WO2014190662A1 - Dual-doped lithium-rich solid solution positive electrode composite and preparation method thereof, lithium-ion battery positive electrode plate, and lithium-ion battery - Google Patents
Dual-doped lithium-rich solid solution positive electrode composite and preparation method thereof, lithium-ion battery positive electrode plate, and lithium-ion battery Download PDFInfo
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- WO2014190662A1 WO2014190662A1 PCT/CN2013/085888 CN2013085888W WO2014190662A1 WO 2014190662 A1 WO2014190662 A1 WO 2014190662A1 CN 2013085888 W CN2013085888 W CN 2013085888W WO 2014190662 A1 WO2014190662 A1 WO 2014190662A1
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- Prior art keywords
- lithium
- solid solution
- double
- rich solid
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 95
- 239000006104 solid solution Substances 0.000 title claims abstract description 93
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 23
- 229910052723 transition metal Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class 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
- 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910013191 LiMO2 Inorganic materials 0.000 abstract 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 31
- 239000010406 cathode material Substances 0.000 description 27
- 239000011572 manganese Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- -1 cationic anion Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M4/1315—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx containing halogen atoms, e.g. LiCoOxFy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- 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
Definitions
- the invention relates to the field of lithium ion batteries, in particular to a double-doped lithium-rich solid solution cathode composite material and a preparation method thereof, a positive electrode sheet for a lithium ion battery and a lithium ion battery. Background technique
- cathode materials for lithium-ion batteries have become a key factor limiting the further increase in energy density of lithium-ion batteries.
- the commonly used cathode materials are: lithium cobalt oxide (LCO), lithium manganate (LMO), lithium iron phosphate (LFP) and nickel-cobalt-manganese (NCM) ternary materials, but the specific capacity of these cathode materials is mostly ⁇ 160 mAh/g.
- LCO lithium cobalt oxide
- LMO lithium manganate
- LFP lithium iron phosphate
- NCM nickel-cobalt-manganese
- LiM0 2 is composed of a transition metal layer, an oxygen layer and a lithium ion layer.
- the structure is schematically shown in Fig. 1.
- the transition metal layer in LiM0 2 is composed of M (M is selected from one of Ni, Co, Mn, Ti, Zr). Or several).
- Li 2 Mn0 3 is also composed of a transition metal layer, an oxygen layer and a lithium ion layer, and the transition metal layer in Li 2 Mn0 3 is composed of +4 Mn and +1 Li Together.
- the lithium-rich solid solution cathode material has a high discharge capacity (>250 mAh/g, a charging voltage of >4.6 V), and the cost is low, which has become the development direction of the next-generation cathode material.
- the lithium-rich solid solution cathode material of this Layered-Layered structure is charged and discharged (>4.5 V), accompanied by the formation of cation Li + and is removed from the lithium ion layer, and oxygen is precipitated from the oxygen layer in the form of oxygen.
- the sensitization reaction occurs on the surface of the lithium-rich solid solution cathode material. The reaction is as follows:
- Thackeray et al also proposed to use a weakly acidic fluorinated solution N PF 6 , (N ) 3 A1F 6 , NH 4 BF 4 to soak the lithium-rich solid solution cathode material, and to modify the surface of the lithium-rich solid solution cathode material by fluorine doping.
- fluorine enters the interior of the lithium-rich solid solution cathode material lattice to replace part of the oxygen position, and the formation of strong fluorine-oxygen bonds inhibits the precipitation of oxygen on the surface of the lithium-rich solid solution cathode material during charge and discharge, which improves lithium enrichment to some extent.
- the surface conductivity of the lithium-rich solid solution cathode material improves the cycle stability of the lithium-rich solid solution cathode material during charge and discharge cycles. Nevertheless, the problem has not been solved, and the energy density of the lithium ion battery produced by the fluorine-doped lithium-rich solid solution cathode material decreases rapidly with increasing cycle.
- the first aspect of the present invention provides a dual-doped lithium-rich solid solution cathode composite material for solving the problem of voltage platform falling due to structural collapse during the recycling process of the lithium-rich solid solution cathode material in the prior art.
- a second aspect of the embodiments of the present invention provides a method of preparing the double-doped lithium-rich solid solution positive electrode composite.
- a third aspect of an embodiment of the present invention provides a positive electrode sheet for a lithium ion battery comprising the double doped lithium-rich solid solution positive electrode composite.
- a fourth aspect of an embodiment of the present invention provides a lithium ion battery comprising the positive electrode sheet of the double doped lithium ion battery.
- an embodiment of the present invention provides a dual-doped lithium-rich solid solution cathode composite material having a chemical formula of: xLi 2 Mn0 3 .(l -x)LiM0 2 .yM a M b , where 0 ⁇ 1 , 0 ⁇ y ⁇ 0.1 , M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, ⁇ is Na One or a combination of K and M, M b is a combination of one or more of F, ⁇ and ⁇ .
- the double-doped lithium-rich solid solution cathode composite material is composed of a layered compound Li 2 Mn0 3 , a layered compound LiM0 2 , and a cationic anion M b , and M is one or more of Ni, Co, Mn, Ti, and Zr.
- a combination of ⁇ is one or a combination of Na and K, and M b is a combination of one or more of F, N, and P.
- the layered compound LiM0 2 is composed of a transition metal layer, an oxygen layer and a lithium ion layer, and the transition metal layer in LiM0 2 is composed of M, and M is one or a combination of Ni, Co, Mn, Ti, Zr.
- the layered compound Li 2 Mn0 3 is composed of a transition metal layer, an oxygen layer and a lithium ion layer, and the transition metal layer in Li 2 Mn0 3 is composed of Mn 4+ and Li + .
- the densely packed layers of the layered compound LiM0 2 and the layered compound Li 2 Mn0 3 have the same layer spacing, and the two components are identical in atomic order.
- the description of the "lithium ion layer in the double-doped lithium-rich solid solution cathode composite material" and the “double-doped lithium-rich solid solution cathode composite material lattice" in the embodiment of the present invention is The layered compound LiM0 2 or the layered compound Li 2 Mn0 3 , and the layered compound LiM0 2 and the layered compound Li 2 Mn0 3 .
- the value of y ranges from 0.02 ⁇ y ⁇ 0.09. More preferably, the value of y is 0.05 y 0.06.
- the double-doped lithium-rich solid solution positive electrode composite material is simultaneously doped with a cation M a and an anion M b .
- the cation M a occupies the position of the lithium ion layer in the double-doped lithium-rich solid solution positive electrode composite, and the cation radius is larger than the Li + radius.
- the cation M a acts as a pillar to keep the structure from collapsing.
- the invention has the advantages of good structural stability and thus solves the prior art.
- the cation M a acts as a pillar to enlarge the interlayer spacing of the double-doped lithium-rich solid solution positive electrode composite material, which facilitates the insertion and extraction of Li + , and improves from the viewpoint of layer spacing.
- the anion M b enters the crystal lattice of the double-doped lithium-rich solid solution cathode composite, forms a strong Mb-0 bond with 0, reduces the precipitation of oxygen during charge and discharge, and makes the double-doped lithium-rich solid solution from the angle of Mb-0 bond.
- the positive electrode composite has good structural stability and enhances charge and discharge efficiency, cycle life and rate performance.
- an embodiment of the present invention provides a method for preparing a dual-doped lithium-rich solid solution cathode composite material, comprising the following steps:
- the soluble M salt is dissolved, and M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, and a transition metal having a M element concentration of 0.5 to 5 mol/L is obtained.
- saline solution take or alkali carbonate dissolution, prepared OH_ concentration of l ⁇ 5mol / L or a concentration of a solution OH_ C0 3 2 _ is l ⁇ 5mol / L solution of C0 3 2 _; stirring was continued And adding the aqueous solution of the transition metal salt to the Off solution or the C0 3 2 - solution, forming a precipitate in the prepared mixed solution, continuing to stir the mixed solution, and then standing to obtain a solid-liquid mixed solution. Filtering, collecting the precipitate in the solid-liquid mixed solution, The collected precipitate is washed and dried to obtain a precursor;
- the mixture is prepared by mixing a lithium salt, M a M b and the precursor according to the ratio of the chemical formula xLi 2 Mn0 3 .(lx)LiM0 2 .yM a M b , 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ 0.1, ⁇ is one or a combination of Na and K, M b is a combination of one or more of F, N and P, ground to obtain an abrasive product, and the ground product is placed at 40 to 200 ° C Drying for 1 ⁇ 48h, to obtain the dried grinding product; placing the dried ground product in a muffle furnace, heating to 400 ⁇ 800 °C, then heating to 800 ⁇ 1500 °C, keeping the temperature constant 0.5 to 48 h, the furnace is cooled to room temperature to obtain a double-doped lithium-rich solid solution cathode composite material, and the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: x Li 2 Mn0 3 '(lx)L
- the M salt is one or a combination of an acetate, an oxalate, an acid salt, a nitrate and a chloride.
- the base is a combination of one or more of LiOH, NaOH, KOH, aqueous ammonia and ammonium salts.
- the carbonate is one or more of Li 2 C0 3 , Na 2 C0 3 , K 2 C0 3 , (N ) 2 C0 3 and (N ) HC 0 3 .
- the lithium salt is one or a combination of lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium carbonate, and lithium chloride.
- y has a value in the range of 0.02 y 0.09. More preferably, the value of y ranges from 0.05 y to 0.06.
- the aqueous solution of the transition metal salt is added to the OH_solution or the C0 3 2 _ solution at a rate of 0.1 to 50 ml/s.
- the grinding is to add ethanol and ball beads to the mixture and place in a planetary ball mill.
- the ball is continuously milled for 0.5-24 h.
- the mixed solution is continuously stirred for 10 min to 12 h, and then allowed to stand for l ⁇ 48 h.
- the dried ground product is placed in a muffle furnace, heated to a temperature of 400 to 800 ° C at a rate of 0.2 to 20 ° C / min, and then heated to a temperature of 800 to 1500 at a rate of 1 to 10 ° C / min. °C.
- the preparation method of the double-doped lithium-rich solid solution cathode composite material in the second aspect of the present invention is a one-step synthesis method comprising the steps of coprecipitation synthesis precursor and high-temperature sintering to obtain a double-doped lithium-rich solid solution cathode composite material.
- the purpose of simultaneously doping the cationic anion M b is achieved: the cation M a occupies the position of the lithium ion layer in the partially doped lithium-rich solid solution positive electrode composite, which solves the prior art and improves the double doping from the viewpoint of layer spacing.
- Cycle performance and rate performance of lithium-rich solid solution cathode composite anion M b enters the lattice of double-doped lithium-rich solid solution cathode composite, forming a strong Mb-0 bond with 0, making double doping from the angle of Mb-0 bond
- the lithium-rich solid solution cathode composite has good structural stability and enhanced charge and discharge efficiency, cycle life and rate performance.
- the preparation method of the double-doped lithium-rich solid solution cathode composite material provided by the second aspect of the present invention is simple and easy, and the obtained double-doped lithium-rich solid solution cathode composite material has good structural stability and enhanced charge and discharge. Efficiency, cycle life and rate performance, voltage platform stability.
- an embodiment of the present invention provides a positive electrode sheet for a lithium ion battery, the positive electrode sheet of the lithium ion battery comprising a current collector and a double-doped lithium-rich solid solution positive electrode composite coated on the current collector, the double-doped rich
- the lithium solid solution positive electrode composite has the chemical formula: xLi 2 Mn0 3 .(lx)LiM0 2 .yM a M b , where 0 ⁇ 1, 0 ⁇ y ⁇ 0.1, M is Ni, Co, Mn, Ti, Ah Zr, A combination of one or more of Fe, V, Mg and W, ⁇ is one or a combination of Na and K, and M b is a combination of one or more of F, ⁇ and ⁇ .
