is also widely used in the fields of electric automobiles and various energy storage.
The positive electrode material is one of the important components of the lithium ion battery, and the quality of the positive electrode material directly determines the performance of the lithium ion battery. The ternary nickel cobalt lithium manganate has higher capacity, excellent cycle and rate performance, and gradually becomes a hotspot of research and application of lithium ion battery anode materials in recent years. Among them, the ternary material is increasingly used in power batteries and high voltage batteries. The conventional ternary agglomerate type secondary polycrystalline particle positive electrode material has low powder compaction density, is easy to generate gas expansion at high temperature, and has poor high-temperature circulation and high-voltage test performance. Therefore, a single-crystal small-particle nickel cobalt lithium manganate material is needed as a positive electrode to improve high-temperature performance, inhibit high-temperature gas generation and improve the compaction density of the positive electrode material.
Compared with the existing mature process for preparing the agglomerate type secondary polycrystalline particles, the synthesis and preparation of the single crystal type ternary nickel cobalt lithium manganate cathode material have higher realization difficulty and are mainly reflected in the aspects of synthesis of precursors with special shapes and sizes and doping of auxiliary agent elements in the sintering process. At present, the number of patents related to single crystal type ternary cathode materials is small, most of the key contents of the patents mainly focus on the aspects of sintering mode, sintering temperature, particle crushing and the like in the preparation process of single crystal lithium nickel cobalt manganese oxide compounds, and detailed description on the types of used precursors and research on doping and fluxing elements in the sintering process is still lacked. The chinese patent with application number CN201610739897.9 uses a conventional nickel-cobalt-manganese hydroxide precursor, and adopts up to 5 stages of sintering process to prepare the single crystal anode material, the process flow is complex, the conditions are strict and not easy to control, and the cost is high. The method for preparing the single crystal cathode material in the Chinese patent with the application number of CN201611037434.4 is to crush a large-particle precursor into small fragments, and then mix and sinter the small fragments with a metal element additive and a lithium source. After the large-particle spherical precursor is forcedly physically crushed into small particles, a plurality of indexes such as the shape, the density and the like of the material can be influenced in different degrees, and the sintering of the final anode material is not facilitated.
The quality of the performance index of the precursor directly determines the quality of the performance of the anode material, so that the nickel-cobalt-manganese hydroxide is important for the performance of the nickel-cobalt-manganese ternary anode material. In view of the particularity of the single crystal material relative to the conventional polycrystalline material, it is necessary to prepare a small-particle nickel-cobalt-manganese hydroxide with a specific morphology as a precursor, and obtain a primary-particle cathode material with a single crystal morphology through high-temperature primary sintering.
Disclosure of Invention
In order to achieve the purpose, the invention aims to provide a nickel cobalt manganese acid lithium positive electrode material precursor, and a small-particle doped multi-element positive electrode material which is high in specific capacity, excellent in cycle performance and typical in single crystal morphology is obtained by controlling the synthesis of a nickel cobalt manganese hydroxide precursor and adding a specific doping element in a sintering process.
The invention also provides a preparation method of the nickel-cobalt-manganese hydroxide and the doped single crystal nickel-cobalt-lithium manganate. Research and development find that in order to prepare a precursor with small particles, large specific surface area, looseness and low density, good dispersibility among the particles needs to be ensured in the coprecipitation process, and the particles cannot be excessively agglomerated and stacked. A certain amount of dispersant is added in the synthesis process, so that agglomeration and compaction among precipitation products can be inhibited. Polyethylene glycol HO (CH)2CH2O)nH. Polyvinyl alcohol (C)2H4O)nPolyglycerol (C)3H8O3)nMacromolecular polymeric alcohols are used as nonionic dispersants, have two hydrophilic groups of hydroxyl and ether bonds without hydrophobic groups, have good water solubility and are not easily affected by acid and alkali. In an aqueous solution, the polymer alcohol molecules are in a chain-shaped long strip shape, and are easy to form strong hydrogen bonds with the surfaces of precursor precipitate particles, and the ether bonds of the polymer alcohol molecules are also easy to generate affinity action with the surfaces of the precipitate particles, so that the polymer alcohol molecules are easily adsorbed on the surfaces of the particles, thereby forming a layer of polymer film to wrap the precursor precipitate particles. On the other hand, the polymeric alcohol chain type molecular bond can extend into a complexing agent system in the reaction, so that the generated coating protective film has a certain thickness, a steric hindrance effect is presented, and the attraction among particles is greatly weakened, thereby effectively preventing the particle growth and inhibiting the particle agglomeration.
