CN117059761A - Sodium ion positive electrode material and preparation method thereof - Google Patents
Sodium ion positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN117059761A CN117059761A CN202310887791.3A CN202310887791A CN117059761A CN 117059761 A CN117059761 A CN 117059761A CN 202310887791 A CN202310887791 A CN 202310887791A CN 117059761 A CN117059761 A CN 117059761A
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- CN
- China
- Prior art keywords
- electrode material
- positive electrode
- sodium ion
- sintering
- ion positive
- Prior art date
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 107
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 100
- 239000011734 sodium Substances 0.000 claims abstract description 91
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 64
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 64
- 239000001301 oxygen Substances 0.000 claims abstract description 62
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 62
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011247 coating layer Substances 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 67
- 238000002156 mixing Methods 0.000 claims description 64
- 239000002245 particle Substances 0.000 claims description 64
- 238000005245 sintering Methods 0.000 claims description 64
- 239000002243 precursor Substances 0.000 claims description 44
- 238000009423 ventilation Methods 0.000 claims description 43
- 238000007873 sieving Methods 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 4
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- 239000011572 manganese Substances 0.000 description 75
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 71
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 54
- 239000011162 core material Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052748 manganese Inorganic materials 0.000 description 16
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- -1 Oxygen ion Chemical class 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
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- 238000011065 in-situ storage Methods 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
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- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
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- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- 229910003176 Mn-O Inorganic materials 0.000 description 2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
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- 241001274216 Naso Species 0.000 description 1
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 1
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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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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- 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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- Organic Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of material preparation, and discloses a sodium ion positive electrode material and a preparation method thereof. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is composite metal oxide, and the chemical formula of the composite metal oxide is Na i Ni a Fe b Mn c M (1‑a‑b‑c) □ d O 2‑d Material for coating layerThe material is metal oxide. Wherein, the oxygen vacancy is represented by ∈m, i is more than 0.7 and less than or equal to 1.0, a is more than 0 and less than or equal to 0.4, b is more than 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.4, a+b+c is less than 1, and d is more than 0 and less than or equal to 0.5. The material has a large amount of oxygen vacancies, is doped and coated with metal, can inhibit phase change of the material, stabilize the crystal structure inside the material, reduce internal defects of the material, and improve specific capacity and cycle performance of the material.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a sodium ion positive electrode material and a preparation method thereof.
Background
Due to the advantages of high working voltage, high energy density, long cycle life and the like, lithium ion batteries are widely applied to 3C electronic products, energy storage equipment and electric automobiles. However, the price of lithium resources is continuously rising, and it is difficult to meet the requirement of large-scale low-cost energy storage. Therefore, there is a need for an energy storage system that is resource-efficient and low cost and that can partially replace lithium ion batteries. The sodium resource is abundant, the cost is low, the safety is higher, the low temperature and the quick charge performance are better, and the principle is similar to that of a lithium ion battery, so that the sodium ion battery can relieve the problem of lithium resource shortage to a certain extent, and the market application of the lithium ion battery is supplemented to a certain extent, especially the application in a large-scale energy storage power grid.
The key battery characteristics such as specific capacity, cycling stability and operating voltage are mainly determined by the intrinsic electrochemical characteristics of the electrode materials, so the most important focus of sodium ion batteries is to find suitable electrode materials, especially positive electrode materials that determine the energy density of the battery.
Currently, the positive electrode materials of sodium ion batteries mainly comprise polyanion materials, prussian blue analogues, layered transition metal oxides and the like. Among these candidate materials, transition metal oxide cathode materials are attracting attention because of their simple structure, ease of synthesis, and high operating potential. The cost is a core element that drives sodium ion batteries to compete with lithium ion batteries. Manganese has the advantages of environmental friendliness, low price and high annual output, and most of sodium ion battery anode materials adopt manganese-containing layered metal oxide materials. Mn (Mn) 3+ With six coordination, the configuration of the complex is octahedral. Oxygen ion ligands with six vertices of octahedronThe ligand is coordinated with Mn 3+ Are connected. According to coordination field theory, when the ion is a regular octahedral configuration complex, d orbit is split into T 2g And E is g Track, T 2g And E is g The energy of the track is the same. Due to high spin Mn 3+ (T 2g 3 Eg 1 ) Represented by the elongation of the two axial Mn-O bonds and the contraction of the other four bonds. When twisted Mn 3+ O 6 When the octahedron directions are collinear, the ginger Taylor effect is easy to occur, and large volume strain and undesirable intragranular cracks are caused, so that the manganese-based layered transition metal oxide has poor structural stability and rapid capacity decay. In addition, manganese-based layered oxides are highly air sensitive and may react with water in the air, resulting in reduced performance.
Disclosure of Invention
In order to solve the problems, the invention provides a sodium ion positive electrode material and a preparation method thereof. The material has a large amount of oxygen vacancies, is doped and coated with metal, can inhibit phase change of the material, stabilize the crystal structure inside the material, reduce internal defects of the material, and improve specific capacity and cycle performance of the material.
To achieve the above object, the first aspect of the present invention provides a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is composite metal oxide, and the chemical formula of the composite metal oxide is Na i Ni a Fe b Mn c M (1-a-b-c) d O 2-d The material of the coating layer is metal oxide. Wherein (1)>Representing oxygen vacancy, M is a metal element, i is more than 0.7 and less than or equal to 1.0, a is more than 0 and less than or equal to 0.4, b is more than 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.4, a+b+c is more than 1, and d is more than 0 and less than or equal to 0.5.