- y has a value in the range of 0.02 y 0.09. More preferably, the value of y ranges from 0.05 y to 0.06.
- the preparation method of the positive electrode sheet of the lithium ion battery is as follows: mixing the double-doped lithium-rich solid solution positive electrode composite material, the conductive agent, the binder and the solvent to prepare a slurry, and coating the slurry on the current collector, followed by drying and pressing Tablet, a positive electrode for lithium ion batteries.
- an embodiment of the present invention provides a lithium ion battery, including a positive electrode sheet of a lithium ion battery, a negative electrode sheet of a lithium ion battery, a separator, and an electrolyte, wherein the positive electrode sheet of the lithium ion battery includes a current collector and is coated on the current collector
- the double-doped lithium-rich solid solution cathode composite material, the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: xLi 2 Mn0 3 lx)LiM0 2 -yM a M b , where 0 ⁇ x ⁇ l, 0 ⁇ y ⁇ 0.1 , M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, and M a is one or a combination of Na
- y has a value in the range of 0.02 y 0.09. More preferably, the value of y ranges from 0.05 y to 0.06.
- the lithium ion battery voltage platform provided by the fourth aspect of the embodiments of the present invention is stable, has a long cycle life, and has excellent rate performance and charge and discharge efficiency.
- FIG. 1 is a schematic view showing the structure of a layered compound LiMC in a lithium-rich manganese-based solid solution cathode material xLi[Li 1/3 Mn 2/3 ]0 2 ⁇ (lx)LiM0 2 .
- FIG. 2 is a schematic view showing the structure of a layered compound LiM0 2 in a double-doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention.
- a preparation method of a double-doped lithium-rich solid solution cathode composite material (0.4Li 2 MnO 3 '0.6LiNi 0 . 38 Co 0 . 24 Mn 0 . 38 O 2 O.05NaF ), comprising the following steps: taking manganese acetate, acetic acid The ratio of nickel to cobalt acetate is 4.4:1.6:1 dissolved in distilled water to prepare a transition metal salt solution with a total concentration of 1 mol/L of manganese, nickel and cobalt; LiOH is dissolved in distilled water to obtain OH.
- a mixture of Li 2 CO 3 , NaF and the precursor was mixed at a molar ratio of 0.712:0.05:1, and 10 ml of ethanol was added to the mixture, which was placed in a mortar.
- the mixture was uniformly mixed to obtain an abrasive product, and the ground product was dried at 80 ° C for 12 hours to obtain a dried product.
- Double-doped lithium-rich solid solution positive electrode composite acetylene black: PVDF: NMP is mixed in a mass ratio of 8:1:1:100, adjusted to a uniform slurry with isopropyl alcohol, uniformly coated on aluminum sheet, at 120 Vacuum drying for 18 h, tableting, to obtain a positive electrode of a lithium ion battery.
- the positive electrode sheet of the lithium ion battery obtained in the present example was assembled into a button cell of No. 2025 in a Ar-protected glove box with a Li metal negative electrode sheet, a separator and an electrolyte, and electrochemical performance was measured.
- a preparation method of a double-doped lithium-rich solid solution positive electrode composite material comprising the following steps: taking manganese nitrate, nitric acid The ratio of nickel to cobalt nitrate is 3.7:1.6:1 dissolved in distilled water to prepare a transition metal salt solution with a total concentration of 1 mol/L of manganese, nickel and cobalt; NaOH is dissolved in distilled water to obtain OH.
- the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: 0.5Li 2 MnO 3 -0.5LiNi 0 . 38 Co 0 . 2 4Mn 0 38 O 2 -0.02 KF.
- the preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
- a method for preparing a double-doped lithium-rich solid solution cathode composite material (0.55Li 2 Mn0 3 -0.45LiNio.o.4Coo.2Mno. 4 0 2 -0.09Na 3 N ) comprises the following steps: taking manganese sulfate, nickel sulfate The cobalt sulfate has a ratio of 8.1:2:1 dissolved in distilled water to prepare a transition metal salt solution with a total concentration of 1 mol/L of manganese, nickel and cobalt; and Na 2 CO 3 is dissolved in distilled water.
- the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: 0.55Li 2 MnO 3 '0.45LiNi 0 0 .4Co 02 Mn 0 .4O 2 '0.09Na 3 N.
- the preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
- a preparation method of a double-doped lithium-rich solid solution cathode composite material (0.6Li 2 Mn0 3 -0.4LiNio. 34 Coo.24Mn 0 . 3 8 Mg 0 .04O 2 -0.06K 3 P ) comprises the following steps:
- a ratio of 7.8: 1.4:0.17:1 in a molar ratio of manganese sulfate, nickel sulfate, magnesium sulfate and cobalt sulfate to distilled water to prepare a transition metal salt aqueous solution having a total concentration of manganese, nickel and cobalt of 1 mol/L; Na 2 C0 3 was dissolved in distilled water to prepare a solution of 0 3 2 _ 2 mol/L of C0 3 2 _ solution; under continuous stirring, 80 ml of the aqueous solution of the transition metal salt was 2 ml/s. The speed is added to 100 ml of CO ⁇ solution, and a precipitate is formed in the prepared mixed solution.
- the color of the mixed solution is gradually changed from white to brown and then stirred for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered. Collecting the brown precipitate in the solid-liquid mixed solution, and washing the collected precipitate 4 times with 400 ml of distilled water, and then drying the precipitate in a drying oven at 120 ° C for 24 h to prepare a precursor;
- the double-doped lithium-rich solid solution cathode composite material has a chemical formula of 0.6Li2Mn0 3 -0.4LiNio.34Coo.24Mn 0 .38 Mg 0 . 04 O 2 '0.06K 3 P.
- the preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
- a preparation method of a lithium-rich solid solution positive electrode composite material (0.55Li 2 Mn0 3 -0.45LiNio.o.4Coo.2Mno. 4 0 2 ), comprising the following steps:
- a transition metal salt solution having a total concentration of manganese, nickel and cobalt of 1 mol/L taking LiOH dissolved in distilled water Preparing an OH_ solution having a concentration of OH_ of 2 mol/L; adding 80 ml of the aqueous solution of the transition metal salt to a solution of 100 ml of C0 3 2- at a rate of 2 ml/s under continuous stirring.
- a precipitate is formed in the prepared mixed solution, the color of the solution to be mixed is gradually changed from white to brown, and stirring is continued for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered to collect brown in the solid-liquid mixed solution.
- the mixture was uniformly mixed, placed in a drying oven at 80 ° C, dried for 12 h to prepare an abrasive product, and the ground product was dried at 80 ° C for 12 hours to prepare a dried ground product;
- the post-grinding product is placed in a muffle furnace, heated to 600 ° C at a rate of 10 ° C / min, then heated to 1000 ° C at a rate of 5 ° C / min, maintained at a constant temperature for 24 h, and cooled to room temperature with the furnace.
- the chemical formula of the solution positive electrode composite is: 0.55Li 2 MnO 3 '0.45LiNi. . . . .4Co. . 2 Mn. . 4 O 2 .
- the preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
- the lithium ion batteries produced in the above examples and comparative examples were experimental batteries for the performance test of the following effect examples.
- the first discharge capacities of the lithium ion batteries obtained in the examples and the comparative examples were measured under the conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively.
- the first discharge capacity and the charge capacity of the lithium ion batteries obtained in the examples and the comparative examples were measured under the conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively, and the first charge and discharge efficiency was calculated.
- First charge and discharge efficiency first discharge capacity / first charge capacity.
- the discharge capacities of the lithium ion batteries obtained in the examples and the comparative examples after 50 cycles were measured under conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively.
- the 50 discharge voltages/first discharge voltages of the lithium ion batteries obtained in the examples and the comparative examples were measured under the conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively.
- Table 1 and Table 2 are the first discharge capacity performance test, the first charge and discharge efficiency performance test, and the 50 cycle capacity performance test results of the examples and comparative examples of the present invention.
- Table 1 Comparison of electrochemical performance at a charge-discharge current of 0.1 C and a charge-discharge voltage range of 2 to 4.6 V
- Table 2 compares the electrochemical performance of the charging and discharging current of 1C and the charging and discharging voltage range of 2 ⁇ 4.6 V.
- the double-doped lithium-rich solid solution positive electrode composite provided in the first embodiment and the second embodiment of the present invention has a higher discharge capacity than the first comparative example
- the dual-doped lithium-rich solid solution cathode composite provided in the first embodiment, the second embodiment and the third embodiment has higher first charge and discharge efficiency, better cycle performance, and higher ratio than the first embodiment. Voltage stability and better rate performance.
- FIG. 2 is a schematic view showing the structure of a layered compound LiM0 2 in a double-doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention.
- 3 is a layered layer of a double doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention; Schematic diagram of the structure of Li 2 MnO 3 .
- the dual-doped lithium-rich solid solution cathode composite provided by the embodiment of the invention is simultaneously doped with a cation M a and an anion M b .
- the cation M a occupies the position of the lithium ion layer in the double-doped lithium-rich solid solution positive electrode composite, and the cation radius is larger than the Li + radius. At the same time as the insertion and extraction of Li + , the cation M a acts as a pillar to keep the structure from collapsing.
- the invention has good structural stability, thereby solving the problem that the voltage platform of the lithium-rich solid solution cathode material in the prior art is reduced due to structural collapse during the cycle.
- the cation is the pillar to enlarge the interlayer spacing of the double-doped lithium-rich solid solution cathode composite, which facilitates the insertion and extraction of Li + , and improves the cycle performance and rate performance of the double-doped lithium-rich solid solution cathode composite from the viewpoint of layer spacing.
- the anion M b enters the crystal lattice of the double-doped lithium-rich solid solution cathode composite, forms a strong Mb-0 bond with 0, reduces the precipitation of oxygen during charge and discharge, and makes the double-doped lithium-rich solid solution from the angle of Mb-0 bond.
- the positive electrode composite has good structural stability and enhances charge and discharge efficiency, cycle life and rate performance.
Abstract
A dual-doped lithium-rich solid solution positive electrode composite, the chemical formula thereof being xLi2MnO3·(1-x)LiMO2·yMaMb, wherein 0＜x＜1, 0＜y＜0.1, M is one of or a combination of Ni, Co, Mn, Ti, Al, Zr, Fe, V, Mg, and W, Ma is one of or a combination of Na and K, and Mb is one of or a combination of F, N, and P; the dual-doped lithium-rich solid solution positive electrode composite solves the problem of the prior art of a voltage plateau drop caused by structural collapse during recirculation of a lithium-rich solid solution positive electrode material. Also provided is a preparation method for the positive electrode composite, containing a lithium-ion battery positive electrode plate of the positive electrode composite and containing a lithium-ion battery of the lithium-ion battery positive electrode plate.
Description
一种双掺杂富锂固溶体正极复合材料及其制备方法、 锂离子电池正极片和 锂离子电池 技术领域 Double-doped lithium-rich solid solution cathode composite material and preparation method thereof, lithium ion battery positive electrode sheet and lithium ion battery
本发明涉及锂离子电池领域， 特别是涉及一种双掺杂富锂固溶体正极复合 材料及其制备方法、 锂离子电池正极片和锂离子电池。 背景技术 The invention relates to the field of lithium ion batteries, in particular to a double-doped lithium-rich solid solution cathode composite material and a preparation method thereof, a positive electrode sheet for a lithium ion battery and a lithium ion battery. Background technique
随着锂离子电池能量密度的进一步提升， 其应用领域将逐步的应用于电动 车 （电动自行车、 电动汽车、 混合动力汽车） 、 电网及其他大规模的储能领域。 锂离子电池正极材料的发展已经成为制约锂离子电池能量密度进一步提升的关 键因素。 目前常用的正极材料为： 钴酸锂 ( LCO ) 、 锰酸锂 ( LMO ) 、 磷酸铁 锂（ LFP )以及镍-钴-锰 ( NCM )三元材料等，但这些正极材料的比容量大都 <160 mAh/g。发展新的高容量的正极材料， 才有希望进一步提升当前锂离子电池的能 量密度。 With the further increase in the energy density of lithium-ion batteries, their applications will gradually be applied to electric vehicles (electric bicycles, electric vehicles, hybrid vehicles), power grids and other large-scale energy storage areas. The development of cathode materials for lithium-ion batteries has become a key factor limiting the further increase in energy density of lithium-ion batteries. The commonly used cathode materials are: lithium cobalt oxide (LCO), lithium manganate (LMO), lithium iron phosphate (LFP) and nickel-cobalt-manganese (NCM) ternary materials, but the specific capacity of these cathode materials is mostly < 160 mAh/g. The development of new high-capacity cathode materials is expected to further increase the energy density of current lithium-ion batteries.