Compared with an aggregate polycrystalline material, the single crystal nickel cobalt lithium manganate oxide usually needs higher temperature in the sintering process to realize single crystallization of particles and enable the formation of grain boundaries to be more stable. A small amount of doping elements such as Na, Si, Ba, Sr, F, Cl and the like with fluxing property and lattice strengthening elements such as Al, Mg, La, Ce and the like are added in the sintering process, so that a low-melting-point melting promoting compound can be formed in the oxidation sintering reaction with lithium, the thermal stress formed by crystals is reduced, the movement of crystal boundaries is promoted, the crystal growth is more uniform and complete, and single crystals are more easily formed. The addition of fluxing doping elements enables the single-crystallized primary particles to be formed at a lower temperature, the size of the primary particles of the single-crystal material is increased, and the stability of the material is improved.
The technical scheme of the invention is as follows:
the precursor of the nickel cobalt lithium manganate positive electrode material provided by the invention is nickel cobalt manganese hydroxide, and the chemical molecular formula is NixCoyMn1-x-y(OH)2Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.5; d of precursor of nickel cobalt lithium manganate positive electrode material502 to 7 μm, and a specific surface area of 7 to 30m2(g), the apparent density AD is 0.5-1.0 g/cm3The tap density TD is 1.0-2.0 g/cm3。
The preparation method of the precursor of the nickel cobalt lithium manganate positive electrode material provided by the invention comprises the following steps:
(1) dissolving nickel salt, cobalt salt and manganese salt into a mixed salt solution with the concentration of 1-3 mol/L according to a certain molar ratio, dissolving a precipitator into a precipitator solution with the concentration of 2-15 mol/L, and dissolving a complexing agent into a complexing agent solution with the concentration of 1-15 mol/L; dissolving a dispersing agent into a dispersing aid solution with the concentration of 1-200 g/L;
(2) introducing the mixed salt solution, the precipitant solution, the complexing agent solution and the dispersing agent solution into a reaction kettle, controlling the reaction temperature to be 40-80 ℃ in an inert atmosphere, controlling the concentration of the complexing agent to be 1-15 mol/L and controlling the pH value to be 10.0-13.0, and reacting to obtain spherical nickel-cobalt-manganese hydroxide with a loose structure;
(3) and (3) washing the nickel-cobalt-manganese hydroxide obtained in the step (2), and drying at 105-130 ℃ to obtain a precursor of the nickel-cobalt-manganese acid lithium positive electrode material.
In the preparation method, the mixed salt in the step (1) is one or more of sulfate, chloride, nitrate and acetate; the precipitator is one or two of NaOH and KOH; the complexing agent is one or more of ammonia water, disodium ethylene diamine tetraacetate, ammonium nitrate, ammonium chloride and ammonium sulfate; the dispersing agent is one or more of polyethylene glycol (PEG), polyvinyl alcohol (PVA) and polyglycerol.
In the preparation method, the inert gas in the step (2) comprises one or two of nitrogen and argon.
In the preparation method, the alkali liquor in the step (3) is one or two of NaOH and KOH.
The nickel cobalt lithium manganate positive electrode material provided by the invention is obtained by the reaction of the precursor, and the chemical molecular formula of the nickel cobalt lithium manganate positive electrode material is LiaNixCoyMn1-x-yM’zM’’wO2-δRδWherein a is more than or equal to 0.95 and less than or equal to 1.25, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.01, w is more than or equal to 0 and less than or equal to 0.05, and delta is more than or equal to 0 and less than or equal to 0.02; m ' is one or more elements of Al, Mg, La, Ce, Y and Hf, M ' ' is one or more elements of Al, Si, Sr, Ba, Na and Ca, and R is one or more elements of Cl and F.
The invention also provides a preparation method of the nickel cobalt lithium manganate positive electrode material, which comprises the following steps: and mixing the precursor of the nickel cobalt lithium manganate positive electrode material with lithium salt and an additive containing a specific element, sintering for 4-20 hours at 700-1200 ℃ in an oxygen or air atmosphere, and crushing and screening to obtain the single crystal nickel cobalt lithium manganate positive electrode material.
In the method, the additive containing the specific element is one or more of oxides, hydroxides, carbonates, oxalates, nitrates, chlorides and fluorides of M ' and M ' ' elements.
In the preparation method, the lithium salt is one or more of lithium carbonate, lithium chloride, lithium hydroxide, lithium fluoride and lithium nitrate.
Compared with the prior art, the invention has the following advantages:
(1) the precursor material has the characteristics of small particle size, loose appearance, small density and large specific surface area, and the precursor with the special structure is easy to react and combine with lithium salt, so that the sintering temperature can be reduced, the sintering process is simplified, and the production efficiency of the single crystal nickel cobalt lithium manganate cathode material is greatly improved.
