CN113247966A - Lithium-rich manganese-based precursor, positive electrode material and preparation method thereof - Google Patents
Lithium-rich manganese-based precursor, positive electrode material and preparation method thereof Download PDFInfo
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- CN113247966A CN113247966A CN202011645566.1A CN202011645566A CN113247966A CN 113247966 A CN113247966 A CN 113247966A CN 202011645566 A CN202011645566 A CN 202011645566A CN 113247966 A CN113247966 A CN 113247966A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 135
- 239000011572 manganese Substances 0.000 title claims abstract description 133
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 128
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 87
- 239000002243 precursor Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 61
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 229910004882 Na2S2O8 Inorganic materials 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000005416 organic matter Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000010406 cathode material Substances 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 229910001868 water Inorganic materials 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 238000011010 flushing procedure Methods 0.000 claims description 7
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 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
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 14
- 239000011029 spinel Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 description 26
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 19
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 230000001351 cycling effect Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 229910008626 Li1.2Ni0.13Co0.13Mn0.54O2 Inorganic materials 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- -1 lithium salt compound Chemical class 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Images
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- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
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- 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
- H01M4/362—Composites
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- 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
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- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium-rich manganese-based precursor, a positive electrode material and a preparation method thereof, wherein the preparation method of the lithium-rich manganese-based positive electrode material comprises the following steps: uniformly mixing the lithium-rich manganese-based precursor with a lithium source compound, calcining, cooling to room temperature after the calcination is finished, heating, preserving heat, and naturally cooling to obtain a lithium-rich manganese-based positive electrode material A; the obtained lithium-rich manganese-based positive electrodeElectrode materials A and Na2S2O8Uniformly mixing, and carrying out heat preservation in a high-temperature air atmosphere to obtain a lithium-rich manganese-based positive electrode material B; uniformly mixing the lithium-rich manganese-based positive electrode material B with a carbon-containing organic matter, and carrying out heat preservation in a high-temperature inert gas atmosphere to obtain a lithium-rich manganese-based positive electrode material; the invention has the beneficial effects that: the positive electrode material obtained by the method is subjected to surface spinel structure construction and carbon layer coating, so that the ion mobility and the electron conductivity of the positive electrode material can be improved simultaneously, and the rate capability and the cycle stability of the positive electrode material are improved.
Description
Technical Field
The invention relates to the field of electrode material preparation, in particular to a lithium-rich manganese-based precursor, a positive electrode material and a preparation method thereof.
Background
Because the lithium ion battery has high energy density, long service life and good safety, the lithium ion battery is firstly suitable for the fields of mobile phones, notebooks, electric tools and the like. With the continuous improvement of the preparation processes of lithium ion battery materials, battery cells and PACK, the lithium ion batteries are gradually applied to the field of power batteries. LiCoO, the earliest commercially available layered cathode material2Because the price is high, the voltage window is low, the percentage of usable Li ions in the structure is only about 0.6, and the lithium ion battery conflicts with the requirements of high energy and low cost pursued by a power battery, and the wide application of the lithium ion battery in the field of the power battery is severely limited. The commercialized layered ternary cathode material has excellent cycle, low price and high discharge specific capacity, but is difficult to synthesize and poor in high-temperature safety performance. The nickel-manganese material with the cobalt-free spinel structure has low raw material price, the discharge voltage can reach about 5V, and the anode material with the energy density of 600Wh/kg can be prepared by matching with proper high-voltage electrolyte. Furthermore, LiFePO of olivine structure4The anode material has low price, good cycle performance and excellent safety, but has low energy density and poor rate performance, so that the anode material is only suitable for being applied to the fields of mobile base stations, buses, ships or commercial vehicles and the like which have low requirements on volume. The layered lithium-manganese-rich cathode material has high capacity and low cost under low multiplying power, but has quick voltage attenuation, poor first effect, multiplying power and cycle performance and the likeBecomes an important factor for restricting the wide application of the lithium ion battery in the field of power batteries.
The lithium-manganese-rich cathode material has a discharge specific capacity of 280mAh/g at a low rate of 0.1C, a discharge voltage of more than 4.5V and a high energy density. However, at high rates, such as 1C, the specific discharge capacity is only 180 mAh/g. The main reason for affecting the rate capability is Li2MnO3Mn in the composite4+Poor conductivity, greater transport resistance between the particle and electrolyte interfaces, formation of a low conductivity interfacial film (CEI) of the positive electrolyte during cycling, poor delithiation kinetics and a smaller delithiation surface of the resultant lithium-rich manganese positive electrode material, hindering the deintercalation and electromigration behavior of lithium ions. Therefore, it is very important to develop a lithium-manganese-rich cathode material with high rate capability.
Chinese patent CN 109537054A discloses a preparation method of a high-magnification lithium-manganese-rich anode material single crystal, which comprises the specific steps and an implementation mode, and the main design idea is that a manganese-based precursor is prepared by adopting a coprecipitation method, the washed and dried precursor is mixed with an auxiliary agent to obtain a manganese-based composite precursor, and the manganese-based composite precursor is mixed with a lithium salt compound and then is subjected to programmed calcination in an oxygen atmosphere to obtain the single crystal type lithium-manganese-rich anode material.
The Chinese patent CN 201610223526.5 coats silicon dioxide on the surface of a lithium-manganese-rich positive electrode material and a precursor thereof by a tetraethyl orthosilicate hydrolysis method, and although the coating layer prepared by the method can effectively isolate an electrode from an electrolyte, inhibit the decomposition of the electrolyte and improve the cycle stability of the lithium-manganese-rich positive electrode material, the electronic conductivity of the SiO is poor2But also reduces the rate capability of the coated anode material and the capacity of the lithium-rich manganese anode material.
Chinese patent CN 201710473738.3 describes a method for constructing spinel structure on the surface of lithium-rich manganese anode material, which is to add the lithium-rich manganese anode material into weak acid solution to make it Li+And H+The anode material after ion exchange is subjected to heat treatment to convert the surface layer lithium-deficient structure into spinelThe structure is adopted to obtain the lithium-manganese-rich cathode material with a spinel structure on the surface layer, and the lithium-manganese-rich cathode material prepared by the method removes Li2O and the spinel structure of the three-dimensional lithium ion diffusion channel is introduced, so that the first effect, the multiplying power and the cycle performance of the anode material can be improved. However, the surface structure of the material is seriously damaged by using the acidic solution to treat the surface of the material, so that the surface Li+Dissolving to reduce active Li+The content of (a) reduces the capacity.
Selection of CeF by Lu et al3For Li1.2Ni0.13Co0.13Mn0.54O2The surface coating is carried out, the cycling stability of the material is obviously improved, but the introduced CeF3The inert layer reduces the rate capability of the cathode material.
In summary, no matter what surface modification method of the lithium-manganese-rich material is adopted, the obtained lithium-manganese-rich positive electrode material cannot give consideration to capacity, multiplying power and cycling stability, and aiming at the defect of surface modification of the lithium-manganese-rich positive electrode material, the invention mainly selects a mild chemical reagent Na2S2O8A spinel structure is introduced to the surface of the anode, and surface carbon coating is carried out, so that the multiplying power and the cycling stability of the anode are improved while the capacity of the material is considered.
Disclosure of Invention
The main purpose of the present application is to provide a method capable of preparing a lithium-rich manganese-based precursor and a positive electrode material having high ion mobility and electron conductivity.
In order to achieve the above purpose, the invention provides the following technical scheme:
in a first aspect of the present invention, a method for preparing a lithium-rich manganese-based precursor is provided, which comprises the following steps:
(1) preparing a mixed salt solution: mixing the components in a molar ratio of 0.1-1: 0.1-1: 1-4 of NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring uniformly to prepare a mixed salt solution with the concentration of 0.5-5 mol/L;
(2) adding Na with the concentration of 1.0-5.0mol/L2CO3Aqueous solution and concentrateMixing and stirring complexing agent with the degree of 0.01-1.0mol/L uniformly to obtain mixed solution;
(3) adding water into a reaction kettle as a solvent, flushing nitrogen into the water, and mixing the mixed salt solution obtained in the step (1) and the mixed solution obtained in the step (2) in a flow rate ratio of 0.1-1: and introducing the mixture into the reaction kettle at a speed of 0.2-2 simultaneously for reaction, filtering and washing the filter residue after the reaction is finished, and drying the washed filter residue to obtain the lithium-rich manganese-based precursor.
As a preferable embodiment, in the step (2), the complexing agent is at least one of sodium citrate, ammonia water, ammonium oxalate, EDTA or oxalic acid.
In the above method for preparing a lithium-rich manganese-based precursor, as a preferred embodiment, in step (3), the reaction conditions in the reaction kettle are as follows: the reaction temperature is 50-80 ℃, the reaction time is 6-10h, and the pH of the reaction solution is 7.0-10.0; standing and aging for 3-12h after the reaction is finished, and then filtering.
As a preferred embodiment, in the step (3), the washing agent used for washing the filter residue is deionized water, and preferably, the drying is performed under vacuum at 120 ℃ for 2 hours.
The preparation method of the precursor adopts Na2CO3As a precipitant in the precursor preparation process, the resulting carbonate precursor (Ni)0.13Co0.13Mn0.54)CO3Is less hydroxide precursor (Ni)0.13Co0.13Mn0.54)(OH)2Can more effectively inhibit Mn2+And (4) oxidizing.
In a second aspect of the present invention, there is provided a lithium-rich manganese-based positive electrode material comprising the precursor according to any one of claims 1 to 4, a lithium source compound, and Na2S2O8Carbon-containing organic substance, the precursor, lithium source compound and Na2S2O8The molar ratio of the carbon-containing organic matters is 10: 12-15: 0.2-1.2: 0.2-0.8.
As a preferred embodiment, the lithium source compound is one of lithium carbonate, lithium hydroxide, lithium phosphate, lithium acetate or lithium nitrate; the carbon-containing organic matter is one of polystyrene, polyethylene glycol, sucrose, polyvinyl alcohol, polyvinylpyrrolidone, glucose or maltose.
In a third aspect of the invention, a preparation method of a lithium-rich manganese-based positive electrode material is provided, which comprises the following steps:
a. uniformly mixing the precursor and a lithium source compound, calcining, cooling to room temperature after calcining is finished, heating, preserving heat, and naturally cooling to obtain a lithium-rich manganese-based positive electrode material A;
b. b, mixing the lithium-rich manganese-based positive electrode material A obtained in the step a with Na2S2O8Uniformly mixing, and carrying out heat preservation in a high-temperature air atmosphere to obtain a lithium-rich manganese-based positive electrode material B;
c. and c, uniformly mixing the lithium-rich manganese-based positive electrode material B obtained in the step B with a carbon-containing organic matter, and preserving heat in a high-temperature inert gas atmosphere to obtain the lithium-rich manganese-based positive electrode material.
The lithium-rich manganese-based cathode material A is treated with Na2S2O8Surface treatment is carried out to remove Li in the nanometer thickness of the surface of the anode material A2And O, introducing a spinel structure with a three-dimensional lithium ion diffusion channel, wherein the spinel structure can improve the first effect, the multiplying power and the cycling stability of the anode material.
In the preparation method of the lithium-rich manganese-based cathode material, as a preferred embodiment, in the step a, the calcination temperature is 300-600 ℃, and the calcination time at the temperature is 2-10 h; preferably, in step a, after the calcination is completed and the temperature is cooled to room temperature, the temperature is raised to 600-900 ℃, the temperature is kept for 10-20 ℃, and then the temperature is naturally reduced.
As a preferable embodiment, in the step b, the high-temperature heating temperature in the step b is 200-.
In the above method for preparing a lithium-rich manganese-based positive electrode material, as a preferred embodiment, in step c, the inert gas is nitrogen; preferably, the high-temperature heating temperature is 300-500 ℃, and the holding time at the temperature is 5-10.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method of the lithium-rich manganese-based precursor adopts Na2CO3As a precipitant in the precursor preparation process, the resulting carbonate precursor (Ni)0.13Co0.13Mn0.54)CO3Is less hydroxide precursor (Ni)0.13Co0.13Mn0.54)(OH)2Can more effectively inhibit Mn2+And (4) oxidizing.
2. The preparation method of the lithium-rich manganese-based positive electrode material adopts Na2S2O8The surface treatment is carried out on the lithium-rich manganese anode material, and Li is removed within the nanometer thickness of the material surface2O, introducing a spinel structure with a three-dimensional lithium ion diffusion channel, so that the first effect, the multiplying power and the cycling stability of the anode material can be improved;
in addition, Na is selected in the present invention2S2O8Compared with the method of introducing the spinel structure by utilizing the heat treatment of ammonium sulfate, ammonium bicarbonate, diammonium hydrogen phosphate and the like or soaking by weak acid, the method of the invention has the advantages that the damage to the surface of the anode material is extremely small, the influence on the initial capacity can be almost ignored,
3. the preparation method of the lithium-rich manganese-based anode material adopts an organic carbon source to carry out carbon coating on the anode material in an inert environment, so that the electronic conductivity of the anode material is improved.
4. The lithium-manganese-rich cathode material prepared by the preparation method of the lithium-manganese-rich cathode material is subjected to surface spinel structure construction and carbon layer coating, so that the ion mobility and the electron conductivity of the cathode material can be improved simultaneously, and the rate capability and the cycling stability of the lithium-manganese-rich cathode material are improved.
Drawings
FIG. 1: XRD (X-ray diffraction) patterns of the lithium-rich manganese-based positive electrode materials obtained in the embodiment 6 and the comparative example 1 are shown;
FIG. 2: SEM images of the lithium-rich manganese-based positive electrode materials obtained in example 7 of the invention and comparative example 2 are as follows: fig. 2a is an SEM image of a lithium-rich manganese-based positive electrode material obtained in comparative example 1, and fig. 2b is an SEM image of a lithium-rich manganese-based positive electrode material obtained in example 7;
FIG. 3: the lithium-rich manganese-based positive electrode materials obtained in the embodiment 8 and the comparative example 3 have the battery cycle performance;
FIG. 4: the battery rate performance of the lithium-rich manganese-based positive electrode materials obtained in example 9 and comparative example 4 of the invention.
Detailed Description
In order to make the technical solutions in the embodiments of the present application better understood, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to examples, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
A preparation method of a lithium-rich manganese-based precursor comprises the following steps:
(1) preparing a mixed salt solution: mixing a mixture of 1: 1: 4 NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring uniformly to prepare a sulfate solution with the concentration of 1 mol/L;
(2) adding Na with the concentration of 2mol/L2CO3Mixing and stirring the aqueous solution and EDTA with the concentration of 0.01mol/L uniformly to obtain a mixed solution;
(3) adding 1L of water into a reaction kettle as a solvent, flushing nitrogen into the water, introducing the mixed salt solution obtained in the step (1) into the reaction kettle at the flow rate of 5mL/min and the mixed solution obtained in the step (2) at the flow rate of 10mL/min at the same time in the nitrogen atmosphere for reacting for 8 hours at the temperature of 50 ℃, maintaining the pH value of the reaction solution at 7.5, standing and aging for 12 hours after the reaction is finished, filtering, washing the filter residue with deionized water, and vacuum-drying the washed filter residue for 2 hours at the temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor.
Example 2
A preparation method of a lithium-rich manganese-based precursor comprises the following steps:
(1) preparing a mixed salt solution: mixing a mixture of 1: 1: 4 NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring uniformly to prepare a sulfate solution with the concentration of 2 mol/L;
(2) na with the concentration of 4mol/L2CO3Mixing and stirring the aqueous solution and EDTA with the concentration of 0.4mol/L uniformly to obtain a mixed solution;
(3) adding 1L of water into a reaction kettle as a solvent, flushing nitrogen into the water, introducing the mixed salt solution obtained in the step (1) into the reaction kettle at the flow rate of 5mL/min and the mixed solution obtained in the step (2) at the flow rate of 10mL/min at the same time in the nitrogen atmosphere for reacting for 6 hours at the temperature of 70 ℃, maintaining the pH of the reaction solution at 9.5, standing and aging for 12 hours after the reaction is finished, filtering, washing the filter residue with deionized water, and drying the washed filter residue in vacuum for 2 hours at the temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor.
Example 3
A preparation method of a lithium-rich manganese-based precursor comprises the following steps:
(1) preparing a mixed salt solution: mixing a mixture of 1: 1: 4 NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring uniformly to prepare a sulfate solution with the concentration of 1 mol/L;
(2) adding Na with the concentration of 2mol/L2CO3Mixing and stirring the aqueous solution and sodium citrate with the concentration of 1.0mol/L uniformly to obtain a mixed solution;
(3) adding 1L of water into a reaction kettle as a solvent, flushing nitrogen into the water, simultaneously introducing the mixed salt solution obtained in the step (1) into the reaction kettle at the flow rate of 5mL/min and the mixed solution obtained in the step (2) at the flow rate of 10mL/min to react for 6 hours at the temperature of 80 ℃ under the nitrogen atmosphere, maintaining the pH of the reaction solution at 8.0, standing and aging for 12 hours after the reaction is finished, filtering, washing the filter residue with deionized water, and vacuum-drying the washed filter residue for 2 hours at the temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor
Example 4
A preparation method of a lithium-rich manganese-based precursor comprises the following steps:
(1) preparing a mixed salt solution: mixing a mixture of 1: 1: 4 NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring uniformly to prepare a sulfate solution with the concentration of 2 mol/L;
(2) na with the concentration of 4mol/L2CO3Mixing and stirring the aqueous solution and sodium citrate with the concentration of 0.5mol/L uniformly to obtain a mixed solution;
(3) adding 1L of water into a reaction kettle as a solvent, flushing nitrogen into the water, simultaneously introducing the mixed salt solution obtained in the step (1) into the reaction kettle at the flow rate of 5mL/min and the mixed solution obtained in the step (2) at the flow rate of 10mL/min to react for 8 hours at the temperature of 60 ℃ under the nitrogen atmosphere, maintaining the pH of the reaction solution at 8.0, standing and aging for 12 hours after the reaction is finished, filtering, washing the filter residue with deionized water, and vacuum-drying the washed filter residue for 2 hours at the temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor
Example 5
A preparation method of a lithium-rich manganese-based precursor comprises the following steps:
(1) preparing a mixed salt solution: mixing a mixture of 1: 1: 4 NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring uniformly to prepare a sulfate solution with the concentration of 2 mol/L;
(2) na with the concentration of 4mol/L2CO3The aqueous solution and ammonium oxalate with the concentration of 0.12mol/L are mixed and stirred evenly to obtain mixed solution;
(3) adding 1L of water into a reaction kettle as a solvent, flushing nitrogen into the water, introducing the mixed salt solution obtained in the step (1) into the reaction kettle at the flow rate of 5mL/min and the mixed solution obtained in the step (2) at the flow rate of 10mL/min at the same time in the nitrogen atmosphere, reacting for 10 hours at the temperature of 50 ℃, maintaining the pH of the reaction solution at 9.0, standing and aging for 12 hours after the reaction is finished, filtering, washing the filter residue with deionized water, and vacuum-drying the washed filter residue for 2 hours at the temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor.
Example 6
The lithium-rich manganese-based precursor obtained in example 1 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.4, uniformly mixing, calcining for 5 hours at 500 ℃, cooling to room temperature after calcining is finished, then heating to 700 ℃, preserving heat for 20 hours, and then naturally cooling to obtain a lithium-rich manganese-based positive electrode material A;
mixing the lithium-rich manganese-based positive electrode material A and Na2S2O8According to the mass ratio of 10: 1.5, uniformly mixing, and keeping the temperature for 5 hours in an air atmosphere at the temperature of 300 ℃ to obtain a lithium-rich manganese-based positive electrode material B;
mixing the lithium-rich manganese-based positive electrode material B and glucose according to a mass ratio of 10: 1, uniformly mixing, and keeping the temperature for 8 hours in a nitrogen atmosphere at the temperature of 400 ℃ to obtain the lithium-rich manganese-based positive electrode material.
Example 7
The lithium-rich manganese-based precursor obtained in example 2 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.2, uniformly mixing, calcining for 10 hours at 500 ℃, cooling to room temperature after calcining is finished, heating to 800 ℃, preserving heat for 20 hours, and naturally cooling to obtain a lithium-rich manganese-based positive electrode material A;
mixing the lithium-rich manganese-based positive electrode material A and Na2S2O8According to the mass ratio of 10: 1, uniformly mixing, and keeping the temperature for 8 hours in an air atmosphere at the temperature of 300 ℃ to obtain a lithium-rich manganese-based positive electrode material B;
mixing the lithium-rich manganese-based positive electrode material B and cane sugar according to a mass ratio of 10: 1.5, uniformly mixing, and keeping the temperature for 8 hours in a nitrogen atmosphere at the temperature of 400 ℃ to obtain the lithium-rich manganese-based positive electrode material.
Example 8
The lithium-rich manganese-based precursor obtained in example 3 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.5, evenly mixing, calcining for 8 hours at 600 ℃, cooling to room temperature after calcining is finished, then heating to 800 ℃, preserving heat for 15 hours, and then naturally cooling to obtain the lithium-rich manganese baseA positive electrode material A;
mixing the lithium-rich manganese-based positive electrode material A and Na2S2O8According to the mass ratio of 10: 2, uniformly mixing, and keeping the temperature for 8 hours in an air atmosphere at the temperature of 400 ℃ to obtain a lithium-rich manganese-based positive electrode material B;
mixing the lithium-rich manganese-based positive electrode material B and glucose according to a mass ratio of 10: 1.5, uniformly mixing, and keeping the temperature for 10 hours in a nitrogen atmosphere at the temperature of 500 ℃ to obtain the lithium-rich manganese-based positive electrode material.
Example 9
The lithium-rich manganese-based precursor obtained in example 4 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.3, uniformly mixing, calcining for 8 hours at 550 ℃, cooling to room temperature after calcining is finished, then heating to 900 ℃, preserving heat for 10 hours, and then naturally cooling to obtain a lithium-rich manganese-based positive electrode material A;
mixing the lithium-rich manganese-based positive electrode material A and Na2S2O8According to the mass ratio of 10: 1, uniformly mixing, and keeping the temperature of the mixture at 400 ℃ for 6 hours in an air atmosphere to obtain a lithium-rich manganese-based positive electrode material B;
mixing the lithium-rich manganese-based positive electrode material B and polyvinyl alcohol according to a mass ratio of 10: 1.5, uniformly mixing, and keeping the temperature for 10 hours in a nitrogen atmosphere at the temperature of 500 ℃ to obtain the lithium-rich manganese-based positive electrode material.
Example 10
The lithium-rich manganese-based precursor obtained in example 5 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.5, uniformly mixing, calcining for 8 hours at 550 ℃, cooling to room temperature after calcining is finished, then heating to 850 ℃, preserving heat for 18 hours, and then naturally cooling to obtain a lithium-rich manganese-based positive electrode material A;
mixing the lithium-rich manganese-based positive electrode material A and Na2S2O8According to the mass ratio of 10: 2.5, uniformly mixing, and keeping the temperature for 10 hours in an air atmosphere at the temperature of 300 ℃ to obtain a lithium-rich manganese-based positive electrode material B;
mixing the lithium-rich manganese-based positive electrode material B and glucose according to a mass ratio of 10: 1, uniformly mixing, and keeping the temperature for 8 hours in a nitrogen atmosphere at the temperature of 450 ℃ to obtain the lithium-rich manganese-based positive electrode material.
Comparative example 1
The preparation method of the lithium-rich manganese-based cathode material in the comparative example 1 comprises the following steps:
the lithium-rich manganese-based precursor obtained in example 1 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.4, uniformly mixing, calcining for 5 hours at 500 ℃, cooling to room temperature after calcining is finished, then heating to 700 ℃, preserving heat for 20 hours, and then naturally cooling to obtain the lithium-rich manganese-based cathode material.
Comparative example 2
The preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
the lithium-rich manganese-based precursor obtained in example 2 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.2, uniformly mixing, calcining for 10 hours at 500 ℃, cooling to room temperature after calcining is finished, then heating to 850 ℃, preserving heat for 20 hours, and then naturally cooling to obtain the lithium-rich manganese-based cathode material.
Comparative example 3
The preparation method of the lithium-rich manganese-based cathode material comprises the following steps:
the lithium-rich manganese-based precursor obtained in example 3 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.5, uniformly mixing, calcining for 8 hours at 600 ℃, cooling to room temperature after calcining, heating to 800 ℃, preserving heat for 15 hours, and naturally cooling to obtain the lithium-rich manganese-based cathode material.
Comparative example 4
Comparative example 4 a method for preparing a lithium-rich manganese-based positive electrode material, comprising the steps of:
the lithium-rich manganese-based precursor obtained in example 4 was reacted with LiOH. H2O is mixed according to a molar ratio of 1: 1.3, uniformly mixing, calcining for 8 hours at 550 ℃, cooling to room temperature after calcining is finished, then heating to 900 ℃, preserving heat for 10 hours, and then naturally cooling to obtain the lithium-rich manganese-based cathode material.
The performance research of the lithium-rich manganese-based anode material obtained by the invention comprises the following steps:
1. the XRD patterns of the lithium-rich manganese-based positive electrode material obtained in example 6 and the lithium-rich manganese-based positive electrode material obtained in comparative example 1 are shown in fig. 1:
as can be seen from fig. 1: after surface treatment and carbon coatingThe lithium-manganese-rich cathode material still maintains a good layered structure, and a small peak appears at 36.5 degrees, which shows that a spinel structure exists in the modified lithium-manganese-rich cathode material, namely the preparation method of the lithium-manganese-rich cathode material provided by the invention, and the obtained cathode material is subjected to Na treatment2S2O8The surface treatment and the carbon coating are carried out, but a good layered structure is still kept, and a spinel structure with a three-dimensional lithium ion diffusion channel is introduced.
2. SEM images of the lithium-rich manganese-based positive electrode material obtained in example 7 and the lithium-rich manganese-based positive electrode material obtained in comparative example 2 are shown in fig. 2:
as can be seen from fig. 2: the lithium-rich manganese-based positive electrode material described in comparative example 2 has good sphericity and good integrity of secondary particles, and the lithium-rich manganese-based positive electrode material described in example 7 has a rough surface and no significant carbon coating layer can be observed. I.e. over Na2S2O8The surface of the treated positive electrode material was roughened compared to that of the untreated positive electrode material, indicating that Na was present2S2O8Has acted on the positive electrode material. No significant carbon layer was visible after carbon coating, indicating that the coating was very small and moderate.
3. The battery cycle performance of the lithium-rich manganese-based positive electrode material obtained in example 8 and the lithium-rich manganese-based positive electrode material obtained in comparative example 3 is shown in fig. 3:
as can be seen from fig. 3, under the constant temperature condition of 25 ℃, the specific discharge capacity of the lithium-rich manganese-based positive electrode material (untreated lithium-rich manganese-based positive electrode material) obtained in comparative example 1 at the first 5 cycles of 0.1C rate is 274.7mAh/g, but the specific discharge capacity after 100 cycles of cycling at 1C rate is reduced from the initial 183.8mAh/g to 133.4mAh/g, and the capacity retention rate is only 72.6%;
although the lithium-rich manganese-based positive electrode material obtained in the embodiment 8 of the invention has an initial capacity of 263.8mAh/g at a multiplying power of 0.1C, the capacity is reduced from 196.6mAh/g to 194.3mAh/g after 100 cycles at a multiplying power of 1C, the capacity retention rate is 98.8%, and good cycle stability is shown.
4. The battery rate performance of the lithium-rich manganese-based positive electrode material obtained in example 9 and the lithium-rich manganese-based positive electrode material obtained in comparative example 4 were investigated, and the results are shown in fig. 4:
as can be seen from fig. 4, the lithium-rich manganese-based positive electrode material (untreated lithium-rich manganese positive electrode material) obtained in comparative example 1 has a high initial capacity at a constant temperature of 25 ℃, but exhibits poor electrical properties at a high rate of 3C. Wherein, the specific discharge capacity of the cathode material shown in the comparative example 1 is 35.4mAh/g at 3C, while the specific discharge capacity of the cathode material obtained in the embodiment 9 of the invention is up to 134.2mAh/g, so that the rate capability is greatly improved.
5. According to the preparation method of the lithium-rich manganese-based anode material, the capacity retention rates of the obtained lithium-rich manganese-based anode material A, the lithium-rich manganese-based anode material B and the lithium-rich manganese-based anode material after first charge, first discharge and first effect under the normal temperature multiplying power of 0.1C and 100 cycles under the multiplying power of 1C are shown in Table 1:
table 1 capacity retention ratio of positive electrode material according to the invention
As can be seen from table 1: the lithium-rich manganese-based positive electrode material is prepared by reacting Na2S2O8The surface spinel structure is constructed and coated by the carbon layer, and the ion mobility and the electron conductivity of the anode material can be improved simultaneously, so that the rate capability and the cycling stability of the lithium-manganese-rich anode material are improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the lithium-rich manganese-based precursor is characterized by comprising the following steps of:
(1) preparing a mixed salt solution: mixing the components in a molar ratio of 0.1-1: 0.1-1: 1-4 of NiSO4·6H2O、CoSO4·7H2O and MnSO4Dissolving in deionized water, mixing and stirring, and making into final productPreparing a mixed salt solution with the concentration of 0.5-5 mol/L;
(2) adding Na with the concentration of 1.0-5.0mol/L2CO3Mixing and stirring the aqueous solution and a complexing agent with the concentration of 0.01-1.0mol/L uniformly to obtain a mixed solution;
(3) adding water into a reaction kettle as a solvent, flushing nitrogen into the water, and mixing the mixed salt solution obtained in the step (1) and the mixed solution obtained in the step (2) in a flow rate ratio of 0.1-1: and introducing the mixture into the reaction kettle at a speed of 0.2-2 simultaneously for reaction, filtering and washing the filter residue after the reaction is finished, and drying the washed filter residue to obtain the lithium-rich manganese-based precursor.
2. The method according to claim 1, wherein in the step (2), the complexing agent is at least one of sodium citrate, ammonia water, ammonium oxalate, EDTA or oxalic acid.
3. The method for preparing a lithium-rich manganese-based precursor according to claim 1, wherein in step (3), the reaction conditions in the reaction vessel are: the reaction temperature is 50-80 ℃, the reaction time is 6-10h, and the pH of the reaction solution is 7.0-10.0; standing and aging for 3-12h after the reaction is finished, and then filtering.
4. The method for preparing the lithium-rich manganese-based precursor according to claim 3, wherein in the step (3), the washing agent used for washing the filter residue is deionized water, and preferably, the drying is performed for 2 hours under vacuum at 120 ℃.
5. The lithium-rich manganese-based cathode material is characterized by comprising the following raw materials: the precursor, the lithium source compound, Na according to any one of claims 1 to 42S2O8Carbon-containing organic substance, the precursor, lithium source compound and Na2S2O8The molar ratio of the carbon-containing organic matters is 10: 12-15: 0.2-1.2: 0.2-0.8.
6. the lithium-rich manganese-based positive electrode material according to claim 5, wherein the lithium source compound is one of lithium carbonate, lithium hydroxide, lithium phosphate, lithium acetate, or lithium nitrate; the carbon-containing organic matter is one of polystyrene, polyethylene glycol, sucrose, polyvinyl alcohol, polyvinylpyrrolidone, glucose or maltose.
7. The method for preparing a lithium-rich manganese-based positive electrode material according to any one of claims 5 to 6, comprising the steps of:
a. uniformly mixing the precursor of any one of claims 1 to 4 with a lithium source compound, calcining, cooling to room temperature after calcining is finished, heating, preserving heat, and naturally cooling to obtain a lithium-rich manganese-based positive electrode material A;
b. b, mixing the lithium-rich manganese-based positive electrode material A obtained in the step a with Na2S2O8Uniformly mixing, and carrying out heat preservation in a high-temperature air atmosphere to obtain a lithium-rich manganese-based positive electrode material B;
c. and c, uniformly mixing the lithium-rich manganese-based positive electrode material B obtained in the step B with a carbon-containing organic matter, and preserving heat in a high-temperature inert gas atmosphere to obtain the lithium-rich manganese-based positive electrode material.
8. The method as claimed in claim 7, wherein the calcining temperature in step a is 300-600 ℃, and the calcining time at the temperature is 2-10 h; preferably, in the step a, after the calcination is finished, the temperature is cooled to room temperature, then the temperature is raised to 600-900 ℃, the temperature is kept for 10-20 h, and then the temperature is naturally reduced.
9. The method as claimed in claim 7, wherein the temperature for heating at high temperature is 200-500 ℃ and the time for maintaining at the temperature is 5-10 h.
10. The method for preparing a lithium-rich manganese-based positive electrode material according to claim 9, wherein in step c, the inert gas is nitrogen; preferably, the high-temperature heating temperature is 300-500 ℃, and the holding time at the temperature is 5-10.
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| CN115286042A (en) * | 2022-09-22 | 2022-11-04 | 河南电池研究院有限公司 | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof |
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