Thackeray等提出了富锂锰基固溶体正极材料 xLi[Li1/3Mn2/3]02 · (l-x)LiM02 ( M=Ni、 Co、 Mn、 Ti、 Zr 中的一种或几种） 。 该富锂固溶体正极材料由层状 化合物 Li[Li1/3Mn2/3]02即 （ Li2Mn03 ) 和层状化合物 LiM02组成， 也可写为 xLi2Mn03 · ( 1-x ) LiM02 ( M=Ni、 Co、 Mn、 Ti、 Zr中的一种或几种） ， 即层 段-层段结构（ layered-layered结构）。 LiM02由过渡金属层、 氧层和锂离子层组 成， 结构示意图如图 1所示， LiM02中的过渡金属层由 M组成（M选自 Ni、 Co、 Mn、 Ti、 Zr中的一种或几种） 。 与 LiM02结构相似， Li2Mn03也由过渡金 属层、 氧层和锂离子层组成， Li2Mn03中的过渡金属层由 +4的 Mn和 +1 的 Li
共同组成。 近年来， 该富锂固溶体正极材料因具有高的放电容量（>250 mAh/g, 充电电压>4.6 V ) , 且成本 ^艮低， 成为下一代正极材料的发展方向。 这种 Layered-Layered 结构的富锂固溶体正极材料在充放电的过程中 （>4.5 V ) , 伴 随阳离子 Li+的生成并从锂离子层中脱出，氧元素会以氧气的形式从氧层中析出， 富锂固溶体正极材料表面会发生敏化反应， 反应如下： Thackeray et al. proposed a lithium-rich manganese-based solid solution cathode material xLi[Li 1/3 Mn 2/3 ]0 2 · (lx)LiM0 2 (one or several of M=Ni, Co, Mn, Ti, Zr) . The lithium-rich solid solution cathode material is composed of a layered compound Li[Li 1/3 Mn 2/3 ]0 2 (Li 2 Mn0 3 ) and a layered compound LiM0 2 , and can also be written as xLi 2 Mn0 3 · ( 1- x ) LiM0 2 (M = one or more of Ni, Co, Mn, Ti, Zr), that is, a layered-layered structure. LiM0 2 is composed of a transition metal layer, an oxygen layer and a lithium ion layer. The structure is schematically shown in Fig. 1. The transition metal layer in LiM0 2 is composed of M (M is selected from one of Ni, Co, Mn, Ti, Zr). Or several). Similar to the structure of LiM0 2 , Li 2 Mn0 3 is also composed of a transition metal layer, an oxygen layer and a lithium ion layer, and the transition metal layer in Li 2 Mn0 3 is composed of +4 Mn and +1 Li Together. In recent years, the lithium-rich solid solution cathode material has a high discharge capacity (>250 mAh/g, a charging voltage of >4.6 V), and the cost is low, which has become the development direction of the next-generation cathode material. The lithium-rich solid solution cathode material of this Layered-Layered structure is charged and discharged (>4.5 V), accompanied by the formation of cation Li + and is removed from the lithium ion layer, and oxygen is precipitated from the oxygen layer in the form of oxygen. The sensitization reaction occurs on the surface of the lithium-rich solid solution cathode material. The reaction is as follows:
LiM02→ Liv_xM02_s + xLi+ + δ / 202 + xe 式 ( 1 ) LiM0 2 → Li v _ x M0 2 _ s + xLi + + δ / 20 2 + xe (1)
Li2Mn03→ Mn02 + 2Li+ + \l 202 + 2e 式 ( 2 ) Li 2 Mn0 3 → Mn0 2 + 2Li + + \l 20 2 + 2e Formula ( 2 )
对电化学性能有如下影响： 02的产生会形成 Li20, 充电过程， Li2C 艮难回 去， 造成首次充放电效率很低（〜70% ) ； 氧层和锂离子层结构的破坏将影响循 环性能和倍率性能， 特别是锂离子层 Li+的脱出将导致局部结构的坍塌从而导致 富锂固溶体正极材料在充放电过程中电压平台的下降。 It has the following effects on electrochemical performance: 0 2 will form Li 2 0, charging process, Li 2 C 艮 is difficult to return, resulting in low initial charge and discharge efficiency (~70%); destruction of oxygen layer and lithium ion layer structure It will affect the cycle performance and rate performance, especially the lithium ion layer Li + will lead to the collapse of the local structure and lead to the decline of the voltage platform during the charge and discharge process of the lithium-rich solid solution cathode material.
Thackeray等也提出了采用弱酸性的氟化溶液 N PF6、（N )3A1F6、 NH4BF4 浸泡富锂固溶体正极材料， 对富锂固溶体正极材料表面进行氟掺杂改性处理。 有研究推测， 氟进入富锂固溶体正极材料晶格内部取代了部分氧位置， 形成的 强氟 -氧键抑制了充放电过程中富锂固溶体正极材料表面氧的析出， 在一定程度 上提高了富锂固溶体正极材料的结构稳定性； 比表面阻抗测试结果同时表明， 氟掺杂后的富锂固溶体正极材料比表面阻抗降低， 这可能是由于氟掺杂导致了 过渡金属离子价态的变化， 从而增加了富锂固溶体正极材料表面电导率， 在一 定程度上提高了富锂固溶体正极材料充放电循环过程中循环稳定性。 虽然如此， 的问题并没有得到解决， 以该氟掺杂的富锂固溶体正极材料制得的锂离子电池 的能量密度随循环增加下降较快。
发明内容 Thackeray et al also proposed to use a weakly acidic fluorinated solution N PF 6 , (N ) 3 A1F 6 , NH 4 BF 4 to soak the lithium-rich solid solution cathode material, and to modify the surface of the lithium-rich solid solution cathode material by fluorine doping. Some studies have speculated that fluorine enters the interior of the lithium-rich solid solution cathode material lattice to replace part of the oxygen position, and the formation of strong fluorine-oxygen bonds inhibits the precipitation of oxygen on the surface of the lithium-rich solid solution cathode material during charge and discharge, which improves lithium enrichment to some extent. The structural stability of the solid solution cathode material; the surface resistance test results show that the surface-impedance of the lithium-rich solid solution cathode material after fluorine doping is lower, which may be due to the change of the valence state of the transition metal ion due to fluorine doping, thereby increasing The surface conductivity of the lithium-rich solid solution cathode material improves the cycle stability of the lithium-rich solid solution cathode material during charge and discharge cycles. Nevertheless, the problem has not been solved, and the energy density of the lithium ion battery produced by the fluorine-doped lithium-rich solid solution cathode material decreases rapidly with increasing cycle. Summary of the invention
有鉴于此 ,本发明实施例第一方面提供了一种双掺杂富锂固溶体正极复合材 料， 用以解决现有技术中富锂固溶体正极材料在循环过程中因结构坍塌导致的 电压平台下降的问题。 本发明实施例第二方面提供了所述双掺杂富锂固溶体正 极复合材料的制备方法。 本发明实施例第三方面提供了包含所述双掺杂富锂固 溶体正极复合材料的锂离子电池正极片。 本发明实施例第四方面提供了包含所 述双掺杂锂离子电池正极片的锂离子电池。 In view of this, the first aspect of the present invention provides a dual-doped lithium-rich solid solution cathode composite material for solving the problem of voltage platform falling due to structural collapse during the recycling process of the lithium-rich solid solution cathode material in the prior art. . A second aspect of the embodiments of the present invention provides a method of preparing the double-doped lithium-rich solid solution positive electrode composite. A third aspect of an embodiment of the present invention provides a positive electrode sheet for a lithium ion battery comprising the double doped lithium-rich solid solution positive electrode composite. A fourth aspect of an embodiment of the present invention provides a lithium ion battery comprising the positive electrode sheet of the double doped lithium ion battery.
第一方面，本发明实施例提供了一种双掺杂富锂固溶体正极复合材料，所述 双掺杂富锂固溶体正极复合材料化学式为： xLi2Mn03.(l -x)LiM02.yMaMb , 其中 0<χ<1 , 0<y<0.1 , M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或 几种的组合， ^^为 Na和 K中的一种或组合， Mb为F、 Ν和 Ρ中的一种或几种 的组合。 In a first aspect, an embodiment of the present invention provides a dual-doped lithium-rich solid solution cathode composite material having a chemical formula of: xLi 2 Mn0 3 .(l -x)LiM0 2 .yM a M b , where 0<χ<1 , 0<y<0.1 , M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, ^^ is Na One or a combination of K and M, M b is a combination of one or more of F, Ν and Ρ.
所述双掺杂富锂固溶体正极复合材料由层状化合物 Li2Mn03、 层状化合物 LiM02、 阳离子 阴离子 Mb组成， M为 Ni、 Co、 Mn、 Ti、 Zr中的一种或 几种的组合， ^^为 Na和 K中的一种或组合， Mb为F、 N和 P中的一种或几种 的组合。 The double-doped lithium-rich solid solution cathode composite material is composed of a layered compound Li 2 Mn0 3 , a layered compound LiM0 2 , and a cationic anion M b , and M is one or more of Ni, Co, Mn, Ti, and Zr. A combination of ^^ is one or a combination of Na and K, and M b is a combination of one or more of F, N, and P.
层状化合物 LiM02由过渡金属层、 氧层和锂离子层组成， LiM02中的过渡 金属层由 M组成， M为 Ni、 Co、 Mn、 Ti、 Zr中的一种或几种的组合。 The layered compound LiM0 2 is composed of a transition metal layer, an oxygen layer and a lithium ion layer, and the transition metal layer in LiM0 2 is composed of M, and M is one or a combination of Ni, Co, Mn, Ti, Zr.
层状化合物 Li2Mn03由过渡金属层、 氧层和锂离子层组成， Li2Mn03中的过 渡金属层由 Mn4+和 Li+共同组成。 The layered compound Li 2 Mn0 3 is composed of a transition metal layer, an oxygen layer and a lithium ion layer, and the transition metal layer in Li 2 Mn0 3 is composed of Mn 4+ and Li + .
层状化合物 LiM02和层状化合物 Li2Mn03的密堆积层具有相同的层间距， 这两种组分在原子等级上一致。 本发明实施例中的 "双掺杂富锂固溶体正极复 合材料中锂离子层" 和 "双掺杂富锂固溶体正极复合材料晶格" 的描述对象是
层状化合物 LiM02或层状化合物 Li2Mn03, 以及层状化合物 LiM02和层状化合 物 Li2Mn03。 The densely packed layers of the layered compound LiM0 2 and the layered compound Li 2 Mn0 3 have the same layer spacing, and the two components are identical in atomic order. The description of the "lithium ion layer in the double-doped lithium-rich solid solution cathode composite material" and the "double-doped lithium-rich solid solution cathode composite material lattice" in the embodiment of the present invention is The layered compound LiM0 2 or the layered compound Li 2 Mn0 3 , and the layered compound LiM0 2 and the layered compound Li 2 Mn0 3 .