(2) According to the preparation method, specific polyalcohol is added as a dispersing agent in the process of nickel cobalt manganese coprecipitation reaction, and the content of a complexing agent, the reaction temperature and the pH value of a reaction mother solution in the coprecipitation reaction are simultaneously adjusted, so that the prepared small-particle precursor has loose appearance, larger specific surface area, smaller apparent density and tap density without changing the original equipment, and can be more easily combined with lithium salt in the sintering process to form the single-crystal nickel cobalt lithium manganate anode material.
(3) According to the preparation method, the specific fluxing element is added in the sintering process to form the low-melting-point lithium composite oxide, so that the thermal stress of crystal growth is reduced, and the formation of single crystals is facilitated; meanwhile, the sintering temperature is reduced, the reaction time is shortened, the primary particle anode material with typical single crystal morphology can be obtained without overhigh sintering temperature and repeated roasting, and the corresponding process cost is greatly reduced.
Drawings
FIG. 1 shows Ni as a precursor of Ni-Co-Mn hydroxide in example 1 of the present invention0.5Co0.2Mn0.3(OH)2Scanning Electron Microscope (SEM) images of (a).
FIG. 2 shows LiNi as the positive electrode material of NiCoMn in example 1 of the present invention0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006Scanning Electron Microscope (SEM) images of (a).
FIG. 3 shows Ni as a precursor of Ni-Co-Mn hydroxide in example 2 of the present invention0.63Co0.17Mn0.2(OH)2Scanning Electron Microscope (SEM) images of (a).
FIG. 4 shows LiNi as the positive electrode material of NiCoMn in example 2 of the present invention0.63Co0.17Mn0.2Al0.004Ba0.001O2.001Cl0.012Scanning Electron Microscope (SEM) images of (a).
FIG. 5 shows Ni as a precursor of Ni-Co-Mn hydroxide in example 3 of the present invention0.82Co0.09Mn0.09(OH)2Scanning Electron Microscope (SEM) images of (a).
FIG. 6 shows an embodiment of the present inventionLiNi as positive electrode material of Ni-Co-Mn acid lithium in example 30.82Co0.09Mn0.09Si0.003Ca0.001O2.00 6F0.002Scanning Electron Microscope (SEM) images of (a).
FIG. 7 shows Ni as a precursor of Ni-Co-Mn hydroxide in comparative example 1 of the present invention0.5Co0.2Mn0.3(OH)2Scanning Electron Microscope (SEM) images of (a).
FIG. 8 shows LiNi as a positive electrode material of nickel cobalt lithium manganate in comparative example 1 of the present invention0.5Co0.2Mn0.3O2Scanning Electron Microscope (SEM) images of (a).
FIG. 9 shows LiNi as a positive electrode material of nickel cobalt lithium manganate in comparative example 2 of the present invention0.5Co0.2Mn0.3O2Scanning Electron Microscope (SEM) images of (a).
FIG. 10 shows LiNi as a positive electrode material of nickel cobalt lithium manganate in comparative example 3 of the present invention0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006Scanning Electron Microscope (SEM) images of (a).
Fig. 11 is a graph of the cycling performance of the button cell of the materials in example 1 and comparative examples 1, 2 and 3.
Detailed Description
Manufacturing the button cell:
firstly, mixing a composite nickel-cobalt-manganese multi-element positive electrode active substance, acetylene black and polyvinylidene fluoride (PVDF) for a non-aqueous electrolyte secondary battery according to a mass ratio of 95: 2.5%, coating the mixture on an aluminum foil, drying the mixture, performing press forming by using 100MPa pressure to form a positive electrode piece with the diameter of 12mm and the thickness of 120 mu m, and then putting the positive electrode piece into a vacuum drying box to dry for 12 hours at 120 ℃.
The negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film having a thickness of 25 μm; the electrolyte solution used was a mixture of 1mol/L of LiPF6, Ethylene Carbonate (EC) and diethyl carbonate (DEC).
Assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5ppm, and taking the cell as an unactivated cell.
The performance evaluation on the button cells made is defined as follows:
placing for 2h after manufacturing the button cell, after the open-circuit voltage is stable, charging the anode to cut-off voltage of 4.3V in a mode that the current density of the anode is 0.1C, then charging for 30min at constant voltage, and then discharging to cut-off voltage of 3.0V at the same current density; the same procedure was repeated 1 more time, and the battery at this time was regarded as an activated battery.