The sodium ion positive electrode material of the invention has at least the following technical effects:
(1) In situ production in the inner core of materialAnd more oxygen vacancies are generated, so that the oxygen vacancies can reduce the average valence state of Mn, realize more sodium ion deintercalation and improve the specific capacity. Meanwhile, the oxygen vacancy reduces the symmetry of the Mn-O ligand, so that the Mn3d electron orbit energy level is reduced, and the specific capacity and the working potential of Mn redox reaction are improved. In the material containing oxygen vacancies, more carriers exist to participate in the conduction process, so that the conduction performance of the material can be improved. In addition, oxygen vacancies can induce excess electrons around a particular metal atom, which can attract Na as a negative charge center + Promote Na + And the diffusion is fast, and the rate performance is improved. At the same time, oxygen vacancies may also provide additional active sites for redox reactions to improve capacitive performance.
(2) Oxygen vacancies act as a defective structure, resulting in collapse of the structure and interlayer slip during long-term cycling. The surface is coated with stable metal oxide, so that the phase change of the core material can be inhibited, and the structural stability of the material is improved. In addition, at a certain temperature, the metal oxide can react with the residual sodium on the surface of the material, so that the residual sodium on the surface of the material is reduced, the contact between the positive electrode material and the electrolyte is isolated, the side reaction of the material is reduced, and the high capacity and high multiplying power of the battery are realized while the cycle performance is improved.
In some embodiments, M is selected from at least one of Mg, zr, cu, al, ti, W, zn and Y.
In some embodiments, the metal oxide comprises ZrO 2 、Al 2 O 3 CuO and TiO 2 At least one of them.
In some embodiments, the metal oxide is present in an amount of 1000ppm to 5000ppm.
In some embodiments, the thickness of the coating is 0.05 μm to 2.00 μm.
In some embodiments, the D50 of the sodium ion positive electrode material is 1 μm to 12 μm.
In some embodiments, the specific surface area of the sodium ion positive electrode material is 0.2m 2 /g to 2.0m 2 /g。
In some embodiments, the sodium ion positive electrode material has a compacted density of 2.0g/cm 3 To 4.0g/cm 3 。
In some embodiments, the sodium ion positive electrode material has a specific capacity for first discharge of greater than or equal to 140mAh/g.
In some embodiments, the first discharge efficiency of the sodium ion positive electrode material is greater than or equal to 90%.
The second aspect of the invention provides a preparation method of the sodium ion positive electrode material, which comprises the steps of (I) premixing, (II) sintering and (III) coating.
Premixing in the step (I): will be of the chemical formula Ni a Fe b Mn c (OH) 2 And a sodium source and a metal source, wherein a+b+c=1.
Sintering in the step (II): pre-sintering the premix in an oxygen-containing atmosphere, performing primary sintering at 800-970 ℃ in an inert atmosphere, cooling to room temperature, crushing and sieving to obtain the composite metal oxide with oxygen vacancies.
Step (III) cladding: mixing the composite metal oxide with oxygen vacancies and the metal oxide, sintering for the second time, crushing and sieving.
In the preparation method, the metal source, the precursor and the sodium source are mixed and sintered for the first time at 800-970 ℃ to dope metal ions so as to inhibit the phase change of the material, stabilize the crystal structure inside the material and reduce the internal defects of the material. After presintering in oxygen-containing atmosphere, sintering in high-temperature inert atmosphere at 800-970 ℃, cooling to room temperature for annealing treatment, so that lattice oxygen can be separated, oxygen is lost, and oxygen vacancies are formed in situ near metal ions of the core. The metal oxide coating layer is formed on the surface of the composite metal oxide with oxygen vacancies, so that the influence of the oxygen vacancies on the material circulation performance can be overcome.
In some embodiments, the sodium source comprises at least one of sodium hydroxide, sodium carbonate, sodium nitrate, and sodium acetate.
In some embodiments, the metal source comprises MgO, zrO 2 、CuO、Al 2 O 3 、TiO 2 、WO 3 ZnO and Y 2 O 3 At least one of them.
In some embodiments, the metal source is present in an amount of 2000ppm to 6000ppm.
In some embodiments, the molar amount of sodium element in the sodium source is m, the sum of the molar amounts of metal in the precursor is n, and m/n is 0.8 to 1.1:1.
In some embodiments, the metal oxide comprises ZrO 2 、Al 2 O 3 CuO and TiO 2 At least one of them.
In some embodiments, the metal oxide content is 800ppm to 4500ppm.
In some embodiments, the mixing is performed in a pre-mix using a VC blender at a speed of 200rpm to 800rpm for a mixing time of 30 minutes to 120 minutes.
In some embodiments, air is introduced during burn-in, the ventilation of the air being 2m 3 /h to 8m 3 /h。
In some embodiments, the pre-firing temperature is 400 ℃ to 800 ℃.
In some embodiments, the soak time for burn-in is 1h to 6h.
In some embodiments, the burn-in has a ramp rate of 0.5 ℃/min to 3.0 ℃/min.
In some embodiments, the inert atmosphere comprises at least one of argon, helium, and neon.
In some embodiments, the inert atmosphere has a ventilation of 2m 3 /h to 8m 3 /h。
In some embodiments, the soak time for the first sintering is from 5 hours to 12 hours.
In some embodiments, the first sintering is at a ramp rate of 0.5 ℃/min to 3.0 ℃/min.
In some embodiments, the coating is mixed using a VC blender at a speed of 200rpm to 800rpm for a period of 30 minutes to 120 minutes.
In some embodiments, air is introduced during the second sintering, the ventilation of the air being 2m 3 /h to 8m 3 /h。
In some embodiments, the temperature of the second sintering is 600 ℃ to 950 ℃.
In some embodiments, the soak time for the second sintering is from 1h to 8h.