优选地， 所述 y的取值范围为 0.02 < y < 0.09。 更优选地， 所述 y的取值范 围为 0.05 y 0.06。 Preferably, the value of y ranges from 0.02 < y < 0.09. More preferably, the value of y is 0.05 y 0.06.
本发明实施例第一方面中，双掺杂富锂固溶体正极复合材料同时掺杂有阳离 子 Ma和阴离子 Mb。 阳离子 Ma占据双掺杂富锂固溶体正极复合材料中锂离子层 的位置， 阳离子 ^^半径大于 Li+半径， 在 Li+的嵌入和脱出的同时， 阳离子 Ma 作为支柱， 保持结构不会坍塌， 具有良好的结构稳定性， 从而解决了现有技术 此外， 阳离子 Ma作为支柱使得双掺杂富锂固溶体正极复合材料的层间距扩大， 利于 Li+的嵌入和脱出， 从层间距的角度提高了双掺杂富锂固溶体正极复合材料 的循环性能和倍率性能。 阴离子 Mb进入双掺杂富锂固溶体正极复合材料晶格， 与 0形成强的 Mb-0键， 减少氧在充放电过程中的析出， 从 Mb-0键的角度使 得双掺杂富锂固溶体正极复合材料具有良好的结构稳定性， 增强了充放电效率、 循环寿命和倍率性能。 In the first aspect of the embodiment of the present invention, the double-doped lithium-rich solid solution positive electrode composite material is simultaneously doped with a cation M a and an anion M b . The cation M a occupies the position of the lithium ion layer in the double-doped lithium-rich solid solution positive electrode composite, and the cation radius is larger than the Li + radius. At the same time as the insertion and extraction of Li + , the cation M a acts as a pillar to keep the structure from collapsing. The invention has the advantages of good structural stability and thus solves the prior art. In addition, the cation M a acts as a pillar to enlarge the interlayer spacing of the double-doped lithium-rich solid solution positive electrode composite material, which facilitates the insertion and extraction of Li + , and improves from the viewpoint of layer spacing. The cycle performance and rate performance of the dual doped lithium-rich solid solution cathode composite. The anion M b enters the crystal lattice of the double-doped lithium-rich solid solution cathode composite, forms a strong Mb-0 bond with 0, reduces the precipitation of oxygen during charge and discharge, and makes the double-doped lithium-rich solid solution from the angle of Mb-0 bond. The positive electrode composite has good structural stability and enhances charge and discharge efficiency, cycle life and rate performance.
第二方面，本发明实施例提供了一种双掺杂富锂固溶体正极复合材料的制备 方法， 包括以下步骤： In a second aspect, an embodiment of the present invention provides a method for preparing a dual-doped lithium-rich solid solution cathode composite material, comprising the following steps:
取可溶性 M盐溶解， M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中 一种或几种的组合， 制得 M元素的浓度为 0.5〜5mol/L的过渡金属盐水溶液； 取 碱或碳酸盐溶解， 制得 OH_的浓度为 l〜5mol/L 的 OH_溶液或 C03 2_的浓度为 l〜5mol/L 的 C03 2_溶液； 在持续搅拌的条件下， 将所述过渡金属盐水溶液加入 Off溶液或 C03 2-溶液中， 在制得的混合溶液中生成沉淀， 继续搅拌所述混合溶 液， 然后静置， 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的沉淀，
将所述收集得到的沉淀进行清洗并干燥， 制得前驱体； The soluble M salt is dissolved, and M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, and a transition metal having a M element concentration of 0.5 to 5 mol/L is obtained. saline solution; take or alkali carbonate dissolution, prepared OH_ concentration of l~5mol / L or a concentration of a solution OH_ C0 3 2 _ is l~5mol / L solution of C0 3 2 _; stirring was continued And adding the aqueous solution of the transition metal salt to the Off solution or the C0 3 2 - solution, forming a precipitate in the prepared mixed solution, continuing to stir the mixed solution, and then standing to obtain a solid-liquid mixed solution. Filtering, collecting the precipitate in the solid-liquid mixed solution, The collected precipitate is washed and dried to obtain a precursor;
按化学式 xLi2Mn03.(l-x)LiM02.yMaMb中的比例取锂盐、 MaMb和所述前驱 体混合制得混合物， 0<x<l , 0<y<0.1 , ^^为 Na和 K中的一种或组合， Mb为 F、 N 和 P 中的一种或几种的组合， 研磨， 制得研磨产物， 将所述研磨产物置于 40〜200°C的条件下干燥 l〜48h,制得干燥后的研磨产物； 将所述干燥后的研磨产 物置于马弗炉内，升温至 400〜800°C ,然后升温至 800〜1500°C ,恒温保持 0.5〜48 h, 随炉冷却至室温， 制得双掺杂富锂固溶体正极复合材料， 所述双掺杂富锂固 溶体正极复合材料化学式为： xLi2Mn03'(l-x)LiM02'yMaMb , 其中 0<χ<1 , 0<y<0.1 , M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或几种的 组合， ^^为 Na和 K中的一种或组合， Mb为 F、 Ν和 Ρ中的一种或几种的组合。 The mixture is prepared by mixing a lithium salt, M a M b and the precursor according to the ratio of the chemical formula xLi 2 Mn0 3 .(lx)LiM0 2 .yM a M b , 0<x<l, 0<y<0.1, ^^ is one or a combination of Na and K, M b is a combination of one or more of F, N and P, ground to obtain an abrasive product, and the ground product is placed at 40 to 200 ° C Drying for 1~48h, to obtain the dried grinding product; placing the dried ground product in a muffle furnace, heating to 400~800 °C, then heating to 800~1500 °C, keeping the temperature constant 0.5 to 48 h, the furnace is cooled to room temperature to obtain a double-doped lithium-rich solid solution cathode composite material, and the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: x Li 2 Mn0 3 '(lx)LiM0 2 'yM a M b , where 0<χ<1 , 0<y<0.1 , M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, ^^ is Na One or a combination of K and M, M b is a combination of one or more of F, Ν and Ρ.
其中， 优选地， 所述 M盐为醋酸盐、 草酸盐、 酸盐、 硝酸盐和氯化物中 的一种或几种的组合。 Preferably, the M salt is one or a combination of an acetate, an oxalate, an acid salt, a nitrate and a chloride.
优选地， 所述碱为 LiOH、 NaOH、 KOH、 氨水和铵盐中的一种或几种的组 合。 Preferably, the base is a combination of one or more of LiOH, NaOH, KOH, aqueous ammonia and ammonium salts.
优选地， 所述碳酸盐为 Li2C03、 Na2C03、 K2C03、 （N )2C03和 (N )HC03 中的一种或几种。 Preferably, the carbonate is one or more of Li 2 C0 3 , Na 2 C0 3 , K 2 C0 3 , (N ) 2 C0 3 and (N ) HC 0 3 .
优选地， 所述锂盐为氢氧化锂、 醋酸锂、 硝酸锂、 草酸锂、 硫酸锂、 碳酸 锂和氯化锂等一种或几种的组合。 Preferably, the lithium salt is one or a combination of lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium carbonate, and lithium chloride.
优选地， y的取值范围为 0.02 y 0.09。 更优选地， 所述 y的取值范围为 0.05 y 0.06。 Preferably, y has a value in the range of 0.02 y 0.09. More preferably, the value of y ranges from 0.05 y to 0.06.
优选地，将所述过渡金属盐水溶液以 0.1〜50ml/s的速度加入 OH_溶液或 C03 2_ 溶液中。 Preferably, the aqueous solution of the transition metal salt is added to the OH_solution or the C0 3 2 _ solution at a rate of 0.1 to 50 ml/s.
优选地，所述研磨为在所述混合物中加入乙醇和球磨珠，置于行星球磨机中，
在 100〜800 r/min, 持续球磨 0.5-24 h。 Preferably, the grinding is to add ethanol and ball beads to the mixture and place in a planetary ball mill. At 100~800 r/min, the ball is continuously milled for 0.5-24 h.
优选地， 继续搅拌所述混合溶液 10min〜12h, 然后静置 l〜48h。 Preferably, the mixed solution is continuously stirred for 10 min to 12 h, and then allowed to stand for l~48 h.
优选地， 将所述干燥后的研磨产物置于马弗炉内， 以 0.2〜20°C/min速度升 温至 400〜800°C , 然后以 l〜10°C/min速度升温至 800〜1500°C。 Preferably, the dried ground product is placed in a muffle furnace, heated to a temperature of 400 to 800 ° C at a rate of 0.2 to 20 ° C / min, and then heated to a temperature of 800 to 1500 at a rate of 1 to 10 ° C / min. °C.
本发明实施例第二方面中双掺杂富锂固溶体正极复合材料的制备方法为一 步合成法， 包括共沉淀合成前驱体和高温烧结制得双掺杂富锂固溶体正极复合 材料这两个步骤， 实现了将阳离子 阴离子 Mb同时掺杂的目的： 阳离子 Ma 占据部分双掺杂富锂固溶体正极复合材料中锂离子层的位置， 解决了现有技术 以及从层间距的角度提高了双掺杂富锂固溶体正极复合材料的循环性能和倍率 性能；阴离子 Mb进入双掺杂富锂固溶体正极复合材料晶格，与 0形成强的 Mb-0 键， 从 Mb-0键的角度使得双掺杂富锂固溶体正极复合材料具有良好的结构稳 定性， 增强了充放电效率、 循环寿命和倍率性能。 The preparation method of the double-doped lithium-rich solid solution cathode composite material in the second aspect of the present invention is a one-step synthesis method comprising the steps of coprecipitation synthesis precursor and high-temperature sintering to obtain a double-doped lithium-rich solid solution cathode composite material. The purpose of simultaneously doping the cationic anion M b is achieved: the cation M a occupies the position of the lithium ion layer in the partially doped lithium-rich solid solution positive electrode composite, which solves the prior art and improves the double doping from the viewpoint of layer spacing. Cycle performance and rate performance of lithium-rich solid solution cathode composite; anion M b enters the lattice of double-doped lithium-rich solid solution cathode composite, forming a strong Mb-0 bond with 0, making double doping from the angle of Mb-0 bond The lithium-rich solid solution cathode composite has good structural stability and enhanced charge and discharge efficiency, cycle life and rate performance.
本发明实施例第二方面提供的一种双掺杂富锂固溶体正极复合材料的制备 方法简单易行， 制得的双掺杂富锂固溶体正极复合材料具有良好的结构稳定性 , 增强了充放电效率、 循环寿命和倍率性能， 电压平台稳定。 The preparation method of the double-doped lithium-rich solid solution cathode composite material provided by the second aspect of the present invention is simple and easy, and the obtained double-doped lithium-rich solid solution cathode composite material has good structural stability and enhanced charge and discharge. Efficiency, cycle life and rate performance, voltage platform stability.
第三方面，本发明实施例提供了锂离子电池正极片，所述锂离子电池正极片 包括集流体和涂布在集流体上的双掺杂富锂固溶体正极复合材料， 所述双掺杂 富锂固溶体正极复合材料化学式为： xLi2Mn03.(l-x)LiM02.yMaMb, 其中 0<χ<1 , 0<y<0.1 , M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或几种的 组合， ^^为 Na和 K中的一种或组合， Mb为 F、 Ν和 Ρ中的一种或几种的组合。 In a third aspect, an embodiment of the present invention provides a positive electrode sheet for a lithium ion battery, the positive electrode sheet of the lithium ion battery comprising a current collector and a double-doped lithium-rich solid solution positive electrode composite coated on the current collector, the double-doped rich The lithium solid solution positive electrode composite has the chemical formula: xLi 2 Mn0 3 .(lx)LiM0 2 .yM a M b , where 0<χ<1, 0<y<0.1, M is Ni, Co, Mn, Ti, Ah Zr, A combination of one or more of Fe, V, Mg and W, ^^ is one or a combination of Na and K, and M b is a combination of one or more of F, Ν and Ρ.