The cycle performance was tested as follows: the high-temperature capacity retention rate of the material is inspected by using an activated battery and circulating for 80 times at the temperature of 45 ℃ in a voltage range of 3.0-4.5V at the current density of 1C.
Example 1
Preparing 1.5mol/L nickel-cobalt-manganese sulfate mixed solution (the mol ratio of Ni: Co: Mn = 50: 20: 30), 3mol/L NaOH solution, 3mol/L ammonia water and 10g/L PEG1000 dispersant aqueous solution, introducing the solutions into a reaction kettle in a parallel flow mode, keeping the reaction temperature at 50 ℃, the reaction pH value at 12.0, washing, drying at 120 ℃ and sieving in a nitrogen protection atmosphere to obtain loose-morphology small-particle nickel-cobalt-manganese hydroxide precursor Ni0.5Co0.2Mn0.3(OH)2. As shown in fig. 1, the nickel-cobalt-manganese hydroxide is in a small plate densely stacked state, and has low density and large specific surface area; test result D505.5 μm, Dmax14.47 μm, a specific surface area of 12.92m2(g), apparent Density AD is 0.86g/cm3The tap density TD is 1.65 g/cm3。
Mixing the obtained precursor of the nickel cobalt lithium manganate positive electrode material, lithium carbonate, strontium carbonate and magnesium oxide in a high-speed mixer according to the proportion of Li/(Ni + Co + Mn)/Sr/Mg =1.03:1:0.005:0.001, roasting for 14h at 950 ℃ in the air atmosphere, naturally cooling, crushing and sieving to obtain the single-crystal doped nickel cobalt lithium manganate positive electrode material LiNi0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006. As shown in figure 2, the nickel cobalt lithium manganate positive electrode material is in a standard single crystal particle shape, and particles are mutually distributedIndependent, does not form secondary particles, and has small specific surface area and high density; testing the nickel cobalt lithium manganate cathode material D50Is 6.90mm, and the specific surface area is 0.48m2(ii)/g, tap density TD of 2.54g/cm3The compacted density of the pole piece is 3.88 g/cm3. The first discharge capacity (0.2C) of the positive electrode material at a voltage of 4.3V was 165.3 mAh/g.
Example 2
Preparing 1.8mol/L nickel cobalt nitrate mixed solution (the mol ratio of Ni: Co: Mn = 63: 17: 20), 5mol/L NaOH solution, 5mol/L ammonia water and 5g/L polyvinyl alcohol dispersant aqueous solution, introducing the solutions into a reaction kettle in a parallel flow mode, setting the reaction temperature to be 55 ℃, setting the pH value to be 12.5, precipitating in an argon protective atmosphere, washing, drying at 115 ℃, and sieving to obtain a loose-morphology small-particle nickel cobalt lithium manganate positive electrode material precursor Ni0.63Co0.17Mn0.2(OH)2(ii) a As shown in fig. 3, the nickel cobalt manganese hydroxide is in a small plate densely stacked shape, similar to the shape of example 1, and has a slightly smaller particle size; d testing the Nickel cobalt manganese hydroxide50Is 4.26 μm, Dmax12.19 μm and a specific surface area of 18.75m2(g), apparent Density AD is 0.82g/cm3The tap density TD is 1.63 g/cm3。
Mixing the obtained nickel-cobalt-manganese hydroxide precursor, lithium nitrate, aluminum chloride and barium carbonate in a high-speed mixer according to the proportion of Li/(Ni + Co + Mn)/Al/Ba =1.04:1:0.004:0.001, roasting for 14h at 900 ℃ in the air atmosphere, naturally cooling, crushing and sieving to obtain a single-crystal doped nickel-cobalt-lithium manganate anode material LiNi0.63Co0.17Mn0.2Al0.004Ba0.00 1O2.001Cl0.012. As shown in fig. 4, the lithium nickel cobalt manganese oxide cathode material has a standard single crystal particle morphology, which is similar to that of example 1, and the particle size is slightly smaller; testing the nickel cobalt lithium manganate cathode material D50Is 5.2mm, and has a specific surface area of 0.52m2(ii)/g, tap density TD of 2.43g/cm3The compacted density of the pole piece is 3.82g/cm3. The first discharge capacity (0.2C) of the positive electrode material at 4.3V was 176.8 mAh/g.