In some embodiments, the second sintering is at a ramp rate of 0.5 ℃/min to 3.0 ℃/min.
In some embodiments, the crushing in sintering is to crush the sintered material after the first sintering into particles with the particle size of 1mm to 3mm by a jaw crusher and a pair of rollers in sequence, and then crush the particles by an air flow mill.
In some embodiments, the crushing in the coating is to crush the sintered material after the second sintering into particles with the particle size of 1mm to 3mm by a jaw crusher and a pair of rollers in sequence, and then crush the particles by an air flow mill.
In some embodiments, the sieving in sintering and the sieving in coating are through a 325 mesh vibrating screen.
The third aspect of the invention provides a sodium ion battery, which comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode material comprises the sodium ion positive electrode material or the sodium ion positive electrode material prepared by the preparation method of the sodium ion positive electrode material.
In some embodiments, the negative electrode material comprises a carbonaceous negative electrode material and/or a silicon-based negative electrode material.
Drawings
Fig. 1 is an SEM electron microscope of the sodium ion cathode material prepared in example 1 of the present invention.
Detailed Description
The sodium ion battery comprises a positive electrode material, a negative electrode material and electrolyte. The preparation process of the sodium ion battery is similar to that of a lithium ion battery, and the positive plate containing positive electrode materials and the negative plate containing negative electrode materials are prepared firstly, and then the positive plate, the negative plate and the isolating film are wound or laminated into a bare cell, filled with electrolyte and sealed in a shell.
The negative electrode plate is obtained by coating negative electrode slurry containing a negative electrode material, a binder and a conductive agent on a negative electrode current collector, drying, cold pressing and die cutting. The mass ratio of the cathode material, the binder and the conductive agent can be 60-99:0.1-20:0.1-20. Negative electrode material bagIncluding carbonaceous anode materials and/or silicon-based anode materials. The carbonaceous negative electrode material may be, but is not limited to, graphite-based material, soft carbon, hard carbon. The silicon-based anode material may be, but is not limited to, siO x Or carbon coated SiO x X is more than or equal to 0 and less than 2. The binder is used for improving the adhesion between the anode material particles and the anode current collector. At least one selected from the group consisting of polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, styrene-butadiene rubber and acrylated styrene-butadiene rubber. The conductive agent is used to improve the conductivity of the negative electrode, and may be, for example, but not limited to, carbon-containing materials such as carbon black, acetylene black, ketjen black, carbon fiber, or metal powder or metal fiber materials such as copper, nickel, aluminum, silver, or conductive polymers such as polyphenylene derivatives, or mixtures thereof. The solvent of the anode slurry may be N-methylpyrrolidone or N-vinylpyrrolidone. The negative electrode current collector may be selected from copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, polymer substrate coated with conductive metal, and the like.
The separator may be a conventional insulating porous polymer film or an inorganic porous film, and may be specifically but not limited to: single layer or combined multiple layers of polypropylene, polyethylene, aramid, polyimide and nonwoven membranes, such as polyethylene/polypropylene double layer membranes, polyethylene/polypropylene/polyethylene triple layer membranes or polypropylene/polyethylene/polypropylene triple layer membranes. An insulating layer which is not electrified by ions and is electrified by electrons can be arranged on the isolating film to prevent the sodium ion battery from being short-circuited when thermal shrinkage occurs, and the thickness of the isolating film is 5-50 mu m.
Similar to lithium ion batteries, the liquid electrolyte for sodium ion batteries includes a nonaqueous organic solvent, sodium salt, and additives. The nonaqueous organic solvent is required to have a large dielectric constant, a low melting point, and a strong sodium ion conductivity, and may be generally a chain carbonate, a cyclic carbonate, a carboxylate or a lactone. The chain carbonate may be dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate or ethylmethyl carbonate. The cyclic carbonate may be ethylene carbonate, propylene carbonate or butylene carbonate. The carboxylic acid ester can be methyl acetate,Ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate or ethyl propionate. The lactone may be gamma-butyrolactone, delta-decalactone, gamma-valerolactone or gamma-caprolactone. The sodium salt may be NaPF 6 、NaClO 4 、NaAlCl 4 、NaFeCl 4 、NaSO 3 CF 3 、NaBCl 4 、NaNO 3 、NaPOF 4 、NaSCN、NaCN、NaAsF 6 、NaCF 3 CO 2 、NaSbF 6 、NaC 6 H 5 CO 2 、Na(CH 3 )C 6 H 4 SO 3 、NaHSO 4 And NaB (C) 6 H 5 ) 4 The molar concentration of the sodium salt is from 0.2M to 2.0M. Additives may also be added to the electrolyte to improve battery performance, and the additives may comprise at least 0.1% and at least 10% by mass of the electrolyte. Including but not limited to, one or more of ethylene sulfite (GS), fluoroethylene carbonate (FEC), vinylene Carbonate (VC), vinyl Ethylene Carbonate (VEC), 1, 3-Propane Sultone (PS), ethylene sulfate (DTD), 4-methyl ethylene sulfate, 4-propyl ethylene sulfate, propylene sulfate, 4-methyl propylene sulfate, and 4-propyl propylene sulfate.
The preparation of the positive electrode sheet generally includes: and (3) coating positive electrode slurry containing a positive electrode material, a binder and a conductive agent on a positive electrode current collector, drying, cold pressing and die cutting. The mass ratio of the positive electrode material, the binder and the conductive agent can be 80-99:0.5-20:0.5-20. The binder may be, for example, but not limited to, at least one of polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, styrene-butadiene rubber, acrylated styrene-butadiene rubber, and epoxy resin. The conductive agent is used to improve the conductivity of the positive electrode, and may be, for example, but not limited to, carbon-containing materials such as carbon black, acetylene black, ketjen black, carbon fiber, or metal powders or metal fiber materials such as copper, nickel, aluminum, silver, or conductive polymers such as polyphenylene derivatives, or mixtures thereof. The positive electrode current collector may be aluminum foil. The solvent of the positive electrode slurry may be N-methylpyrrolidone or N-vinylpyrrolidone. The positive electrode material can adopt the sodium ion positive electrode material.
The sodium ion positive electrode material comprises a core and a coating layer. The first discharge specific capacity of the sodium ion positive electrode material is more than or equal to 140mAh/g. In some embodiments, the morphology of the sodium ion cathode material is single crystal, polycrystalline, or a mixed phase of single crystal and polycrystalline. The first discharge specific capacity of the sodium ion positive electrode material is more than or equal to 145mAh/g. As an example, the specific first discharge capacity may be, but is not limited to, 140.0mAh/g, 141.0mAh/g, 142.0mAh/g, 143.0mAh/g, 144.0mAh/g, 145.0mAh/g, 146.0mAh/g, 147.0mAh/g, 148.0mAh/g, 149.0mAh/g, 150.0mAh/g. The first discharge efficiency of the sodium ion positive electrode material is more than or equal to 90 percent. In some embodiments, the first discharge efficiency is greater than or equal to 91%. In still other embodiments, the first charge-discharge efficiency is greater than or equal to 93%. As an example, the first discharge efficiency of the sodium ion positive electrode material may be, but is not limited to, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%. The D50 of the sodium ion positive electrode material is 1 μm to 12 μm, in some embodiments the D50 is 3 μm to 10 μm, and in other embodiments the D50 is 5 μm to 8 μm. By way of example, the D50 may be, but is not limited to, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm. The specific surface area of the sodium ion positive electrode material is 0.2m 2 /g to 2.0m 2 Per gram, in some embodiments, the specific surface area is 0.5m 2 /g to 1.5m 2 In other embodiments, the specific surface area is 0.5m 2 /g to 1.0m 2 And/g. As an example, the specific surface area of the sodium ion positive electrode material may be, but is not limited to, 0.2m 2 /g、0.4m 2 /g、0.8m 2 /g、1.0m 2 /g、1.3m 2 /g、1.5m 2 /g、1.7m 2 /g、2.0m 2 And/g. The compacted density of the sodium ion positive electrode material is 2.0g/cm 3 To 4.0g/cm 3 In some embodiments, the compacted density is 2.0g/cm 3 To 3.5g/cm 3 In other embodiments, the compacted density is 2.5g/cm 3 To 3.5g/cm 3 As an example, the compacted density of the sodium ion positive electrode material may be, but is not limited to, 2.0g/cm 3 、2.2g/cm 3 、2.4g/cm 3 、2.6g/cm 3 、2.8g/cm 3 、3.0g/cm 3 、3.2g/cm 3 、3.4g/cm 3 、3.6g/cm 3 、3.8g/cm 3 、4.0g/cm 3 。
The material of the inner core is composite metal oxide, and the chemical formula of the composite metal oxide is Na i Ni a Fe b Mn c M (1-a-b-c) d O 2-d Wherein->Representing oxygen vacancy, M is a metal element, i is more than 0.7 and less than or equal to 1.0, a is more than 0 and less than or equal to 0.4, b is more than 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.4, a+b+c is more than 1, and d is more than 0 and less than or equal to 0.5. By way of example, i may be, but is not limited to, 0.75, 0.80, 0.85, 0.90, 1.0.a may be, but is not limited to, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40.b may be, but is not limited to, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40.c may be, but is not limited to, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40.d may be, but is not limited to, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50. In some embodiments, M is selected from at least one of Mg, zr, cu, al, ti, W, zn and Y.
The thickness of the coating layer is 0.05 μm to 2.00 μm, and as an example, the thickness of the coating layer may be, but is not limited to, 0.05 μm, 0.10 μm, 0.15 μm, 0.25 μm, 0.55 μm, 0.75 μm, 0.85 μm, 1.00 μm, 1.15 μm, 1.35 μm, 1.45 μm, 1.55 μm, 1.65 μm, 1.75 μm, 1.85 μm, 1.95 μm, 2.00 μm. The material of the coating layer is metal oxide, and the metal oxide comprises ZrO 2 、Al 2 O 3 CuO and TiO 2 At least one of them. The content of the metal oxide is 1000ppm to 5000ppm, and as an example, the content of the metal oxide may be, but is not limited to, 1000ppm, 1300ppm, 1700ppm, 2000ppm, 2300ppm, 2500ppm, 2700ppm, 3000ppm, 3300ppm, 3700ppm, 4000ppm, 4500ppm, 5000ppm.
The preparation method of the sodium ion positive electrode material comprises the steps of premixing in the step (I), sintering in the step (II) and coating in the step (III).
The premixing in the step (I) comprises the following steps: will be of the chemical formula Ni a Fe b Mn c (OH) 2 And a sodium source and a metal source, wherein a+b+c=1.
Wherein the precursor may be prepared by conventional methods. As an example, the precursor may be obtained by performing a coprecipitation reaction using a nickel salt, a ferrite salt, a manganese salt, a complexing agent, and a precipitant. The method comprises the following steps: adding nickel salt, ferrous salt, manganese salt, complexing agent and precipitant into a reaction kettle with bottom liquid for coprecipitation, continuously introducing inert gas in the reaction process, continuously reacting until the granularity of the product reaches the target granularity, and aging, centrifuging, drying, screening, removing iron and packaging the product to obtain the nickel-iron-manganese ternary precursor.
Wherein, the nickel salt can be nickel sulfate, nickel chloride, nickel acetate or nickel nitrate. The ferrous salt can be ferrous sulfate, ferrous chloride, ferrous acetate or ferrous nitrate. The manganese salt may be manganese sulfate, manganese chloride, manganese acetate or manganese nitrate. The complexing agent may be an oxalic acid solution. The precipitant is sodium hydroxide solution, potassium hydroxide solution or ammonia water solution. The concentration of nickel salt, ferrous salt and manganese salt is less than or equal to 2.0mol/L, the concentration of precipitant is less than or equal to 11.0mol/L, and the concentration of complexing agent is less than or equal to 1.0mol/L. The base solution can be prepared by heating pure water to 40-70 ℃, then adding oxalic acid solution, adjusting the concentration of oxalate ions to 0.1-0.5 mol/L, and adding alkali liquor to adjust the pH value to 11-12. The pH value of the granulating stage control system reaching the target granularity is 10-11.5 and is smaller than the pH value in the base solution.
The sodium source includes at least one of sodium hydroxide, sodium carbonate, sodium nitrate, and sodium acetate. The molar amount of sodium element in the sodium source is m, the sum of the molar amounts of metal in the precursor is n, m/n is 0.8-1.1:1, and as an example, m/n can be but is not limited to 0.8:1, 0.9:1, 1.0:1, 1.1:1. The metal source comprises MgO, zrO 2 、CuO、Al 2 O 3 、TiO 2 、WO 3 ZnO and Y 2 O 3 At least one of them. The content of the metal source is 2000ppm to 6000ppm as an illustration For example, the content of the metal source may be, but is not limited to, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 5000ppm, 5500ppm, 6000ppm. In the premixing, a VC mixer is adopted for mixing, the rotating speed of the VC mixer is 200rpm to 800rpm, and the mixing time is 30min to 120min. As an example, the rotational speed of the VC mixer may be, but is not limited to, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm. The mixing time of the VC mixer is 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min and 120min.
The step (II) sintering comprises the following steps: pre-sintering the premix in an oxygen-containing atmosphere, performing primary sintering at 800-970 ℃ in an inert atmosphere, cooling to room temperature, crushing and sieving to obtain the composite metal oxide with oxygen vacancies.
Wherein, air is introduced during presintering, and the ventilation amount of the air is 2m 3 /h to 8m 3 By way of example, the ventilation of air may be, but is not limited to, 2m 3 /h、3m 3 /h、4m 3 /h、5m 3 /h、6m 3 /h、7m 3 /h、8m 3 And/h. The temperature of the burn-in is 400 to 800 ℃, and as an example, the temperature of the burn-in may be, but not limited to, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃. The soak time for burn-in is 1h to 6h, and as an example, the soak time for burn-in may be, but not limited to, 1h, 2h, 3h, 4h, 5h, 6h. The pre-firing rate of temperature rise is 0.5 to 3.0 c/min, as examples, the pre-firing rate of temperature rise may be, but is not limited to, 0.5 c/min, 1.0 c/min, 1.5 c/min, 2.0 c/min, 2.5 c/min, 3.0 c/min. The inert atmosphere comprises at least one of argon, helium and neon. The ventilation of the inert atmosphere was 2m 3 /h to 8m 3 And/h. As an example, the aeration of the inert atmosphere may be, but is not limited to, 2m 3 /h、3m 3 /h、4m 3 /h、5m 3 /h、6m 3 /h、7m 3 /h、8m 3 And/h. The heat preservation time of the first sintering is 5h to 12h. As an example, the soak time for the first sintering may be, but is not limited to, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h. First firingThe temperature rise rate of the junction is 0.5 ℃/min to 3.0 ℃/min. As an example, the rate of temperature rise of the first sintering may be, but is not limited to, 0.5 ℃/min, 1.0 ℃/min, 1.5 ℃/min, 2.0 ℃/min, 2.5 ℃/min, 3.0 ℃/min. Crushing into particles with the particle diameter of 1mm to 3mm after the sintered material after the first sintering is crushed by a jaw crusher and a pair roller machine in sequence, and crushing by an air flow mill. Sieving with 325 mesh vibrating sieve.
The step (III) coating comprises: mixing the composite metal oxide with oxygen vacancies and the metal oxide, sintering for the second time, crushing and sieving.
Wherein the metal oxide comprises ZrO 2 、Al 2 O 3 CuO and TiO 2 At least one of them. The metal oxide content is 800ppm to 4500ppm. By way of example, the metal oxide content may be, but is not limited to, 800ppm, 1000ppm, 1300ppm, 1500ppm, 1800ppm, 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm. In the coating, a VC mixer is adopted for mixing, the rotating speed of the VC mixer is 200rpm to 800rpm, and the mixing time is 30min to 120min. As an example, the rotational speed of the VC mixer may be, but is not limited to, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm. The mixing time of the VC mixer is 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min and 120min. Introducing air during the second sintering, wherein the ventilation amount of the air is 2m 3 /h to 8m 3 And/h. As an example, the ventilation of air may be, but is not limited to, 2m 3 /h、3m 3 /h、4m 3 /h、5m 3 /h、6m 3 /h、7m 3 /h、8m 3 And/h. The temperature of the second sintering is 600 ℃ to 950 ℃. As an example, the temperature of the second sintering may be, but is not limited to, 600 ℃, 630 ℃, 650 ℃, 670 ℃, 700 ℃, 730 ℃, 760 ℃, 780 ℃, 800 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃, 950 ℃. The heat preservation time of the second sintering is 1h to 8h. As an example, the soak time for the second sintering may be, but is not limited to, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h. The temperature rising rate of the second sintering is 0.5 ℃/min to 3.0 ℃/min. As an example, the secondThe rate of temperature rise for the secondary sintering may be, but is not limited to, 0.5 ℃/min, 1.0 ℃/min, 1.5 ℃/min, 2.0 ℃/min, 2.5 ℃/min, 3.0 ℃/min. Crushing into particles with the particle diameter of 1mm to 3mm after the sintered material after the second sintering is crushed by a jaw crusher and a pair roller machine in sequence, and crushing by an air flow mill. Sieving with 325 mesh vibrating sieve.
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
Example 1
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.95 Ni 0.329 Fe 0.333 Mn 0.334 Zr 0.004 0.48 O 1.52 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 /h, 2 ℃/min riseHeating to 600 ℃ at a temperature rate, and preserving heat for 5 hours. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
The obtained sodium ion positive electrode material was subjected to SEM electron microscopy, and the result is shown in fig. 1. As can be seen from fig. 1, the particles of the prepared sodium ion positive electrode material have a polycrystalline structure, and a coating layer is formed on the surface of the material.
Example 2
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.90 Ni 0.329 Fe 0.334 Mn 0.333 Zr 0.004 0.40 O 1.60 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein, the rotational speed of VC blendor 600rpm, mixing time of 90min, precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.02:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas nitrogen is introduced, and the ventilation is 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Example 3
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.94 Ni 0.327 Fe 0.332 Mn 0.334 Ti 0.007 0.42 O 1.58 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、TiO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.TiO (titanium dioxide) 2 The content of (2) was 5000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 860 ℃ at a heating rate of 2 ℃/min, preserving heat for 4h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Example 4
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.97 Ni 0.396 Fe 0.398 Mn 0.200 Zr 0.006 0.50 O 1.50 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer is Al 2 O 3 ，Al 2 O 3 The content of (C) was 3000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 2/5 Fe 2/5 Mn 1/5 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (2) was 5000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 970 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
Composite metal oxide with oxygen vacancy and Al by VC blendor 2 O 3 Mixing, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and Al 2 O 3 The content of (C) was 3000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Passing the sinter through jaw crusherCrushing the particles with the particle size of about 2mm by a roller machine, crushing the particles by using an air flow mill, and passing through a 325-mesh vibrating screen.
Example 5
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.93 Ni 0.328 Fe 0.334 Mn 0.334 Zr 0.004 0.45 O 1.55 . The thickness of the coating layer was 0.80. Mu.m. The material of the coating layer is Al 2 O 3 ，Al 2 O 3 The content of (2) was 1000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And sodium acetate, zrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na in sodium acetate and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
Complex with oxygen vacancy using VC blendorMetal oxide and Al 2 O 3 Mixing, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and Al 2 O 3 The content of (2) was 1000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Example 6
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.92 Ni 0.331 Fe 0.333 Mn 0.332 Zr 0.004 0.48 O 1.52 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 400rpm, the mixing time is 120min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 7m 3 And/h, heating to 750 ℃ at a heating rate of 1.0 ℃/min, and preserving heat for 3h. Then inert gas argon is introduced, and the ventilation is 7m 3 Heating at a heating rate of 2 ℃/minTo 950 ℃ and preserving heat for 10 hours, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 700rpm, the mixing time is 60min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Example 7
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.91 Ni 0.331 Fe 0.331 Mn 0.334 Zr 0.004 0.38 O 1.62 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 900 ℃ at a heating rate of 2.5 ℃/min, preserving heat for 7h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 6m 3 And/h, heating to 850 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Comparative example 1
The present embodiment is a sodium ion positive electrode material having a chemical formula of Na 0.95 Ni 0.329 Fe 0.333 Mn 0.334 Zr 0.004 0.48 O 1.52 The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps. />
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
Comparative example 2
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.95 Ni 0.329 Fe 0.333 Mn 0.334 Zr 0.004 0.05 O 1.95 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Continuously introducing air with ventilation volume of 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Comparative example 3
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.85 Ni 0.330 Fe 0.335 Mn 0.331 Zr 0.004 0.30 O 1.70 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or by the foregoingThe preparation method. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing inert gas argon with the ventilation of 5m 3 And/h, heating to 950 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Comparative example 4
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.8 Ni 0.329 Fe 0.333 Mn 0.334 Zr 0.004 0.10 O 1.90 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer was CuO, and the content of CuO was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Premixing
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 Mixing by VCAnd mixing by a feeder to obtain premix. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) sintering
Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Then inert gas argon is introduced, and the ventilation is 5m 3 And/h, heating to 750 ℃ at a heating rate of 2 ℃/min, preserving heat for 10h, and cooling to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and then crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide with oxygen vacancies.
(III) coating
And mixing the composite metal oxide with oxygen vacancies and CuO by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
Comparative example 5
This example is a sodium ion positive electrode material. The sodium ion positive electrode material comprises a core and a coating layer. The material of the inner core is Na 0.92 Ni 0.328 Fe 0.334 Mn 0.334 Zr 0.004 0.04 O 1.96 . The thickness of the coating layer was 1.00. Mu.m. The material of the coating layer is CuO with oxygen vacancies and the CuO with oxygen vacancies containsThe amount was 2000ppm.
The preparation method of the sodium ion positive electrode material of the embodiment comprises the following steps.
(I) Sintering
Precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 And Na (Na) 2 CO 3 、ZrO 2 And mixing by adopting a VC mixer to obtain premix. Placing the premix into a box-type furnace, and introducing air with ventilation volume of 5m 3 And/h, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 5h. Air is continuously introduced, the mixture is heated to 950 ℃ at a heating rate of 2 ℃/min, the temperature is kept for 10 hours, and the mixture is cooled to room temperature. Crushing the sintered material by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, and crushing by a jet mill and sieving by a 325-mesh vibrating screen to obtain the composite metal oxide. Wherein the rotating speed of the VC mixer is 600rpm, the mixing time is 90min, and the precursor Ni 1/3 Fe 1/3 Mn 1/3 (OH) 2 Commercially available or prepared by the methods described above. Na (Na) 2 CO 3 Medium Na and precursor Ni 1/3 Fe 1/ 3 Mn 1/3 (OH) 2 The ratio of the sum of the moles of Ni, fe and Mn is 1.05:1.ZrO (ZrO) 2 The content of (C) was 3000ppm.
(II) reduction of oxides
And (3) placing the CuO nano-particles in a tube furnace with the temperature rising rate of 5 ℃/min, sintering for 6 hours at 450 ℃ under the mixed atmosphere of 5vol.% of hydrogen and 95vol.% of argon, and cooling to room temperature along with the furnace to obtain the CuO with oxygen vacancies.
(III) coating
Mixing the CuO with oxygen vacancies and the composite metal oxide by adopting a VC mixer, wherein the rotating speed of the VC mixer is 450rpm, the mixing time is 110min, and the content of the CuO with oxygen vacancies is 2000ppm. Placing the mixed material into a box-type furnace, and introducing air with the ventilation volume of 5m 3 And/h, heating to 850 ℃ at a heating rate of 2 ℃/min, preserving heat for 5h, and cooling to room temperature along with the furnace. Crushing the sinter by a jaw crusher and a pair roller in turn, granulating to obtain particles with the particle diameter of about 2mm, crushing by an air flow mill, and sieving by a 325-mesh vibrating screen.
The sodium ion positive electrode materials of examples 1 to 7 and comparative examples 1 to 5 were tested for D50, specific surface area, and compacted density. The sodium ion positive electrode materials of examples 1 to 7 and comparative examples 1 to 5 were subjected to electrochemical performance tests. The correlation results are shown in Table 1.
Wherein, D50 is tested by a particle size analyzer, specific surface area is tested by a specific surface area tester, and PRCD3100 (IEST-Yuan energy technology) is adopted for testing compaction density of the material.
Electrochemical performance test: the sodium ion positive electrode materials of examples 1 to 7 and comparative examples 1 to 5 were respectively used as active materials, mixed with a binder PVDF and a conductive agent (Super-P) in a mass ratio of 95:1.5:3.5, added with an appropriate amount of N-vinylpyrrolidone as a solvent to prepare a slurry, coated on an aluminum foil, and vacuum-dried and rolled to prepare a negative electrode sheet. Lithium metal was used as a counter electrode, and 1mol/L LiPF was used 6 And mixing the three components of mixed solvents according to the ratio of EC to DMC to emc=1:1:1 (v/v) to form an electrolyte, and adopting a polypropylene microporous membrane as a diaphragm to assemble the CR2032 button cell in a glove box filled with inert gas. The charge and discharge test of the button cell is carried out on a cell test system of blue electric power electronic Co-Ltd in Wuhan city, the constant current charge and discharge of 0.1C is carried out to 0.01V at 25 ℃, then the constant current discharge of 0.02C is carried out to 0.005V, finally the constant current charge of 0.1C is carried out to 4.0V, the capacity charged to 4.0V is the first discharge specific capacity, the ratio of the discharge capacity and the charge capacity is the first charge and discharge efficiency, and the capacity retention rate after 100 circles of circulation is calculated.
Table 1 electrochemical properties of each example and comparative example
As shown in the results of Table 1, the sodium ion positive electrode materials prepared in examples 1 to 7 have a large D50, a large specific surface area and a high compaction density, and can be used as a rate-type material, and the sodium ion positive electrode material has a specific capacity of 140mAh/g or more after the initial discharge of 90% or more and a capacity retention of 92% or more after 100 cycles, so that the sodium ion positive electrode material can be used as a high-performance material.
As can be seen from comparative examples 1 to 7 and comparative examples 1 to 5, the sodium ion positive electrode materials of examples 1 to 7 are superior in various aspects of performance, mainly because the present invention is prepared by sintering under a high temperature inert atmosphere, cooling to room temperature and annealing treatment, lattice oxygen can be released, oxygen is lost to form oxygen vacancies in situ near the metal ions of the core, the existence of the oxygen vacancies can improve specific capacity and improve the structure and air stability of the materials, and the metal doping and metal oxide coating layer can enhance the cycle performance of the materials.
In contrast, comparative example 1 has no coating layer, and it is difficult to suppress phase transition of the material and reduce internal defects of the material, so that cycle performance is poor. Comparative example 2 did not perform high temperature sintering under an inert atmosphere, did not form oxygen vacancies in situ near the metal, and was difficult to improve the structure and air stability of the material, so the performance of the material was poor. While comparative example 3 was not preheated, and direct high temperature sintering resulted in incomplete material reaction, poor crystallization properties, and a large impact on the electrochemical properties of the material. In comparative example 4, the sintering temperature was low, below 800 ℃, fewer oxygen vacancies were formed, and the electrochemical properties of the material were poor. In comparative example 5, since oxygen vacancies exist in the coating layer, the coating layer is generally thin, and it is difficult to completely and uniformly coat, and metal oxide having vacancies is easily detached during a long-time cycle, so that the cycle performance is relatively poor.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The sodium ion positive electrode material is characterized by comprising an inner core and a coating layer, wherein the inner core is made of composite metal oxide, and the chemical formula of the composite metal oxide is Na i Ni a Fe b Mn c M (1-a-b-c) □ d O 2-d The material of the coating layer is metal oxide, wherein, the material of the coating layer is represented by the oxygen vacancy, M is a metal element, i is more than 0.7 and less than or equal to 1.0, a is more than 0 and less than or equal to 0.4, b is more than 0 and less than or equal to 0.4, c is more than 0 and less than or equal to 0.4, a+b+c is less than 1, and d is more than 0 and less than or equal to 0.5.
2. The sodium ion positive electrode material according to claim 1, wherein M is selected from at least one of Mg, zr, cu, al, ti, W, zn and Y.
3. The sodium ion positive electrode material according to claim 1, wherein the metal oxide comprises ZrO 2 、Al 2 O 3 CuO and TiO 2 At least one of them.
4. The sodium ion positive electrode material according to claim 1, wherein the content of the metal oxide is 1000ppm to 5000ppm.
5. The sodium ion positive electrode material according to claim 1, wherein the thickness of the coating layer is 0.05 μm to 2.00 μm.
6. The sodium ion positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (6):
(1) the D50 of the sodium ion positive electrode material is 1-12 μm;
(2) The specific surface area of the sodium ion positive electrode material is 0.2m 2 /g to 2.0m 2 /g；
(3) The compacted density of the sodium ion positive electrode material is 2.0g/cm 3 To 4.0g/cm 3 ；
(4) The first discharge specific capacity of the sodium ion positive electrode material is more than or equal to 140mAh/g;
(5) the first discharge efficiency of the sodium ion positive electrode material is more than or equal to 90%;
(6) the morphology of the sodium ion positive electrode material is single crystal, polycrystal or a mixed phase of single crystal and polycrystal.
7. The preparation method of the sodium ion positive electrode material is characterized by comprising the following steps:
(I) Premixing
Will be of the chemical formula Ni a Fe b Mn c (OH) 2 Mixing the precursor of (a) with a sodium source and a metal source to obtain a premix, wherein a+b+c=1;
(II) sintering
Pre-sintering the premix in an oxygen-containing atmosphere, performing primary sintering at 800-970 ℃ in an inert atmosphere, cooling to room temperature, crushing and sieving to obtain the composite metal oxide with oxygen vacancies;
(III) coating
And mixing the composite metal oxide with oxygen vacancies and the metal oxide, performing secondary sintering, crushing and sieving.
8. The method of producing a sodium ion positive electrode material according to claim 7, characterized by comprising at least one of the following features (1) to (23):
(1) The sodium source comprises at least one of sodium hydroxide, sodium carbonate, sodium nitrate and sodium acetate;
(2) The metal source comprises MgO, zrO 2 、CuO、Al 2 O 3 、TiO 2 、WO 3 ZnO and Y 2 O 3 At least one of (a) and (b);
(3) The metal source is contained in an amount of 2000ppm to 6000ppm;
(4) The molar quantity of sodium element in the sodium source is m, the sum of the molar quantity of metal in the precursor is n, and m/n is 0.8-1.1:1;
(5) The metal oxide comprises ZrO 2 、Al 2 O 3 CuO and TiO 2 At least one of (a) and (b);
(6) The metal oxide content is 800ppm to 4500ppm;
(7) Mixing is carried out by adopting a VC mixer in the premixing, the rotating speed of the VC mixer is 200rpm to 800rpm, and the mixing time is 30min to 120min;
(8) Air is introduced during presintering, and the airVentilation of 2m 3 /h to 8m 3 /h；
(9) The presintering temperature is 400-800 ℃;
(10) The heat preservation time of presintering is 1h to 6h;
(11) The temperature rising rate of the presintering is 0.5 ℃/min to 3.0 ℃/min;
(12) The inert atmosphere comprises at least one of argon, helium and neon;
(13) The ventilation of the inert atmosphere is 2m 3 /h to 8m 3 /h；
(14) The heat preservation time of the first sintering is 5 to 12 hours;
(15) The heating rate of the first sintering is 0.5 ℃/min to 3.0 ℃/min;
(16) Mixing is carried out by adopting a VC mixer in the coating, the rotating speed of the VC mixer is 200rpm to 800rpm, and the mixing time is 30min to 120min;
(17) Introducing air during the second sintering, wherein the ventilation amount of the air is 2m 3 /h to 8m 3 /h；
(18) The temperature of the second sintering is 600 ℃ to 950 ℃;
(19) The heat preservation time of the second sintering is 1h to 8h;
(20) The temperature rising rate of the second sintering is 0.5 ℃/min to 3.0 ℃/min;
(21) Crushing in the sintering process, namely crushing the sintered material after the first sintering by a jaw crusher and a pair roller in sequence, and then crushing by an air flow mill to obtain particles with the particle size of 1mm to 3 mm;
(22) Crushing in the coating, namely crushing the sintered material after the second sintering by a jaw crusher and a pair roller in sequence, and then crushing by an air flow mill to obtain particles with the particle size of 1mm to 3 mm;
(23) The sieving in the sintering and the sieving in the cladding are through a 325 mesh vibrating screen.
9. A sodium ion battery comprising a positive electrode material, a negative electrode material and an electrolyte, wherein the positive electrode material comprises the sodium ion positive electrode material according to any one of claims 1 to 6 or the sodium ion positive electrode material prepared by the method for preparing a sodium ion positive electrode material according to claim 7 or 8.
10. The sodium ion battery of claim 9, wherein the negative electrode material comprises a carbonaceous negative electrode material and/or a silicon-based negative electrode material.
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| CN117550656B (en) * | 2024-01-09 | 2024-04-23 | 阜阳海钠科技有限责任公司 | Positive electrode material, preparation method thereof and sodium battery |
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