优选地， y的取值范围为 0.02 y 0.09。 更优选地， 所述 y的取值范围为 0.05 y 0.06。
锂离子电池正极片的制备方法为： 将双掺杂富锂固溶体正极复合材料、导电 剂、 粘结剂和溶剂混合制得浆料， 将浆料涂布在集流体上， 随后进行干燥和压 片， 制得锂离子电池正极片。 Preferably, y has a value in the range of 0.02 y 0.09. More preferably, the value of y ranges from 0.05 y to 0.06. The preparation method of the positive electrode sheet of the lithium ion battery is as follows: mixing the double-doped lithium-rich solid solution positive electrode composite material, the conductive agent, the binder and the solvent to prepare a slurry, and coating the slurry on the current collector, followed by drying and pressing Tablet, a positive electrode for lithium ion batteries.
本发明实施例第三方面提供的锂离子电池正极片可用于制备锂离子电池。 第四方面， 本发明实施例提供了一种锂离子电池， 包括锂离子电池正极片、 锂离子电池负极片、 隔膜和电解液， 所述锂离子电池正极片包括集流体和涂布 在集流体上的双掺杂富锂固溶体正极复合材料， 所述双掺杂富锂固溶体正极复 合材料化学式为： xLi2Mn03 l-x)LiM02-yMaMb, 其中 0<x<l , 0<y<0.1 , M 为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或几种的组合， Ma为 Na 和 K中的一种或组合， ^1¾为 F、 N和 P中的一种或几种的组合。 The positive electrode sheet of the lithium ion battery provided by the third aspect of the embodiment of the present invention can be used for preparing a lithium ion battery. In a fourth aspect, an embodiment of the present invention provides a lithium ion battery, including a positive electrode sheet of a lithium ion battery, a negative electrode sheet of a lithium ion battery, a separator, and an electrolyte, wherein the positive electrode sheet of the lithium ion battery includes a current collector and is coated on the current collector The double-doped lithium-rich solid solution cathode composite material, the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: xLi 2 Mn0 3 lx)LiM0 2 -yM a M b , where 0<x<l, 0<y <0.1 , M is a combination of one or more of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, and M a is one or a combination of Na and K, and ^1 3⁄4 is F , a combination of one or more of N and P.
优选地， y的取值范围为 0.02 y 0.09。 更优选地， 所述 y的取值范围为 0.05 y 0.06。 Preferably, y has a value in the range of 0.02 y 0.09. More preferably, the value of y ranges from 0.05 y to 0.06.
本发明实施例第四方面提供的锂离子电池电压平台稳定，循环寿命长，具有 优良的倍率性能和充放电效率。 The lithium ion battery voltage platform provided by the fourth aspect of the embodiments of the present invention is stable, has a long cycle life, and has excellent rate performance and charge and discharge efficiency.
本发明实施例的优点将会在下面的说明书中部分阐明，一部分根据说明书是 显而易见的， 或者可以通过本发明实施例的实施而获知。 附图说明 The advantages of the embodiments of the present invention will be set forth in part in the description which follows. DRAWINGS
图 1为背景技术富锂锰基固溶体正极材料 xLi[Li1/3Mn2/3]02 · (l-x)LiM02中层 状化合物 LiMC 结构示意图。 1 is a schematic view showing the structure of a layered compound LiMC in a lithium-rich manganese-based solid solution cathode material xLi[Li 1/3 Mn 2/3 ]0 2 · (lx)LiM0 2 .
图 2为本发明实施例双掺杂富锂锰基固溶体正极材料中层状化合物 LiM02的 结构示意图。 2 is a schematic view showing the structure of a layered compound LiM0 2 in a double-doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention.
图 3为本发明实施例双掺杂富锂锰基固溶体正极材料中层状化合物 Li2Mn03
的结构示意图 具体实施方式 3 is a layered compound Li 2 Mn0 3 in a dual doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention ; Schematic diagram of the structure
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普 通技术人员来说， 在不脱离本发明实施例原理的前提下， 还可以做出若干改进 和润饰， 这些改进和润饰也视为本发明实施例的保护范围。 The following are the preferred embodiments of the embodiments of the present invention, and it should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.
下面以扣式锂离子电池（型号为 2025 ) 的制作和测试为例， 分多个实施例 对本发明实施例进行进一步的说明。 其中， 本发明实施例不限定于以下的具体 实施例。 在不变主权利的范围内， 可以适当的进行变更实施。 In the following, the fabrication and testing of a button-type lithium ion battery (model 2025) is taken as an example, and the embodiments of the present invention are further described in various embodiments. The embodiments of the present invention are not limited to the following specific embodiments. Changes can be implemented as appropriate within the scope of the invariable principal rights.
实施例一 Embodiment 1
一 种 双 掺 杂 富 锂 固 溶 体 正 极 复 合 材 料 ( 0.4Li2MnO3'0.6LiNi0.38Co0.24Mn0.38O2O.05NaF ) 的制备方法， 包括以下步骤： 取醋酸锰、 醋酸镍、 醋酸钴按摩尔比为 4.4:1.6:1 的比例溶于蒸馏水中， 制 得锰、镍和钴的总浓度为 lmol/L的过渡金属盐水溶液； 取 LiOH溶于蒸馏水中， 制得 OH_的浓度为 2mol/L的 OH_溶液； 在持续搅拌的条件下， 将 80 ml所述过 渡金属盐水溶液以 2ml/s的速度加入 lOO ml OH-溶液中，在制得的混合溶液中生 成沉淀， 待混合溶液的颜色由白色逐渐变成棕色后继续搅拌 lh, 然后静置 24h, 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的棕色的沉淀， 将所述收 集得到的沉淀用 400 ml蒸馏水清洗 4次， 随后将沉淀置于 120°C干燥箱中干燥 24 h, 制得前驱体； A preparation method of a double-doped lithium-rich solid solution cathode composite material (0.4Li 2 MnO 3 '0.6LiNi 0 . 38 Co 0 . 24 Mn 0 . 38 O 2 O.05NaF ), comprising the following steps: taking manganese acetate, acetic acid The ratio of nickel to cobalt acetate is 4.4:1.6:1 dissolved in distilled water to prepare a transition metal salt solution with a total concentration of 1 mol/L of manganese, nickel and cobalt; LiOH is dissolved in distilled water to obtain OH. _ concentration of 2mol / L OH_ solution; under continuous stirring, 80 ml of the aqueous solution of the transition metal salt was added to 100 ml of OH-solution at a rate of 2 ml / s, and was formed in the prepared mixed solution. Precipitating, the color of the solution to be mixed is gradually changed from white to brown, and stirring is continued for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered, and the brown precipitate in the solid-liquid mixed solution is collected, and the collection is obtained. The precipitate was washed 4 times with 400 ml of distilled water, and then the precipitate was placed in a drying oven at 120 ° C for 24 h to prepare a precursor;
取 5g所述前驱体， 按摩尔比为 0.712:0.05: 1的比例将 Li2C03、 NaF和所述 前驱体混合制得混合物， 在所述混合物中加入 10ml乙醇， 置于研钵中， 混合均 匀， 制得研磨产物， 将所述研磨产物置于 80°C的条件下干燥 12h, 制得干燥后
的研磨产物； 将所述干燥后的研磨产物置于马弗炉内， 以 0.2°C/min速度升温至 400 °C , 然后以 rC/min速度升温至 800°C , 恒温保持 0.5h, 随炉冷却至室温， 制得双掺杂富锂固溶体正极复合材料， 所述双掺杂富锂固溶体正极复合材料化 学式为： 0.4Li2MnO3'0.6LiNi0.38Co0 24Mn0 38O2'0.05NaF。 Taking 5 g of the precursor, a mixture of Li 2 CO 3 , NaF and the precursor was mixed at a molar ratio of 0.712:0.05:1, and 10 ml of ethanol was added to the mixture, which was placed in a mortar. The mixture was uniformly mixed to obtain an abrasive product, and the ground product was dried at 80 ° C for 12 hours to obtain a dried product. Grinding product; placing the dried ground product in a muffle furnace, raising the temperature to 400 ° C at a rate of 0.2 ° C / min, then raising the temperature to 800 ° C at a rate of r C / min, maintaining a constant temperature for 0.5 h, with The furnace is cooled to room temperature to obtain a double-doped lithium-rich solid solution cathode composite material having a chemical formula of: 0.4Li 2 MnO 3 '0.6LiNi 0 . 38 Co 0 2 4Mn 0 38 O 2 '0.05 NaF.
锂离子电池正极片的制备方法 Method for preparing positive electrode sheet of lithium ion battery
将双掺杂富锂固溶体正极复合材料： 乙炔黑： PVDF: NMP 按质量比为 8:1:1 :100比例混合， 用异丙醇调成均匀浆料， 均匀涂布在铝片上， 于 120 真 空干燥 18 h, 压片， 制得锂离子电池正极片。 Double-doped lithium-rich solid solution positive electrode composite: acetylene black: PVDF: NMP is mixed in a mass ratio of 8:1:1:100, adjusted to a uniform slurry with isopropyl alcohol, uniformly coated on aluminum sheet, at 120 Vacuum drying for 18 h, tableting, to obtain a positive electrode of a lithium ion battery.
锂离子电池的制备方法 Method for preparing lithium ion battery
将本实施例中制得的锂离子电池正极片在 Ar保护的手套箱中与 Li金属负 极片、 隔膜和电解液组装成型号为 2025的扣式电池， 并进行电化学性能检测。 The positive electrode sheet of the lithium ion battery obtained in the present example was assembled into a button cell of No. 2025 in a Ar-protected glove box with a Li metal negative electrode sheet, a separator and an electrolyte, and electrochemical performance was measured.