Example 3
Preparing 2mol/L nickel cobalt manganese sulfate mixed solution (the mol ratio of Ni: Co: Mn = 82: 9: 9), 8mol/L NaOH solution, 8mol/L ammonia water and 20g/L polyglycerol dispersant aqueous solution, introducing the solutions into a reaction kettle in a parallel flow mode, setting the reaction temperature at 60 ℃ and the pH value at 12.8, precipitating in a nitrogen protection atmosphere, washing, drying at 115 ℃, and sieving to obtain loose-morphology small-particle nickel cobalt lithium manganate anode material precursor Ni0.82Co0.09Mn0.09(OH)2. As shown in FIG. 5, the NiCoMn hydroxide is in the form of small densely packed pellets with smaller particles, similar to the morphology of example 1, D50Is 3.98 μm, Dmax9.93 μm, a specific surface area of 21.28m2(g), apparent Density AD is 0.80g/cm3The tap density TD is 1.51 g/cm3。
Mixing the obtained nickel-cobalt-manganese hydroxide precursor, lithium hydroxide, silicon dioxide and calcium fluoride in a high-speed mixer according to the proportion of Li/(Ni + Co + Mn)/Si/Ca/=1.05:1:0.003:0.001, roasting for 10 hours at 800 ℃ in an oxygen atmosphere, naturally cooling, crushing and sieving to obtain a single-crystal doped nickel-cobalt-lithium manganate anode material LiNi0.82Co0.09Mn0.09Si0.003Ca0.001O2.006F0.002. As shown in fig. 6, the lithium nickel cobalt manganese oxide positive electrode material has a standard single crystal particle morphology, and the particles are not adhered to each other, which is similar to the morphology of the lithium nickel cobalt manganese oxide positive electrode material in example 1; testing the nickel cobalt lithium manganate cathode material D50Is 4.40mm, and has a specific surface area of 0.62m2(ii)/g, tap density TD of 2.36g/cm3The compacted density of the pole piece is 3.75 g/cm3. The first discharge capacity (0.2C) of the positive electrode material at a voltage of 4.3V was 201.6 mAh/g.
Comparative example 1
Preparing 1.5mol/L nickel-cobalt-manganese sulfate mixed solution (the mol ratio of Ni: Co: Mn = 50: 20: 30), 2mol/L NaOH solution and 1mol/L ammonia water, introducing the solutions into a reaction kettle in a cocurrent flow mode, keeping the reaction temperature at 50 ℃, reacting the pH value at 11.0, precipitating under the protection of nitrogen, washing, and drying at 120 DEG CSieving to obtain Ni-Co-Mn hydroxide precursor Ni0.5Co0.2Mn0.3(OH)2. As shown in fig. 7, the nickel-cobalt-manganese hydroxide has smaller particles, compact appearance and higher density; test result D50Is 3.91 μm, Dmax10.94 μm, the specific surface area is 6.55m2(g), apparent Density AD is 1.20g/cm3The tap density TD is 2.09 g/cm3。
Lithium carbonate and the obtained nickel-cobalt-manganese hydroxide precursor Ni0.5Co0.2Mn0.3(OH)2Mixing in a high-speed mixer according to the proportion of Li/(Ni + Co + Mn) =1.03:1, roasting for 14h at 950 ℃ in air atmosphere, naturally cooling, reducing the temperature, crushing and sieving to obtain LiNi0.5Co0.2Mn0.3And (5) finishing. As shown in FIG. 8, the nickel cobalt lithium manganate positive electrode material is in a polycrystalline small particle shape, D50Is 4.5mm, and has a specific surface area of 0.76m2(ii)/g, tap density TD of 2.26g/cm3The compacted density of the pole piece is 3.10 g/cm3. The first discharge capacity (0.2C) of the positive electrode material at a voltage of 4.3V was 164.5 mAh/g.
Comparative example 2
The same Ni-Co-Mn hydroxide precursor Ni as in example 1 was used0.5Co0.2Mn0.3(OH)2Mixing lithium carbonate and Li/(Ni + Co + Mn) =1.03:1 in a high-speed mixer, roasting at 950 ℃ for 14h in air atmosphere, naturally cooling, crushing and sieving to obtain LiNi0.5Co0.2Mn0.3O2And (5) finishing. As shown in FIG. 9, the lithium nickel cobalt manganese oxide positive electrode material is in a single crystal-like particle shape, and the lithium nickel cobalt manganese oxide positive electrode material D is tested50Is 6.5mm, and has a specific surface area of 0.56m2(ii)/g, tap density TD of 2.31g/cm3(ii) a The compacted density of the pole piece is 3.27 g/cm3. The first discharge capacity (0.2C) of the positive electrode material at a voltage of 4.3V was 164.7 mAh/g.
