CN116605921A - Lithium-rich manganese-based positive electrode precursor and preparation method and application thereof - Google Patents
Lithium-rich manganese-based positive electrode precursor and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 64
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 60
- 239000002243 precursor Substances 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000975 co-precipitation Methods 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 27
- 230000008859 change Effects 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 33
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 oxalic acid radical ions Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000006138 lithiation reaction 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
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- PVIFNYFAXIMOKR-UHFFFAOYSA-M manganese(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Mn+3] PVIFNYFAXIMOKR-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The invention provides a lithium-rich manganese-based positive electrode precursor, and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing a nickel source, a manganese source and a solvent to obtain a solution A, and mixing a nickel source, a manganese source and a tungsten source with the solvent to obtain a solution B; (2) Adding the solution A, alkali liquor and ammonia water into a reaction container in parallel to perform one-step coprecipitation reaction, and stopping feeding when the particle size reaches 3/4-5/6 of the required size; (3) The solution B, oxalic acid and alkali liquor are added in parallel to a reaction vessel for two-step coprecipitation reaction, and the lithium-rich manganese-based positive electrode precursor is obtained after aging. After W doping, structural collapse caused by material phase change can be relieved, impedance is reduced, charge transfer capacity is improved, thermal stability of the material is improved, and good cycle performance and rate capability are finally displayed.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium-rich manganese-based positive electrode precursor, and a preparation method and application thereof.
Background
Lithium-rich manganese-based cathode materials that can provide specific capacities in excess of 250mAh/g (0.1C), almost twice the actual capacity of currently commercialized cathode materials, are considered to be the most potential lithium ion battery cathode materials. Meanwhile, the material mainly contains cheaper manganese element, has low noble metal content, and has lower cost and better safety compared with the common ternary positive electrode material of lithium cobalt oxide and nickel cobalt manganese (aluminum).
Due to Li during charge and discharge 2 MnO 3 The irreversible activation and the lower ionic and electronic conductivities thereof have limitations in application, such as reversible capacity loss and low coulombic efficiency of first charge and discharge, capacity and voltage attenuation, poor rate capability and the like. Studies have shown that its primary failure mechanisms include: irreversible oxidation of lattice oxygen, structural phase change caused by transition metal ion migration, electrode/electrolyte interface side reaction and the like.
CN111204813a discloses a preparation method of vanadium doped lithium-rich manganese-based positive electrode material, which comprises the steps of uniformly mixing manganese sulfate solution, cobalt sulfate solution, ammonium metavanadate solution and sodium carbonate solution, regulating the pH to 8-10 by ammonia water, stirring for 1h at a constant temperature of 50 ℃, filtering, washing, centrifuging and drying to obtain a mixture A; mixing and grinding the mixture A, sodium carbonate and lithium carbonate, heating to 450 ℃ at a constant speed, preserving heat for 4 hours, heating to 770-800 ℃ and preserving heat for 8-10 hours, and cooling along with a furnace to obtain a mixture B; and fully mixing the mixture B with lithium nitrate and lithium chloride, uniformly heating to 280 ℃ in a tube furnace, performing ion exchange for 4 hours, and performing centrifugation and drying to obtain the vanadium-doped lithium-rich manganese-based anode material.
CN112158893a discloses a preparation method of a lithium-rich manganese-based positive electrode material precursor, which comprises the following steps: preparing a mixed salt solution A of nickel and manganese, a mixed salt solution B of nickel, cobalt and manganese, introducing inert gas into a reaction kettle containing a base solution, respectively adding the mixed salt solution A, ammonia water and an alkaline solution into the reaction kettle, stirring, adding the mixed salt solution B, the ammonia water and the alkaline solution, and controlling pH, ammonia-base concentration, reaction temperature, reaction time, stirring speed and the like in the reaction process to obtain a precursor with the particle size of 13-18 mu m.
The single precipitant has different precipitation effects on the host material and the doping element, which may cause uneven distribution of the doping element, and thus the purpose of stabilizing the material structure by introducing doping cannot be achieved. In addition, the hydroxide coprecipitation method has certain disadvantages when the lithium-rich manganese-based precursor is a precursor with higher manganese content. In the preparation process, divalent manganese is easily oxidized into trivalent to form hydroxyl manganese oxide, so that the stoichiometric ratio between elements is influenced; and the generated manganese-rich hydroxide precursor is generally irregular in shape and low in bulk density, and influences energy density and electrochemical performance.