实施例二 Embodiment 2
一 种 双 掺 杂 富 锂 固 溶 体 正 极 复 合 材 料 ( 0.5Li2MnO3'0.5LiNi。.38Co。.24Mn。.38O2O.02KF ) 的制备方法， 包括以下步骤： 取硝酸锰、 硝酸镍、 硝酸钴按摩尔比为 3.7:1.6:1 的比例溶于蒸馏水中， 制 得锰、镍和钴的总浓度为 lmol/L的过渡金属盐水溶液；取 NaOH溶于蒸馏水中 , 制得 OH_的浓度为 2mol/L的 OH_溶液； 在持续搅拌的条件下， 将 80 ml所述过 渡金属盐水溶液以 2ml/s的速度加入 lOO ml OH-溶液中，在制得的混合溶液中生 成沉淀， 待混合溶液的颜色由白色逐渐变成棕色后继续搅拌 lh, 然后静置 24h, 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的棕色的沉淀， 将所述收 集得到的沉淀用 400 ml蒸馏水清洗 4次， 随后将沉淀置于 120°C干燥箱中干燥 24 h, 制得前驱体； A preparation method of a double-doped lithium-rich solid solution positive electrode composite material (0.5Li 2 MnO 3 '0.5LiNi.. 38 Co.. 24 Mn.. 38 O 2 O.02KF), comprising the following steps: taking manganese nitrate, nitric acid The ratio of nickel to cobalt nitrate is 3.7:1.6:1 dissolved in distilled water to prepare a transition metal salt solution with a total concentration of 1 mol/L of manganese, nickel and cobalt; NaOH is dissolved in distilled water to obtain OH. _ concentration of 2mol / L OH_ solution; under continuous stirring, 80 ml of the aqueous solution of the transition metal salt was added to 100 ml of OH-solution at a rate of 2 ml / s, and was formed in the prepared mixed solution. Precipitating, the color of the solution to be mixed is gradually changed from white to brown, and stirring is continued for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered, and the brown precipitate in the solid-liquid mixed solution is collected, and the collection is obtained. The precipitate was washed 4 times with 400 ml of distilled water, and then the precipitate was placed in a drying oven at 120 ° C for 24 h to prepare a precursor;
取 5g所述前驱体， 按摩尔比为 0.773:0.02: 1的比例取 Li2C03、 KF和所述前
驱体混合制得混合物，在所述混合物中加入 10ml乙醇， 置于研钵中， 混合均匀， 置于 80°C的干燥箱中， 干燥 12 h, 制得研磨产物， 将所述研磨产物置于 80 °C的 条件下干燥 12h, 制得干燥后的研磨产物； 将所述干燥后的研磨产物置于马弗炉 内， 以 20°C/min速度升温至 800°C , 然后以 10°C/min速度升温至 1500°C , 恒温 保持 48h, 随炉冷却至室温， 制得双掺杂富锂固溶体正极复合材料， 所述双掺杂 富 锂 固 溶 体 正 极 复 合 材 料 化 学 式 为 ： 0.5Li2MnO3-0.5LiNi0.38Co0.24Mn0 38O2-0.02KF。 Taking 5 g of the precursor, taking Li 2 C0 3 , KF and the former in a ratio of a molar ratio of 0.773:0.02:1 The mixture was prepared by mixing the mixture, 10 ml of ethanol was added to the mixture, placed in a mortar, uniformly mixed, placed in a drying oven at 80 ° C, and dried for 12 h to prepare an abrasive product, and the ground product was set. Drying at 80 ° C for 12 h to prepare a dried ground product; placing the dried ground product in a muffle furnace, raising the temperature to 800 ° C at a rate of 20 ° C / min, then 10 ° The C/min speed is raised to 1500 ° C, the temperature is maintained for 48 h, and the furnace is cooled to room temperature to obtain a double-doped lithium-rich solid solution cathode composite material. The chemical formula of the double-doped lithium-rich solid solution cathode composite material is: 0.5Li 2 MnO 3 -0.5LiNi 0 . 38 Co 0 . 2 4Mn 0 38 O 2 -0.02 KF.
锂离子电池正极片的制备方法和锂离子电池的制备方法均与实施例一中相 同。 The preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
实施例三 Embodiment 3
一 种 双 掺 杂 富 锂 固 溶 体 正 极 复 合 材 料 ( 0.55Li2Mn03-0.45LiNio.o.4Coo.2Mno.402-0.09Na3N ) 的制备方法， 包括以下步骤： 取硫酸锰、 硫酸镍、 硫酸钴按摩尔比为 8.1 :2:1 的比例溶于蒸馏水中， 制得 锰、 镍和钴的总浓度为 lmol/L的过渡金属盐水溶液； 取 Na2C03溶于蒸馏水中， 制得 C03 2_的浓度为 2mol/L的 C03 2_溶液； 在持续搅拌的条件下， 将 80 ml所述 过渡金属盐水溶液以 2ml/s的速度加入 100 ml CO^溶液中， 在制得的混合溶液 中生成沉淀， 待混合溶液的颜色由白色逐渐变成棕色后继续搅拌 lh, 然后静置 24h, 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的棕色的沉淀， 将所 述收集得到的沉淀用 400 ml蒸馏水清洗 4次， 随后将沉淀置于 120°C干燥箱中 干燥 24 h, 制得前驱体； A method for preparing a double-doped lithium-rich solid solution cathode composite material (0.55Li 2 Mn0 3 -0.45LiNio.o.4Coo.2Mno. 4 0 2 -0.09Na 3 N ) comprises the following steps: taking manganese sulfate, nickel sulfate The cobalt sulfate has a ratio of 8.1:2:1 dissolved in distilled water to prepare a transition metal salt solution with a total concentration of 1 mol/L of manganese, nickel and cobalt; and Na 2 CO 3 is dissolved in distilled water. to give a concentration of C0 3 2 _ 2mol / L solution of C0 3 2 _; With continued stirring, 80 ml of the transition metal salt aqueous solution at a rate of 2ml / s was added 100 ml CO ^ solution, prepared A precipitate is formed in the obtained mixed solution, the color of the solution to be mixed is gradually changed from white to brown, and stirring is continued for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered to collect a brown precipitate in the solid-liquid mixed solution. The collected precipitate is washed 4 times with 400 ml of distilled water, and then the precipitate is dried in a 120 ° C dry box for 24 h to prepare a precursor;
取 5g所述前驱体， 按摩尔比为 0.798:0.03: 1的比例取 Li2C03、 Na3N和所述 前驱体混合制得混合物， 在所述混合物中加入 10ml乙醇， 置于研钵中， 混合均 匀，置于 80°C的干燥箱中，干燥 12 h,制得研磨产物，将所述研磨产物置于 80°C
的条件下干燥 12h, 制得干燥后的研磨产物； 将所述干燥后的研磨产物置于马弗 炉内， 以 10°C/min速度升温至 600°C , 然后以 5°C/min速度升温至 1000°C , 恒 温保持 24h, 随炉冷却至室温， 制得双掺杂富锂固溶体正极复合材料， 所述双掺 杂 富 锂 固 溶 体 正 极 复 合 材 料 化 学 式 为 ： 0.55Li2MnO3'0.45LiNi0 0.4Co02Mn0.4O2'0.09Na3N。 5 g of the precursor was taken, and a mixture of Li 2 CO 3 , Na 3 N and the precursor was mixed at a molar ratio of 0.798:0.03:1 to prepare a mixture, and 10 ml of ethanol was added to the mixture, and the mixture was placed in a mortar. Medium, uniformly mixed, placed in a drying oven at 80 ° C, dried for 12 h, to obtain an abrasive product, and the ground product was placed at 80 ° C Drying for 12 h, to obtain a dried ground product; placing the dried ground product in a muffle furnace, raising the temperature to 600 ° C at a rate of 10 ° C / min, and then at a rate of 5 ° C / min The temperature is raised to 1000 ° C, the temperature is maintained for 24 h, and the furnace is cooled to room temperature to obtain a double-doped lithium-rich solid solution cathode composite material. The chemical formula of the double-doped lithium-rich solid solution cathode composite material is: 0.55Li 2 MnO 3 '0.45LiNi 0 0 .4Co 02 Mn 0 .4O 2 '0.09Na 3 N.
锂离子电池正极片的制备方法和锂离子电池的制备方法均与实施例一中相 同。 The preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
实施例四 Embodiment 4
一种双掺杂富锂固溶体正极复合材料 ( 0.6Li2Mn03-0.4LiNio.34Coo.24Mn0.38 Mg0.04O2-0.06K3P ) 的制备方法， 包括以下步骤： A preparation method of a double-doped lithium-rich solid solution cathode composite material (0.6Li 2 Mn0 3 -0.4LiNio. 34 Coo.24Mn 0 . 3 8 Mg 0 .04O 2 -0.06K 3 P ) comprises the following steps:
取硫酸锰、 硫酸镍、 硫酸镁、 硫酸钴按摩尔比为 7.8: 1.4:0.17:1 的比例溶于 蒸馏水中， 制得锰、镍和钴的总浓度为 lmol/L的过渡金属盐水溶液； 取 Na2C03 溶于蒸馏水中，制得 ( 03 2_的浓度为 2mol/L的 C03 2_溶液；在持续搅拌的条件下， 将 80 ml所述过渡金属盐水溶液以 2ml/s的速度加入 100 ml CO^溶液中， 在制 得的混合溶液中生成沉淀， 待混合溶液的颜色由白色逐渐变成棕色后继续搅拌 lh, 然后静置 24h, 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的棕色 的沉淀， 将所述收集得到的沉淀用 400 ml蒸馏水清洗 4 次， 随后将沉淀置于 120°C干燥箱中干燥 24 h, 制得前驱体； Taking a ratio of 7.8: 1.4:0.17:1 in a molar ratio of manganese sulfate, nickel sulfate, magnesium sulfate and cobalt sulfate to distilled water to prepare a transition metal salt aqueous solution having a total concentration of manganese, nickel and cobalt of 1 mol/L; Na 2 C0 3 was dissolved in distilled water to prepare a solution of 0 3 2 _ 2 mol/L of C0 3 2 _ solution; under continuous stirring, 80 ml of the aqueous solution of the transition metal salt was 2 ml/s. The speed is added to 100 ml of CO^ solution, and a precipitate is formed in the prepared mixed solution. The color of the mixed solution is gradually changed from white to brown and then stirred for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered. Collecting the brown precipitate in the solid-liquid mixed solution, and washing the collected precipitate 4 times with 400 ml of distilled water, and then drying the precipitate in a drying oven at 120 ° C for 24 h to prepare a precursor;
取 5g所述前驱体， 按摩尔比为 0.824:0.02:1的比例取 Li2C03、 K3P和所述 前驱体混合制得混合物， 置于 50ml的研磨罐中， 在所述混合物中加入 10ml乙 醇， 同时加入一定量的球磨珠（球磨珠： 混合物 =10:1 wt% ), 行星球磨机中 400 转 /min球磨 4h, 混合均匀， 置于 80 °C的干燥箱中， 干燥 12 h, 制得研磨产物， 将所述研磨产物置于 80 °C的条件下干燥 12h, 制得干燥后的研磨产物； 将所述
干燥后的研磨产物置于马弗炉内，以 10°C/min速度升温至 600 °C ,然后以 5°C/min 速度升温至 1000°C , 恒温保持 24h, 随炉冷却至室温， 制得双掺杂富锂固溶体 正极复合材料， 所述双掺杂富锂固溶体正极复合材料化学式为： 0.6Li2Mn03-0.4LiNio.34Coo.24Mn0.38 Mg0.04O2'0.06K3P。 Taking 5 g of the precursor, mixing Li 2 C0 3 , K 3 P and the precursor in a molar ratio of 0.824:0.02:1 to prepare a mixture, which is placed in a 50 ml grinding tank in the mixture. Add 10ml of ethanol, add a certain amount of ball beads (ball mill beads: mixture = 10:1 wt%), ball mill for 400h/min ball milling for 4h, mix evenly, place in a drying oven at 80 °C, dry for 12 h , grinding the product, and drying the ground product at 80 ° C for 12 h to prepare a dried abrasive product; The dried grinding product is placed in a muffle furnace, heated to 600 ° C at a rate of 10 ° C / min, then heated to 1000 ° C at a rate of 5 ° C / min, kept at a constant temperature for 24 h, and cooled to room temperature with the furnace. The double-doped lithium-rich solid solution cathode composite material has a chemical formula of 0.6Li2Mn0 3 -0.4LiNio.34Coo.24Mn 0 .38 Mg 0 . 04 O 2 '0.06K 3 P.