Comparative example 3
The same Ni-Co-Mn hydroxide precursor Ni as in comparative example 1 was used0.5Co0.2Mn0.3(OH)2Lithium carbonate is mixed with the lithium carbonate according to Li/(Ni + Co)Mixing the materials in a ratio of + Mn)/Sr/Mg =1.03:1:0.005:0.001 in a high-speed mixer, roasting the mixture for 14 hours at 950 ℃ in air atmosphere, naturally cooling the mixture, crushing and sieving the cooled mixture to obtain LiNi0.5Co0.2Mn0.3Sr0.005Mg0.001O2.006And (5) finishing. As shown in FIG. 5, the nickel cobalt lithium manganate positive electrode material is in a polycrystalline small particle shape, D505.7mm, and a specific surface area of 0.73m2(ii)/g, tap density TD of 1.88g/cm3The compacted density of the pole piece is 3.35 g/cm3. The first discharge capacity (0.2C) of the positive electrode material at a voltage of 4.3V was 165.1 mAh/g.
Comparing the electron microscope morphology of the precursor in example 1 with that of the precursors in comparative examples 1, 2 and 3 and the electron microscope morphology of the cathode material, it can be seen that the addition of the polyalcohol dispersant plays an important role in a plurality of indexes such as the morphology, the density, the specific surface area and the like of the precursor, and the addition of the doping element with a specific fluxing action in the sintering process plays an important role in the formation of the single crystal nickel cobalt lithium manganate cathode material.
Compared with the non-single crystal shape comparative examples 1, 2 and 3, the single crystal nickel cobalt lithium manganate positive electrode material in the embodiment 1 has stronger particle strength and higher pole piece compaction density. As can be seen from the cycle comparison of FIG. 11, the single crystal lithium nickel cobalt manganese oxide positive electrode material obtained by sintering the loose-morphology precursor synthesized by the dispersant and the specific fluxing doping element has the optimal cycle performance, and the capacity retention rate is about 98% after 80-week cycle. The cycle life of comparative examples 1, 2, 3, to which no doping element was added and no dispersant was added under the same conditions, was significantly lower than that of example 1, and the downward trend was significant.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. The preparation method of the nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps of:
(1) dissolving nickel salt, cobalt salt and manganese salt into a mixed salt solution with the concentration of 1-3 mol/L according to a certain molar ratio, dissolving a precipitator into a precipitator solution with the concentration of 2-15 mol/L, and dissolving a complexing agent into a complexing agent solution with the concentration of 1-15 mol/L; dissolving a dispersing agent into a dispersing aid solution with the concentration of 1-200 g/L;
(2) introducing the mixed salt solution, the precipitant solution, the complexing agent solution and the dispersing agent solution into a reaction kettle, controlling the reaction temperature to be 40-80 ℃ in nitrogen and/or argon, controlling the concentration of the complexing agent to be 1-15 mol/L and the pH value to be 10.0-13.0, and reacting to obtain spherical nickel-cobalt-manganese hydroxide with a loose structure;
(3) washing the nickel-cobalt-manganese hydroxide obtained in the step (2), and drying at 105-130 ℃ to obtain a precursor of the nickel-cobalt-manganese lithium anode material;
the chemical molecular formula of the precursor of the nickel cobalt lithium manganate positive electrode material is NixCoyMn1-x-y(OH)2Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.5; d of precursor of nickel cobalt lithium manganate positive electrode material502 to 7 μm, and a specific surface area of 7 to 30m2(g), the apparent density AD is 0.5-1.0 g/cm3The tap density TD is 1.0-2.0 g/cm3(ii) a Wherein x and y are not 0;
(4) mixing the precursor of the nickel cobalt lithium manganate positive electrode material, lithium salt and/or lithium hydroxide and an additive containing a specific element, sintering for 4-20 hours at 700-1200 ℃ in an oxygen or air atmosphere, crushing and screening to obtain the nickel cobalt lithium manganate positive electrode material;
the additive containing specific elements is one or more of oxides, hydroxides, carbonates, oxalates, nitrates, chlorides and fluorides of M ' and M ' ' elements;
m ' is one or more elements of Al, Mg, La, Ce, Y and Hf, and M ' ' is one or more elements of Al, Si, Sr, Ba, Na and Ca.
2. The method for preparing the lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the mixed salt in the step (1) is one or more of sulfate, chloride, nitrate and acetate; the precipitator is one or two of NaOH and KOH; the complexing agent is one or more of ammonia water, disodium ethylene diamine tetraacetate, ammonium nitrate, ammonium chloride and ammonium sulfate.
3. The method for preparing the nickel cobalt lithium manganate positive electrode material of claim 1, wherein the dispersant in step (1) is one or more of polyethylene glycol (PEG), polyvinyl alcohol (PVA) and polyglycerol.
4. The method for preparing the lithium nickel cobalt manganese oxide cathode material according to claim 1, wherein the lithium salt is one or more of lithium carbonate, lithium chloride, lithium fluoride and lithium nitrate.