Disclosure of Invention
The invention aims to provide a lithium-rich manganese-based positive electrode precursor, a preparation method and application thereof. After W doping, structural collapse caused by material phase change can be relieved, impedance is reduced, charge transfer capacity is improved, thermal stability of the material is improved, and good cycle performance and rate capability are finally displayed.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium-rich manganese-based positive electrode precursor, the method comprising the steps of:
(1) Mixing a nickel source, a manganese source and a solvent to obtain a solution A, and mixing a nickel source, a manganese source and a tungsten source with the solvent to obtain a solution B;
(2) Adding the solution A, alkali liquor and ammonia water into a reaction container in parallel to perform one-step coprecipitation reaction to obtain a one-step precursor, and stopping feeding when the particle size of the one-step precursor reaches 3/4-5/6 of the required size;
(3) And adding the solution B, oxalic acid and alkali liquor in parallel flow into a reaction container to perform a two-step coprecipitation reaction, and aging to obtain the lithium-rich manganese-based positive electrode precursor.
According to the invention, through the coprecipitation reaction of two stages of synthesizing the main body material by ammonia water and synthesizing the doped part by oxalic acid, the lithium-rich manganese-based precursor with the surface doped with W is synthesized, the environment of combining transition metal and oxygen is changed, the oxygen release on the surface of the material is inhibited, and the capacity attenuation of the material is relieved.
Ammonia water has relatively lower price and can be recycled, oxalic acid and sodium hydroxide are combined to generate sodium oxalate, oxalic acid radical ions in the solution have the dual functions of a precipitator and a complexing agent, and oxalic acid radical ions are used as ligands to form a metal complex, so that the precipitation rate is slowed down, the nucleation and growth processes are more controllable, and products with narrower particle size distribution can be synthesized.
Preferably, in the solution a of step (1), ni: mn=x: 1-x, where x is 0.2 to 0.3, for example: 0.2, 0.22, 0.25, 0.28 or 0.3, etc.
Preferably, ni: mn: w=x: y: z in the solution B, where x is 0.2 to 0.3 and y is 0.7 to 0.8, for example: 0.7, 0.72, 0.75, 0.78, 0.8, or the like, z is 0.0005 to 0.005, and x+y+z=1.
Preferably, the nickel source comprises any one or a combination of at least two of nickel chloride, nickel sulfate or nickel nitrate.
Preferably, the manganese source comprises any one or a combination of at least two of manganese chloride, manganese sulfate or manganese nitrate.
Preferably, the tungsten source comprises ammonium tungstate and/or ammonium metatungstate.
Preferably, the concentration of the solution A in the step (1) is 1-3 mol/L, for example: 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, etc.
Preferably, the concentration of the solution B is 1-3 mol/L, for example: 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, etc.
Preferably, the lye of step (2) comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the concentration of the lye is 3 to 5mol/L, for example: 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, etc.
Preferably, the concentration of the ammonia water is 8 to 12mol/L, for example: 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, etc.
Preferably, the temperature of the one-step coprecipitation reaction of step (2) is 40 to 70 ℃, for example: 40 ℃, 45 ℃, 50 ℃, 60 ℃ or 70 ℃ and the like.
Preferably, the pH of the one-step coprecipitation reaction is 10 to 12, for example: 10. 10.5, 11, 11.5 or 12, etc.
Preferably, the stirring speed of the one-step coprecipitation reaction is 200 to 400rpm, for example: 200rpm, 250rpm, 300rpm, 350rpm or 400rpm, etc.
Preferably, the lye of step (3) comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the concentration of the lye is 3 to 5mol/L, for example: 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, etc.
Preferably, the oxalic acid concentration is 10-15 mol/L, for example: 10mol/L, 11mol/L, 12mol/L, 13mol/L, 14mol/L, 15mol/L, etc.
Preferably, the temperature of the two-step coprecipitation reaction in step (3) is 40 to 70 ℃, for example: 40 ℃, 45 ℃, 50 ℃, 60 ℃ or 70 ℃ and the like.
Preferably, the pH of the two-step coprecipitation reaction is 10 to 12, for example: 10. 10.5, 11, 11.5 or 12, etc.
Preferably, the stirring speed of the two-step coprecipitation reaction is 200 to 400rpm, for example: 200rpm, 250rpm, 300rpm, 350rpm or 400rpm, etc.
In a second aspect, the present invention provides a lithium-rich manganese-based positive electrode precursor prepared by the method of the first aspect.
Preferably, the median particle diameter D50 of the lithium-rich manganese-based positive electrode precursor is 5 to 20 μm, for example: 5 μm, 8 μm, 10 μm, 15 μm or 20 μm, etc.
In a third aspect, the present invention provides a lithium-rich manganese-based cathode material, which is prepared by mixing and sintering the lithium-rich manganese-based cathode precursor and a lithium source according to the second aspect.
In a fourth aspect, the present invention provides a lithium ion battery comprising a lithium-rich manganese-based cathode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation process of the lithium-rich manganese-based precursor, different complexing agents are adopted in the coprecipitation process of two stages, the price of ammonia water is relatively lower, the ammonia water can be recycled, the complexing effect of oxalic acid is better, and the morphology of the synthesized product is better. The method combines the cost and performance advantages, adopts ammonia water in the main material stage and oxalic acid in the surface doping stage, and synthesizes the doped lithium-rich manganese-based precursor with uniform distribution and good sphericity of doping elements in the precursor.
(2) According to the invention, different coprecipitation systems are respectively adopted in the two stages of precursor main body material and surface doping, so that the optimal balance of doping effect and cost is realized. After W doping, structural collapse caused by material phase change can be relieved, impedance is reduced, charge transfer capacity is improved, thermal stability of the material is improved, and good cycle performance and rate capability are finally displayed.
(3) The initial specific capacity of the battery prepared from the lithium-rich manganese-based positive electrode precursor can reach more than 216.8mAh/g, the capacity retention rate after 200 circles can reach more than 82.6%, the material can exert higher capacity due to proper W doping amount, stable chemical components and crystal structure, the high capacity retention rate after long circulation can be realized, the material performance is judged by comparing the initial discharge specific capacity and the circulation capacity retention rate after lithiation sintering of the lithium-rich manganese-based precursor in different preparation modes, the test is simple and convenient, and the result reliability is high, so that the best performance under the condition of adopting proper W doping amount and complexing agent is proved.
Drawings
Fig. 1 is an SEM image of a lithium-rich manganese-based positive electrode precursor described in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a lithium-rich manganese-based precursor, and the preparation method of the lithium-rich manganese-based precursor comprises the following steps:
(1) Mixing nickel sulfate and manganese sulfate according to the molar ratio of Ni to Mn of 0.25:0.75 to obtain 2mol/L solution A, and mixing nickel sulfate, manganese sulfate and ammonium tungstate according to the molar ratio of Ni to Mn of 0.25:0.748:0.002 to obtain 2mol/L solution B;
(2) In the atmosphere of nitrogen, adding the solution A, a sodium hydroxide solution with the concentration of 4mol/L and ammonia water with the concentration of 10mol/L into a reaction kettle through a metering pump to carry out coprecipitation reaction, and stopping the metering pump of the ammonia water and the solution A when the granularity of precursor particles in the reaction kettle reaches 12 mu m with the required size;
(3) Starting an oxalic acid metering pump for solution B and 14mol/L to perform coprecipitation reaction, stopping feeding when the particle size of the precursor reaches 15 mu m, transferring the materials in the reaction kettle into an aging tank, aging for 6 hours at 60 ℃, and centrifugally washing and drying to obtain the lithium-rich manganese-based positive electrode precursor, wherein an SEM (scanning electron microscope) diagram of the lithium-rich manganese-based positive electrode precursor is shown in figure 1;
and (3) controlling the pH value of the whole coprecipitation reaction process in the step (2) and the step (3) to be 10.5-11, and reacting at 50 ℃ for 75 hours.
Example 2
The embodiment provides a lithium-rich manganese-based precursor, and the preparation method of the lithium-rich manganese-based precursor comprises the following steps:
(1) Mixing nickel sulfate and manganese sulfate according to the molar ratio of Ni to Mn of 0.2:0.8 to obtain a solution A with the concentration of 2.5mol/L, and mixing nickel sulfate, manganese sulfate and ammonium tungstate according to the molar ratio of Ni to Mn of 0.2:0.797:0.003 to obtain a solution B with the concentration of 2.5 mol/L;
(2) In the atmosphere of nitrogen, adding the solution A, a sodium hydroxide solution with the concentration of 4.5mol/L and ammonia water with the concentration of 9mol/L into a reaction kettle through a metering pump for coprecipitation reaction, and stopping the metering pump of the ammonia water and the solution A when the granularity of precursor particles in the reaction kettle reaches 10 mu m of the required size;
(3) Starting an oxalic acid metering pump for solution B and 12mol/L to perform coprecipitation reaction, stopping feeding when the particle size of the precursor reaches 12.5 mu m, transferring materials in a reaction kettle into an aging tank, aging for 6 hours at 60 ℃, and centrifugally washing and drying to obtain the lithium-rich manganese-based positive electrode precursor;
and (3) controlling the pH value of the whole coprecipitation reaction process in the step (2) and the step (3) to be 11-11.2, and reacting at the temperature of 52 ℃ for 70h.
Example 3
This example differs from example 1 only in that the W element in solution B is 0.03% of all elements, and other conditions and parameters are exactly the same as in example 1.
Example 4
This example differs from example 1 only in that the W element in solution B is 0.6% of all elements, and other conditions and parameters are exactly the same as in example 1.
Comparative example 1
The comparative example provides a lithium-rich manganese-based precursor, which is prepared as follows:
(1) According to the mole ratio Ni: mn is 1:3 mixing nickel sulfate and manganese sulfate in proportion, and mixing a mixed salt solution A with the concentration of 2 mol/L;
(2) In the atmosphere of nitrogen, adding the mixed salt solution A, the sodium hydroxide solution with the concentration of 4mol/L and the ammonia water with the concentration of 10mol/L in the step 1 into a reaction kettle respectively through a metering pump, and stirring to perform coprecipitation reaction;
(3) Stopping feeding when the granularity of the precursor particles in the reaction kettle reaches the required size of 15 mu m, controlling the pH value to be 10.5-11 in a process control manner, reacting for 75 hours at 50 ℃, and centrifugally washing and drying to obtain the lithium-rich manganese-based precursor.
Comparative example 2
This comparative example differs from example 1 only in that ammonia was used as the complexing agent for both the co-precipitation reactions of step (2) and step (3), and other conditions and parameters were exactly the same as in example 1.
Performance test:
5Kg of the lithium-rich manganese-based precursor and LiOH of the examples and comparative examples . H 2 O is uniformly mixed in a Henschel mixer according to the mol ratio of 1:1.5, the mixture is dried after being fully ground, the mixture is presintered for 6 hours at 600 ℃, the mixture is calcined for 20 hours in a muffle furnace at 800 ℃ under the oxygen atmosphere, the calcined material is sieved to finally obtain a lithium-rich manganese-based positive electrode material, the positive electrode material is assembled into a CR2025 rechargeable battery, and electrochemical performance detection test results are shown in table 1 under the charging and discharging conditions of 25 ℃ and 2-4.55V and 0.33C/0.33C:
TABLE 1
As can be seen from Table 1, the initial specific capacity of the battery prepared from the lithium-rich manganese-based positive electrode precursor prepared by the method disclosed by the invention can be more than 216.8mAh/g, the capacity retention rate after 200 circles can be more than 82.6%, and the material can exert higher capacity due to proper W doping amount and stable chemical components and crystal structure, and can realize high capacity retention rate after long cycles.
As can be seen from comparison of examples 1 and 3-4, in the preparation process of the lithium-rich manganese-based precursor, the ratio of the W element in the solution B to the total metal elements affects the performance of the prepared lithium-rich manganese-based precursor, the ratio of the W element in the solution B to the total metal elements is controlled to be 0.05-0.5%, the performance of the prepared lithium-rich manganese-based precursor is better, if the ratio of the W element is too low, lattice distortion caused by sufficiently introducing doping elements cannot be realized, and the effect of widening lithium ion transmission channels cannot be achieved, so that the electrochemical performance of the material is improved to a limited extent; if the ratio of W element is too high, besides the capacity of the material is reduced, new defects can be generated, the structure of the material is destroyed, and the performance of the material is deteriorated.
As can be obtained by comparing the example 1 with the comparative example 1, the introduction of the high valence state W doped on the surface of the lithium-rich manganese-based precursor reduces the valence states of Mn and Ni, reduces the activity of surface lattice oxygen, shortens the 4.5V platform length, and inhibits oxygen release. In addition, the strong bonding action caused by hybridization of W (f) and O (p) causes local electronic structure change, and stabilizes the precursor crystal lattice. The ion phase doping effectively inhibits the irreversible oxidation-reduction reaction of oxygen on the surface of the material by changing the binding capacity between the transition metal cations and the oxygen anions, and reduces the occurrence of transition metal ion migration induced material phase transition.
The method has the advantages that compared with the method in the embodiment 1 and the comparative example 2, ammonia water is relatively lower in price and recoverable, the complexing effect of oxalic acid is better, the morphology of the synthesized product is better, the method integrates the cost and performance advantages, the main material stage adopts ammonia water, the surface doping stage adopts oxalic acid, and the doped lithium-rich manganese-based precursor with uniform distribution and good sphericity of doped elements in the precursor is synthesized.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the lithium-rich manganese-based positive electrode precursor is characterized by comprising the following steps of:
(1) Mixing a nickel source, a manganese source and a solvent to obtain a solution A, and mixing a nickel source, a manganese source and a tungsten source with the solvent to obtain a solution B;
(2) Adding the solution A, alkali liquor and ammonia water into a reaction container in parallel to perform one-step coprecipitation reaction to obtain a one-step precursor, and stopping feeding when the particle size of the one-step precursor reaches 3/4-5/6 of the required size;
(3) And adding the solution B, oxalic acid and alkali liquor in parallel flow into a reaction container to perform a two-step coprecipitation reaction, and aging to obtain the lithium-rich manganese-based positive electrode precursor.
2. The method of claim 1, wherein Ni: mn=x: 1-x in the solution a in step (1), wherein x is 0.2 to 0.3;
preferably, in the solution B, ni: mn: w=x: y: z, wherein x is 0.2 to 0.3, y is 0.7 to 0.8, z is 0.0005 to 0.005, and x+y+z=1;
preferably, the nickel source comprises any one or a combination of at least two of nickel chloride, nickel sulfate or nickel nitrate;
preferably, the manganese source comprises any one or a combination of at least two of manganese chloride, manganese sulfate or manganese nitrate;
preferably, the tungsten source comprises ammonium tungstate and/or ammonium metatungstate.
3. The preparation method according to claim 1 or 2, wherein the concentration of the solution a in the step (1) is 1 to 3mol/L;
preferably, the concentration of the solution B is 1-3 mol/L.
4. A process according to any one of claims 1 to 3, wherein the lye of step (2) comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the concentration of the alkali liquor is 3-5 mol/L;
preferably, the concentration of the ammonia water is 8-12 mol/L.
5. The method of any one of claims 1-4, wherein the one-step coprecipitation reaction in step (2) is at a temperature of 40-70 ℃;
preferably, the pH of the one-step coprecipitation reaction is 10 to 12;
preferably, the stirring speed of the one-step coprecipitation reaction is 200 to 400rpm.
6. The process according to any one of claims 1 to 5, wherein the lye of step (3) comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the concentration of the alkali liquor is 3-5 mol/L;
preferably, the concentration of the oxalic acid is 10-15 mol/L.
7. The method of any one of claims 1-6, wherein the temperature of the two-step coprecipitation reaction in step (3) is 40-70 ℃;
preferably, the pH of the two-step coprecipitation reaction is 10-12;
preferably, the stirring speed of the two-step coprecipitation reaction is 200 to 400rpm.
8. A lithium-rich manganese-based positive electrode precursor, characterized in that it is produced by the method according to any one of claims 1 to 7, and has a median particle diameter D50 of 5 to 20 μm.
9. The lithium-rich manganese-based positive electrode material is characterized in that the lithium-rich manganese-based positive electrode material is prepared by mixing and sintering the lithium-rich manganese-based positive electrode precursor according to claim 8 and a lithium source.
10. A lithium ion battery comprising the lithium-rich manganese-based positive electrode material of claim 9.
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