锂离子电池正极片的制备方法和锂离子电池的制备方法均与实施例一中相 同。 The preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
对比例一 Comparative example one
一种富锂固溶体正极复合材料 ( 0.55Li2Mn03-0.45LiNio.o.4Coo.2Mno.402 )的制 备方法， 包括以下步骤： A preparation method of a lithium-rich solid solution positive electrode composite material (0.55Li 2 Mn0 3 -0.45LiNio.o.4Coo.2Mno. 4 0 2 ), comprising the following steps:
取硫酸锰、 硫酸镍、 硫酸钴按摩尔比为 8.1 :2:1 的比例溶于蒸馏水中， 制得 锰、 镍和钴的总浓度为 lmol/L的过渡金属盐水溶液； 取 LiOH溶于蒸馏水中， 制得 OH_的浓度为 2mol/L的 OH_溶液； 在持续搅拌的条件下， 将 80 ml所述过 渡金属盐水溶液以 2ml/s的速度加入 100 ml C03 2-溶液中， 在制得的混合溶液中 生成沉淀,待混合溶液的颜色由白色逐渐变成棕色后继续搅拌 lh,然后静置 24h, 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的棕色的沉淀， 将所述收 集得到的沉淀用 400 ml蒸馏水清洗 4次， 随后将沉淀置于 120°C干燥箱中干燥 24 h, 制得前驱体； Taking a molar ratio of manganese sulfate, nickel sulfate and cobalt sulfate to a molar ratio of 8.1:2:1 in distilled water to prepare a transition metal salt solution having a total concentration of manganese, nickel and cobalt of 1 mol/L; taking LiOH dissolved in distilled water Preparing an OH_ solution having a concentration of OH_ of 2 mol/L; adding 80 ml of the aqueous solution of the transition metal salt to a solution of 100 ml of C0 3 2- at a rate of 2 ml/s under continuous stirring. A precipitate is formed in the prepared mixed solution, the color of the solution to be mixed is gradually changed from white to brown, and stirring is continued for 1 hour, and then allowed to stand for 24 hours to prepare a solid-liquid mixed solution, which is filtered to collect brown in the solid-liquid mixed solution. Precipitating, washing the collected precipitate with 400 ml of distilled water 4 times, and then drying the precipitate in a 120 ° C drying oven for 24 h to prepare a precursor;
取 5g所述前驱体， 按摩尔比为 0.798:1的比例取 Li2C03、 Na3N和所述前驱 体混合制得混合物， 在所述混合物中加入 10ml乙醇， 置于研钵中， 混合均匀， 置于 80°C的干燥箱中， 干燥 12 h, 制得研磨产物， 将所述研磨产物置于 80 °C的 条件下干燥 12h, 制得干燥后的研磨产物； 将所述干燥后的研磨产物置于马弗炉 内， 以 10°C/min速度升温至 600°C , 然后以 5°C/min速度升温至 1000°C , 恒温 保持 24h, 随炉冷却至室温， 制得双掺杂富锂固溶体正极复合材料， 所述富锂固
溶体正极复合材料化学式为： 0.55Li2MnO3'0.45LiNi。.。.4Co。.2Mn。.4O2。 锂离子电池正极片的制备方法和锂离子电池的制备方法均与实施例一中相 同。 5 g of the precursor was taken, and a mixture of Li 2 CO 3 , Na 3 N and the precursor was mixed at a molar ratio of 0.798:1 to prepare a mixture, and 10 ml of ethanol was added to the mixture, which was placed in a mortar. The mixture was uniformly mixed, placed in a drying oven at 80 ° C, dried for 12 h to prepare an abrasive product, and the ground product was dried at 80 ° C for 12 hours to prepare a dried ground product; The post-grinding product is placed in a muffle furnace, heated to 600 ° C at a rate of 10 ° C / min, then heated to 1000 ° C at a rate of 5 ° C / min, maintained at a constant temperature for 24 h, and cooled to room temperature with the furnace. Double doped lithium-rich solid solution cathode composite material, said lithium-rich solid The chemical formula of the solution positive electrode composite is: 0.55Li 2 MnO 3 '0.45LiNi. . . . .4Co. . 2 Mn. . 4 O 2 . The preparation method of the positive electrode sheet of the lithium ion battery and the preparation method of the lithium ion battery are the same as those in the first embodiment.
以上实施例和对比例中制得的锂离子电池为实验电池， 用于下述效果实施 例性能测试。 The lithium ion batteries produced in the above examples and comparative examples were experimental batteries for the performance test of the following effect examples.
效果实施例 Effect embodiment
为对本发明实施例技术方案带来的有益效果进行有力支持， 特提供以下性 能测试： In order to strongly support the beneficial effects brought by the technical solutions of the embodiments of the present invention, the following performance tests are provided:
1. 首次放电容量性能测试 1. First discharge capacity performance test
分别在充放电速率为 0.1C和 1C, 以及充放电电压范围 2〜4.6 V的条件下测 量实施例和对比例中制得的锂离子电池的首次放电容量。 The first discharge capacities of the lithium ion batteries obtained in the examples and the comparative examples were measured under the conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively.
2.首次充放电效率性能测试 2. First charge and discharge efficiency performance test
分别在充放电速率为 0.1C和 1C, 以及充放电电压范围 2〜4.6 V的条件下测 量实施例和对比例中制得的锂离子电池的首次放电容量和充电容量， 计算首次 充放电效率， 首次充放电效率 =首次放电容量 /首次充电容量。 The first discharge capacity and the charge capacity of the lithium ion batteries obtained in the examples and the comparative examples were measured under the conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively, and the first charge and discharge efficiency was calculated. First charge and discharge efficiency = first discharge capacity / first charge capacity.
3. 50次循环容量性能测试 3. 50 cycle capacity performance test
分别在充放电速率为 0.1C和 1C, 以及充放电电压范围 2〜4.6 V的条件下测 量实施例和对比例中制得的锂离子电池的循环 50次后的放电容量。 The discharge capacities of the lithium ion batteries obtained in the examples and the comparative examples after 50 cycles were measured under conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively.
4.50次放电电压 /首次放电电压 4.50 discharge voltage / first discharge voltage
分别在充放电速率为 0.1C和 1C, 以及充放电电压范围 2〜4.6 V的条件下测 量实施例和对比例中制得的锂离子电池的 50次放电电压 /首次放电电压。 The 50 discharge voltages/first discharge voltages of the lithium ion batteries obtained in the examples and the comparative examples were measured under the conditions of a charge and discharge rate of 0.1 C and 1 C, and a charge and discharge voltage range of 2 to 4.6 V, respectively.
表 1和表 2为本发明实施例和对比例首次放电容量性能测试、 首次充放电 效率性能测试和 50次循环容量性能测试结果。
表 1 在充放电电流为 0.1C, 充放电电压区间为 2〜4.6 V的电化学性能比较 Table 1 and Table 2 are the first discharge capacity performance test, the first charge and discharge efficiency performance test, and the 50 cycle capacity performance test results of the examples and comparative examples of the present invention. Table 1 Comparison of electrochemical performance at a charge-discharge current of 0.1 C and a charge-discharge voltage range of 2 to 4.6 V
( 1 )本发明实施例一和实施例二提供的双掺杂富锂固溶体正极复合材料相 比对比例一具有更高的放电容量； (1) The double-doped lithium-rich solid solution positive electrode composite provided in the first embodiment and the second embodiment of the present invention has a higher discharge capacity than the first comparative example;
( 2 )本发明实施例一、 实施例二和实施例三提供的双掺杂富锂固溶体正极 复合材料相比对比例一具有更高的首次充放电效率、 更好的循环性能、 更高的 电压稳定性以及更优秀的倍率性能。 (2) The dual-doped lithium-rich solid solution cathode composite provided in the first embodiment, the second embodiment and the third embodiment has higher first charge and discharge efficiency, better cycle performance, and higher ratio than the first embodiment. Voltage stability and better rate performance.
图 2为本发明实施例双掺杂富锂锰基固溶体正极材料中层状化合物 LiM02 的结构示意图。 图 3 为本发明实施例双掺杂富锂锰基固溶体正极材料中层状化
合物 Li2Mn03的结构示意图。 本发明实施例提供的双掺杂富锂固溶体正极复合 材料同时掺杂有阳离子 Ma和阴离子 Mb。 阳离子 Ma占据双掺杂富锂固溶体正极 复合材料中锂离子层的位置， 阳离子 ^^半径大于 Li+半径， 在 Li+的嵌入和脱出 的同时， 阳离子 Ma作为支柱， 保持结构不会坍塌， 具有良好的结构稳定性， 从 而解决了现有技术中富锂固溶体正极材料在循环过程中因结构坍塌导致的电压 平台下降的问题。 此外， 阳离子 为支柱使得双掺杂富锂固溶体正极复合材 料的层间距扩大， 利于 Li+的嵌入和脱出， 从层间距的角度提高了双掺杂富锂固 溶体正极复合材料的循环性能和倍率性能。 阴离子 Mb进入双掺杂富锂固溶体正 极复合材料晶格， 与 0形成强的 Mb-0键， 减少氧在充放电过程中的析出， 从 Mb-0键的角度使得双掺杂富锂固溶体正极复合材料具有良好的结构稳定性 ,增 强了充放电效率、 循环寿命和倍率性能。
2 is a schematic view showing the structure of a layered compound LiM0 2 in a double-doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention. 3 is a layered layer of a double doped lithium-rich manganese-based solid solution cathode material according to an embodiment of the present invention; Schematic diagram of the structure of Li 2 MnO 3 . The dual-doped lithium-rich solid solution cathode composite provided by the embodiment of the invention is simultaneously doped with a cation M a and an anion M b . The cation M a occupies the position of the lithium ion layer in the double-doped lithium-rich solid solution positive electrode composite, and the cation radius is larger than the Li + radius. At the same time as the insertion and extraction of Li + , the cation M a acts as a pillar to keep the structure from collapsing. The invention has good structural stability, thereby solving the problem that the voltage platform of the lithium-rich solid solution cathode material in the prior art is reduced due to structural collapse during the cycle. In addition, the cation is the pillar to enlarge the interlayer spacing of the double-doped lithium-rich solid solution cathode composite, which facilitates the insertion and extraction of Li + , and improves the cycle performance and rate performance of the double-doped lithium-rich solid solution cathode composite from the viewpoint of layer spacing. . The anion M b enters the crystal lattice of the double-doped lithium-rich solid solution cathode composite, forms a strong Mb-0 bond with 0, reduces the precipitation of oxygen during charge and discharge, and makes the double-doped lithium-rich solid solution from the angle of Mb-0 bond. The positive electrode composite has good structural stability and enhances charge and discharge efficiency, cycle life and rate performance.
Claims
1、 一种双掺杂富锂固溶体正极复合材料， 其特征在于， 所述双掺杂富锂固 溶体正极复合材料化学式为： xLi2Mn03'(l-x)LiM02'yMaMb , 其中 0<χ<1 , 0<y<0.1 , M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或几种的 组合， ^^为 Na和 K中的一种或组合， Mb为 F、 Ν和 Ρ中的一种或几种的组合。 1. A double-doped lithium-rich solid solution cathode composite material, characterized in that the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: x Li 2 Mn0 3 '(lx)LiM0 2 'yM a M b , where 0<χ<1, 0<y<0.1, M is one or a combination of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, ^^ is one of Na and K Kind or combination, M b is one or a combination of several of F, N and P.
2、如权利要求 1所述的一种双掺杂富锂固溶体正极复合材料，其特征在于， 所述 y的取值范围为 0.02 y 0.09。 2. A double-doped lithium-rich solid solution cathode composite material as claimed in claim 1, characterized in that the value range of y is 0.02 y 0.09.
3、 一种双掺杂富锂固溶体正极复合材料的制备方法， 其特征在于， 包括以 下步骤： 3. A method for preparing a double-doped lithium-rich solid solution cathode composite material, which is characterized by including the following steps:
取可溶性 M盐溶解， M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中 一种或几种的组合， 制得 M元素的浓度为 0.5〜5mol/L的过渡金属盐水溶液； 取 碱或碳酸盐溶解， 制得 OH_的浓度为 l〜5mol/L 的 OH_溶液或 C03 2_的浓度为 l〜5mol/L 的 C03 2_溶液； 在持续搅拌的条件下， 将所述过渡金属盐水溶液加入 Off溶液或 C03 2-溶液中， 在制得的混合溶液中生成沉淀， 继续搅拌所述混合溶 液， 然后静置， 制得固液混合溶液， 过滤， 收集所述固液混合溶液中的沉淀， 将所述收集得到的沉淀进行清洗并干燥， 制得前驱体； Dissolve the soluble M salt, where M is one or a combination of Ni, Co, Mn, Ti, Ah Zr, Fe, V, Mg and W, to obtain a transition metal with a concentration of M element of 0.5~5 mol/L Salt water solution; Dissolve alkali or carbonate to obtain an OH_ solution with an OH_ concentration of 1~5mol/L or a C032_ solution with a C032_ concentration of 1 ~ 5mol /L; stir continuously Under the conditions of , add the transition metal aqueous solution to Off solution or C0 3 2 - solution, generate a precipitate in the prepared mixed solution, continue to stir the mixed solution, and then let it stand to prepare a solid-liquid mixed solution, Filter, collect the precipitates in the solid-liquid mixed solution, wash and dry the collected precipitates to prepare a precursor;
按化学式 xLi2Mn03.(l-x)LiM02.yMaMb中的比例取锂盐、 MaMb和所述前驱 体混合制得混合物， 0<x<l , 0<y<0.1 , ^^为 Na和 K中的一种或组合， Mb为 F、 N 和 P 中的一种或几种的组合， 研磨， 制得研磨产物， 将所述研磨产物置于 40〜200°C的条件下干燥 l〜48h,制得干燥后的研磨产物； 将所述干燥后的研磨产
物置于马弗炉内，升温至 400〜800°C ,然后升温至 800〜1500°C ,恒温保持 0.5〜48 h, 随炉冷却至室温， 制得双掺杂富锂固溶体正极复合材料， 所述双掺杂富锂固 溶体正极复合材料化学式为： xLi2Mn03'(l-x)LiM02'yMaMb , 其中 0<χ<1 , 0<y<0.1 , M为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或几种的 组合， ^^为 Na和 K中的一种或组合， Mb为 F、 Ν和 Ρ中的一种或几种的组合。 According to the chemical formula xLi 2 Mn0 3 .(lx)LiM0 2 .yM a M b , the lithium salt, M a M b and the precursor are mixed to prepare a mixture, 0<x<l, 0<y<0.1, ^ is one or a combination of Na and K, M b is one or a combination of F, N and P, grind to obtain a ground product, and place the ground product at 40~200°C Dry under the conditions for 1~48h to obtain the dried grinding product; The dried grinding product is The material is placed in a muffle furnace, heated to 400~800°C, then raised to 800~1500°C, kept at a constant temperature for 0.5~48 hours, and cooled to room temperature with the furnace to prepare a double-doped lithium-rich solid solution cathode composite material, so The chemical formula of the double-doped lithium-rich solid solution cathode composite material is: x Li 2 Mn0 3 '(lx)LiM0 2 'yM a M b , where 0<χ<1, 0<y<0.1, M is Ni, Co, Mn , Ti, Ah Zr, Fe, V, Mg and W, one or more of them, ^^ is one or more of Na and K, M b is one or more of F, N and P The combination.
4、 如权利要求 3所述的一种双掺杂富锂固溶体正极复合材料的制备方法， 其特征在于， 所述 M盐为醋酸盐、 草酸盐、 酸盐、 硝酸盐和氯化物中的一种 或几种的组合。 4. The preparation method of a double-doped lithium-rich solid solution cathode composite material as claimed in claim 3, wherein the M salt is acetate, oxalate, acid salt, nitrate and chloride. one or a combination of several.
5、 如权利要求 3所述的一种双掺杂富锂固溶体正极复合材料的制备方法， 其特征在于， 所述碱为 LiOH、 NaOH、 KOH、 氨水和铵盐中的一种或几种的组 合。 5. The method for preparing a double-doped lithium-rich solid solution cathode composite material as claimed in claim 3, wherein the base is one or more of LiOH, NaOH, KOH, ammonia and ammonium salts. combination.
6、 如权利要求 3所述的一种双掺杂富锂固溶体正极复合材料的制备方法， 其特征在于， 所述碳酸盐为 Li2C03、 Na2C03、 K2C03、 （NH4)2C03和 (N )HC03 中的一种或几种。 6. The method for preparing a double-doped lithium-rich solid solution cathode composite material as claimed in claim 3, wherein the carbonate is Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , ( One or more of NH 4 ) 2 CO 3 and (N ) HCO 3 .
7、 如权利要求 3所述的一种双掺杂富锂固溶体正极复合材料的制备方法， 其特征在于， 所述锂盐为氢氧化锂、 醋酸锂、 硝酸锂、 草酸锂、 硫酸锂、 碳酸 锂和氯化锂等一种或几种的组合。 7. The preparation method of a double-doped lithium-rich solid solution cathode composite material as claimed in claim 3, wherein the lithium salt is lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, carbonic acid One or a combination of lithium and lithium chloride.
8、 如权利要求 3所述的一种双掺杂富锂固溶体正极复合材料的制备方法,
其特征在于， 所述 y的取值范围为 0.02 y 0.09。 8. The preparation method of a double-doped lithium-rich solid solution cathode composite material as claimed in claim 3, It is characterized in that the value range of y is 0.02 y 0.09.
9、 一种锂离子电池正极片， 其特征在于， 所述锂离子电池正极片包括集流 体和涂布在集流体上的双掺杂富锂固溶体正极复合材料， 所述双掺杂富锂固溶 体正极复合材料化学式为： xLi2Mn03'(l-x)LiM02'yMaMb,其中 0<x<l , 0<y<0.1 , Μ为 Ni、 Co、 Mn、 Ti、 Ah Zr、 Fe、 V、 Mg和 W中一种或几种的组合， Ma 为 Na和 K中的一种或组合， Mb为F、 Ν和 Ρ中的一种或几种的组合。 9. A lithium-ion battery cathode sheet, characterized in that, the lithium-ion battery cathode sheet includes a current collector and a double-doped lithium-rich solid solution cathode composite material coated on the current collector, and the double-doped lithium-rich solid solution The chemical formula of the cathode composite material is: xLi 2 Mn0 3 '(lx)LiM0 2 'yM a M b , where 0<x<l, 0<y<0.1, M is Ni, Co, Mn, Ti, Ah Zr, Fe, One or a combination of one or more of V, Mg and W, M a is one or a combination of Na and K, M b is one or a combination of one or more of F, N and P.
10、 一种锂离子电池， 包括锂离子电池正极片、 锂离子电池负极片、 隔膜 和电解液， 其特征在于， 所述锂离子电池正极片包括集流体和涂布在集流体上 的双掺杂富锂固溶体正极复合材料， 所述双掺杂富锂固溶体正极复合材料化学 式为： xLi2Mn03'(l-x)LiM02'yMaMb, 其中 0<x<l , 0<y<0.1 , M 为 Ni、 Co、 Mn、 Ti、 Al、 Zr、 Fe、 V、 Mg和 W中一种或几种的组合， Ma为 Na和 K中的 一种或组合， Mb为F、 Ν和 Ρ中的一种或几种的组合。
10. A lithium ion battery, including a lithium ion battery positive electrode sheet, a lithium ion battery negative electrode sheet, a separator and an electrolyte, characterized in that the lithium ion battery positive electrode sheet includes a current collector and a double doped coating coated on the current collector Hybrid lithium-rich solid solution cathode composite material, the chemical formula of the double-doped lithium-rich solid solution cathode composite material is: xLi 2 Mn0 3 '(lx)LiM0 2 'yM a M b , where 0<x<l, 0<y<0.1 , M is one or a combination of Ni, Co, Mn, Ti, Al, Zr, Fe, V, Mg and W, M a is one or a combination of Na and K, M b is F, N and P or a combination of several.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105098158A (en) * | 2015-08-19 | 2015-11-25 | 上海电力学院 | Zirconium-doped lithium-rich cathode material of lithium ion battery and preparation method of zirconium-doped lithium-rich cathode material |
| CN110323432A (en) * | 2019-07-10 | 2019-10-11 | 河南电池研究院有限公司 | A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof |
| CN114229922A (en) * | 2022-02-21 | 2022-03-25 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, positive electrode material and preparation method |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102015217747A1 (en) * | 2015-09-16 | 2017-03-16 | Robert Bosch Gmbh | Active material for a positive electrode of a battery cell, postitive electrode and battery cell |
| CN106910887B (en) * | 2015-12-22 | 2020-05-26 | 国联汽车动力电池研究院有限责任公司 | Lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery containing positive electrode material |
| DE102016223246A1 (en) * | 2016-11-24 | 2018-05-24 | Robert Bosch Gmbh | Active material for a positive electrode of a battery cell, positive electrode and battery cell |
| CN108091858B (en) * | 2017-12-14 | 2022-09-13 | 桑顿新能源科技(长沙)有限公司 | Li-O-site lithium manganate-doped lithium-rich cathode material and preparation method thereof |
| CN108987726B (en) * | 2018-08-22 | 2021-07-20 | 成都巴莫科技有限责任公司 | Preparation method of carbon dynamic coated lithium-rich oxide solid solution material |
| CN110808370A (en) * | 2019-10-25 | 2020-02-18 | 合肥国轩高科动力能源有限公司 | Ternary cathode material of lithium ion battery and preparation method and application thereof |
| CN111342008A (en) * | 2020-02-25 | 2020-06-26 | 华南理工大学 | Potassium fluoride doped lithium-rich manganese-based material and preparation method and application thereof |
| CN114940520A (en) * | 2022-06-24 | 2022-08-26 | 蜂巢能源科技股份有限公司 | Cobalt-free lithium-rich material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| CN102569775A (en) * | 2011-12-23 | 2012-07-11 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and positive electrode active material thereof |
| US20120282522A1 (en) * | 2011-05-02 | 2012-11-08 | Washington University | Spray Pyrolysis Synthesis of Mesoporous Positive Electrode Materials for High Energy Lithium-Ion Batteries |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090127520A1 (en) * | 2003-05-28 | 2009-05-21 | Pamela Whitfield | Lithium metal oxide compositions |
| WO2008054547A2 (en) * | 2006-05-31 | 2008-05-08 | Uchicago Argonne, Llc | Surface stabilized electrodes for lithium batteries |
| CN101237044A (en) * | 2008-02-29 | 2008-08-06 | 厦门大学 | Positive material rock salt Mn lithium of nano lithium ion battery and its making method |
| KR20120089845A (en) * | 2009-08-27 | 2012-08-14 | 엔비아 시스템즈 인코포레이티드 | Layer-layer lithium rich complex metal oxides with high specific capacity and excellent cycling |
| CN102639443B (en) * | 2009-12-07 | 2015-04-15 | 住友化学株式会社 | Method for producing lithium composite metal oxide, lithium composite metal oxide, and nonaqueous electrolyte secondary battery |
-
2013
- 2013-05-31 CN CN201310211352.7A patent/CN104218235B/en active Active
- 2013-10-24 WO PCT/CN2013/085888 patent/WO2014190662A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101156260A (en) * | 2005-04-15 | 2008-04-02 | 能原材公司 | Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same |
| US20120282522A1 (en) * | 2011-05-02 | 2012-11-08 | Washington University | Spray Pyrolysis Synthesis of Mesoporous Positive Electrode Materials for High Energy Lithium-Ion Batteries |
| CN102569775A (en) * | 2011-12-23 | 2012-07-11 | 东莞新能源科技有限公司 | Lithium-ion secondary battery and positive electrode active material thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105098158A (en) * | 2015-08-19 | 2015-11-25 | 上海电力学院 | Zirconium-doped lithium-rich cathode material of lithium ion battery and preparation method of zirconium-doped lithium-rich cathode material |
| CN110323432A (en) * | 2019-07-10 | 2019-10-11 | 河南电池研究院有限公司 | A kind of miscellaneous modification lithium-ion battery anode material of cation-anion co-doping and preparation method thereof |
| CN114229922A (en) * | 2022-02-21 | 2022-03-25 | 浙江帕瓦新能源股份有限公司 | Nickel-cobalt-manganese ternary precursor, positive electrode material and preparation method |
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| CN104218235A (en) | 2014-12-17 |
| CN104218235B (en) | 2018-11-20 |
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