5. A lithium nickel cobalt manganese oxide positive electrode material, characterized by being prepared by the preparation method of claim 1, and having a chemical formula of LiaNixCoyMn1-x-yM’zM’’wO2-δRδWherein a is more than or equal to 0.95 and less than or equal to 1.25, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.01, w is more than or equal to 0 and less than or equal to 0.05, and delta is more than or equal to 0 and less than or equal to 0.02; m ' is one or more elements of Al, Mg, La, Ce, Y and Hf, M ' ' is one or more elements of Al, Si, Sr, Ba, Na and Ca, R is one or more elements of Cl and F, wherein x and Y are not 0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810713401.XA CN109461925B (en) | 2018-06-29 | 2018-06-29 | Single crystal nickel cobalt lithium manganate positive electrode material, precursor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810713401.XA CN109461925B (en) | 2018-06-29 | 2018-06-29 | Single crystal nickel cobalt lithium manganate positive electrode material, precursor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109461925A CN109461925A (en) | 2019-03-12 |
| CN109461925B true CN109461925B (en) | 2022-01-25 |
Family
ID=65606308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810713401.XA Active CN109461925B (en) | 2018-06-29 | 2018-06-29 | Single crystal nickel cobalt lithium manganate positive electrode material, precursor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109461925B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110048118B (en) * | 2019-04-15 | 2021-01-26 | 金驰能源材料有限公司 | High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material |
| CN110422890A (en) * | 2019-06-25 | 2019-11-08 | 当升科技(常州)新材料有限公司 | Anode material for lithium-ion batteries and preparation method thereof and lithium ion cell positive and lithium ion battery |
| CN110534733A (en) * | 2019-07-21 | 2019-12-03 | 浙江美都海创锂电科技有限公司 | A kind of large single crystal lithium ion battery nickle cobalt lithium manganate method for preparing anode material |
| CN110459760B (en) * | 2019-08-20 | 2022-05-24 | 湖北融通高科先进材料有限公司 | Method for preparing nickel cobalt lithium manganate single crystal ternary material |
| CN110957463A (en) * | 2019-10-30 | 2020-04-03 | 深圳市卓能新能源股份有限公司 | Positive pole piece, lithium ion battery and manufacturing method thereof |
| CN112750994B (en) * | 2019-10-31 | 2023-08-29 | 深圳市贝特瑞纳米科技有限公司 | Positive electrode material, preparation method and application thereof |
| CN110993936B (en) * | 2019-12-02 | 2021-08-27 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN111009646B (en) * | 2019-12-09 | 2022-10-11 | 宁波容百新能源科技股份有限公司 | High-rate monocrystal-like nickel-cobalt lithium aluminate cathode material with coating layer and preparation method thereof |
| CN111153443B (en) * | 2020-01-02 | 2021-02-19 | 宁夏中化锂电池材料有限公司 | Nickel cobalt manganese hydroxide and preparation method thereof |
| US11862794B2 (en) * | 2020-05-06 | 2024-01-02 | Battelle Memorial Institute | Cost effective synthesis of oxide materials for lithium ion batteries |
| CN111540890A (en) * | 2020-05-09 | 2020-08-14 | 宁夏中化锂电池材料有限公司 | Nickel cobalt lithium manganate ternary cathode material and preparation method thereof |
| CN112194199A (en) * | 2020-08-27 | 2021-01-08 | 浙江美都海创锂电科技有限公司 | Preparation method of long-cycle ternary cathode material |
| CN112310387A (en) * | 2020-10-26 | 2021-02-02 | 中科(马鞍山)新材料科创园有限公司 | Positive electrode precursor material and preparation method and application thereof |
| CN112531158B (en) * | 2020-12-09 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | High-nickel ternary single crystal material and preparation method thereof |
| CN112226820B (en) * | 2020-12-14 | 2021-02-26 | 河南科隆新能源股份有限公司 | Single-crystal lithium nickel cobalt manganese oxide precursor, preparation method thereof and single-crystal lithium nickel cobalt manganese oxide |
| CN112645395A (en) * | 2020-12-23 | 2021-04-13 | 厦门厦钨新能源材料股份有限公司 | Nickel-cobalt-manganese composite material and preparation method and application thereof |
| 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 |
| CN115084506A (en) * | 2022-05-18 | 2022-09-20 | 广东邦普循环科技有限公司 | Large-particle-size single crystal ternary cathode material and preparation method and application thereof |
| CN114804235B (en) * | 2022-05-26 | 2024-03-12 | 广东邦普循环科技有限公司 | High-voltage nickel cobalt lithium manganate positive electrode material and preparation method and application thereof |
| CN115536071A (en) * | 2022-10-17 | 2022-12-30 | 广西师范大学 | Method for preparing spherical nano metal salt precipitate particles by precipitation method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393476B2 (en) * | 2001-11-22 | 2008-07-01 | Gs Yuasa Corporation | Positive electrode active material for lithium secondary cell and lithium secondary cell |
| TWI392134B (en) * | 2010-01-12 | 2013-04-01 | 成都晶元新材料技術有限公司 | Nickel - cobalt - manganese multicomponent lithium - ion battery cathode material and its preparation method |
| CN103253717B (en) * | 2013-04-23 | 2015-01-14 | 宁夏东方钽业股份有限公司 | Method for preparing small-size nickel-cobalt lithium manganate precursor |
| CN104300117A (en) * | 2014-11-10 | 2015-01-21 | 厦门首能科技有限公司 | Cathode composition for lithium ion battery and preparation method thereof |
| CN104835957B (en) * | 2015-03-19 | 2017-01-18 | 江苏乐能电池股份有限公司 | Preparation method of high-nickel ternary material used for lithium ion battery |
| CN105870414A (en) * | 2016-04-22 | 2016-08-17 | 柳州凯通新材料科技有限公司 | Process for synthesizing lithium nickel manganese cobalt positive electrode material by co-precipitation method |
| CN106892464B (en) * | 2017-03-03 | 2018-10-02 | 北京理工大学 | A kind of preparation method of ternary anode material precursor |
| CN108172819A (en) * | 2017-12-18 | 2018-06-15 | 佛山市德方纳米科技有限公司 | The method of low temperature preparation monocrystalline ternary material and monocrystalline ternary material |
-
2018
- 2018-06-29 CN CN201810713401.XA patent/CN109461925B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109461925A (en) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109461925B (en) | Single crystal nickel cobalt lithium manganate positive electrode material, precursor and preparation method thereof | |
| CN110993936B (en) | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN106505195B (en) | High-nickel cathode material, preparation method thereof and lithium ion battery | |
| US10790506B2 (en) | Spherical or spherical-like cathode material for lithium-ion battery and lithium-ion battery | |
| KR102177799B1 (en) | Method for producing positive electrode active material | |
| US20180175368A1 (en) | Spherical or spherical-like cathode material for a lithium battery, a battery and preparation method and application thereof | |
| KR101313575B1 (en) | Manufacturing method of positive active material precursor and lithium metal composite oxides for lithium secondary battery | |
| KR20170102293A (en) | Multicomponent materials having a classification structure for lithium ion batteries, a method for manufacturing the same, an anode of a lithium ion battery and a lithium ion battery | |
| JPWO2002086993A1 (en) | Positive electrode active material and method for producing the same, positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery | |
| US20220340446A1 (en) | Cobalt-free lamellar cathode material and method for preparing cobalt-free lamellar cathode material, cathode piece and lithium ion battery | |
| JP7398015B2 (en) | Single-crystal multi-component cathode material, manufacturing method and use thereof | |
| CN113603154B (en) | High-voltage nickel-cobalt-manganese ternary precursor and preparation method thereof | |
| CN112993241B (en) | Preparation method of single-crystal lithium manganate material | |
| US20220246978A1 (en) | Lithium ion battery positive electrode material, preparation method therefor, and lithium ion battery | |
| KR20160083638A (en) | Cathode active material for lithium secondary and lithium secondary batteries comprising the same | |
| CN115043387B (en) | Preparation method of ammonium ferromanganese phosphate, lithium ferromanganese phosphate and application thereof | |
| JP4159640B2 (en) | Anode active material for lithium ion battery and method for producing the same | |
| KR101525000B1 (en) | Method for preparing nickel-manganese complex hydroxides for cathode materials in lithium batteries, nickel-manganese complex hydroxides prepared by the method and cathode materials in lithium batteries comprising the same | |
| KR102131738B1 (en) | Method for producing positive electrode active material | |
| CN113871603A (en) | High-nickel ternary cathode material and preparation method thereof | |
| CN113213556A (en) | Porous nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof | |
| JPH10162830A (en) | Positive electrode active material for lithium secondary battery, and secondary battery using same | |
| CN114804235B (en) | High-voltage nickel cobalt lithium manganate positive electrode material and preparation method and application thereof | |
| KR20060122452A (en) | Manganese oxides by co-precipitation method, spinel type cathode active material for lithium secondary batteries using thereby and preparation of the same | |
| CN111634961A (en) | Positive electrode material for lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |