CN116282222A - Nickel-iron-manganese layered oxide and preparation method and application thereof - Google Patents
Nickel-iron-manganese layered oxide and preparation method and application thereof Download PDFInfo
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- CN116282222A CN116282222A CN202310237987.8A CN202310237987A CN116282222A CN 116282222 A CN116282222 A CN 116282222A CN 202310237987 A CN202310237987 A CN 202310237987A CN 116282222 A CN116282222 A CN 116282222A
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- iron
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- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 74
- 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 abstract description 67
- 239000011734 sodium Substances 0.000 claims abstract description 67
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 67
- 239000002562 thickening agent Substances 0.000 claims abstract description 49
- 238000001354 calcination Methods 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 51
- 239000000463 material Substances 0.000 abstract description 26
- 239000011148 porous material Substances 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 238000004904 shortening Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000003483 aging Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000006978 adaptation 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
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
-
- 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
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a nickel-iron-manganese layered oxide, a preparation method and application thereof, and relates to the technical field of sodium ion batteries. According to the invention, the liquid phase method is adopted for mixing sodium, so that sodium element is uniformly distributed on precursor particles, and the sodium element can enter the material more easily in the calcining stage, thereby being beneficial to reducing the calcining temperature and shortening the calcining time, and further reducing the loss of sodium element at high temperature; the thickener is introduced, so that the aggregation and sedimentation of particles in the slurry in the drying process can be prevented, and a better effect of fixing a sodium source is achieved; filled in the precursor Ni x Fe y Mn z (OH) 2 The thickener in the pores of the particles only has partial carbon remained after calcination, so that on one hand, the conductivity of the material can be increased, and on the other hand, the thickener plays a supporting role on the physical structure of the particles, and the structural stability of the material is enhanced. By the inventionThe sodium ion battery prepared by taking the bright nickel-iron-manganese layered oxide as the positive electrode material has high specific capacity and good cycling stability.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a nickel-iron-manganese layered oxide and a preparation method and application thereof.
Background
In recent years, energy storage devices represented by lithium ion batteries have been widely used in small electronic products, and continue to grow rapidly in new energy automobiles and energy storage industries. However, lithium resources as core raw materials are becoming important factors affecting their development due to supply and demand mismatch and economic problems. The sodium resource reserves are rich, the sodium ion battery produced by using the sodium ion battery as a raw material is basically consistent with the lithium ion battery in the aspects of working principle and production process, and is better in low-temperature performance, multiplying power performance and economy, but the cycle life and energy density of the sodium ion battery are inferior to those of the lithium ion battery, and the sodium ion battery can be effectively supplemented in the fields of energy storage, partial passenger cars and two-wheelers.
The sodium-containing nickel-iron-manganese layered oxide serving as the positive electrode material of the sodium ion battery has higher energy density and stable crystal structure, can be matched with the existing synthetic route of the lithium battery ternary material, and can quickly reach the market, so that the lithium battery ternary material has been widely focused. However, in the process of preparing the sodium-containing nickel-iron-manganese layered oxide, the temperature in the calcination stage is as high as 900 ℃ due to the high melting point of sodium carbonate, so that the loss of sodium element in the material is caused. In order to supplement sodium element in high-temperature loss part, excessive sodium salt is often added during sodium mixing>1.05 Resulting in residual and maldistribution of sodium salt on the surface of the material after sintering and CO in air 2 Combined with water, sodium carbonate and sodium hydroxide exist to form residual alkali on the surface of the material, so that the subsequent processing capability of the material is poor, the irreversible capacity loss is increased, and the cycle life is greatly shortened.
Disclosure of Invention
The invention aims to provide a nickel-iron-manganese layered oxide, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of nickel-iron-manganese layered oxide, which comprises the following steps:
dissolving a thickener into a solvent to obtain a thickener solution;
ni is added with x Fe y Mn z (OH) 2 Mixing a sodium source with the thickener solution to obtain precursor slurry; na and Ni in the sodium source x Fe y Mn z (OH) 2 The molar ratio of (2) is 0.98-1.03:1;
sequentially drying and calcining the precursor slurry to obtain the nickel-iron-manganese layered oxide; the calcining temperature is 600-850 ℃, and the heat preservation time is 6-15 h;
the chemical composition of the nickel-iron-manganese layered oxide is shown in formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
Preferably, the thickener is one or more of citric acid, glucose, sucrose, carboxymethyl cellulose, acrylic acid, polyacrylate and polyurethane.
Preferably, the solvent is water or a water-ethanol mixed solvent, and the volume content of ethanol in the water-ethanol mixed solvent is below 20%.
Preferably, the Ni x Fe y Mn z (OH) 2 Is prepared by a coprecipitation method.
Preferably, the sodium source is one or more of sodium hydroxide, sodium carbonate, sodium oxalate, sodium chloride and sodium nitrate.
Preferably, the calcination is performed under an air atmosphere or an oxygen atmosphere.
Preferably, the mass concentration of the thickener solution is 1-10%.
Preferably, the solid content of the precursor slurry is 30-80%, and the viscosity is 1000-10000 mPa.s.
The invention provides the nickel-iron-manganese layered oxide prepared by the preparation method, which has the chemical composition shown in the formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
The invention provides application of the nickel-iron-manganese layered oxide as a positive electrode material in a sodium ion battery.
The invention provides a preparation method of nickel-iron-manganese layered oxide, which comprises the following steps: dissolving a thickener into a solvent to obtain a thickener solution; ni is added with x Fe y Mn z (OH) 2 Mixing a sodium source with the thickener solution to obtain precursor slurry; na and Ni in the sodium source x Fe y Mn z (OH) 2 The molar ratio of (2) is 0.98-1.03:1; sequentially drying and calcining the precursor slurry to obtain the nickel-iron-manganese layered oxide; the calcining temperature is 600-850 ℃, and the heat preservation time is 6-15 h; the chemical composition of the nickel-iron-manganese layered oxide is shown in formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
According to the invention, the liquid phase method is adopted for mixing sodium, so that sodium element is uniformly distributed on precursor particles, and the sodium element can enter the material more easily in the calcining stage, thereby being beneficial to reducing the calcining temperature and shortening the calcining time, and further reducing the loss of sodium element at high temperature; the thickener is introduced, so that the aggregation and sedimentation of particles in the slurry in the drying process can be prevented, and a better effect of fixing a sodium source is achieved; filled in the precursor Ni x Fe y Mn z (OH) 2 The thickener in the particle pores only remains part of carbon after calcination, so that on one hand, the conductivity of the material can be increased, on the other hand, the physical structure of the particles is supported, the structural stability of the material is enhanced, and the sodium ion battery prepared by taking the nickel-iron-manganese layered oxide as the anode material has high specific capacity and good cycle stability.
Drawings
FIG. 1 shows the NaNi obtained in example 1 0.4 Fe 0.2 Mn 0.4 O 2 SEM image of particles;
FIG. 2 is Ni obtained in example 1 0.4 Fe 0.2 Mn 0.4 (OH) 2 SEM image of particle surface;
FIG. 3 is an SEM image of the surface of particles of the precursor slurry prepared in example 1 after drying and pulverizing;
FIG. 4 shows the NaNi obtained in example 1 0.4 Fe 0.2 Mn 0.4 O 2 SEM image of particle surface;
FIG. 5 is an XRD pattern of the nickel-iron-manganese layered oxide obtained in example 1;
FIG. 6 is an SEM image of the surface of nickel-iron-manganese layered oxide particles prepared in comparative example 1;
FIG. 7 is an XRD pattern of the nickel-iron-manganese layered oxide obtained in comparative example 1;
fig. 8 is a 1C cycle test life curve of the positive electrode material prepared in example 1.
Detailed Description
The invention provides a preparation method of nickel-iron-manganese layered oxide, which comprises the following steps:
dissolving a thickener into a solvent to obtain a thickener solution;
ni is added with x Fe y Mn z (OH) 2 Mixing a sodium source with the thickener solution to obtain precursor slurry; na and Ni in the sodium source x Fe y Mn z (OH) 2 The molar ratio of (2) is 0.98-1.03:1;
sequentially drying and calcining the precursor slurry to obtain the nickel-iron-manganese layered oxide; the calcining temperature is 600-850 ℃, and the heat preservation time is 6-15 h;
the chemical composition of the nickel-iron-manganese layered oxide is shown in formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The invention dissolves the thickener into the solvent to obtain the thickener solution.
In the present invention, the thickener is preferably one or more of citric acid, glucose, sucrose, carboxymethyl cellulose, acrylic acid, polyacrylate, and polyurethane; the solvent is preferably water or a water-ethanol mixed solvent; when the solvent is a water-ethanol mixed solvent, the volume content of ethanol in the water-ethanol mixed solvent is preferably 20% or less, more preferably 5 to 20%, and still more preferably 8 to 15%.
In the present invention, the mass concentration of the thickener solution is preferably 1 to 10%, more preferably 2 to 8%, and even more preferably 3 to 6%. In the invention, the thickener can prevent particles from agglomerating and settling in the drying process of the slurry, and plays a better role in fixing a sodium source.
After the thickener solution is obtained, ni is added into the invention x Fe y Mn z (OH) 2 And mixing a sodium source with the thickener solution to obtain a precursor slurry.
In the present invention, the Ni x Fe y Mn z (OH) 2 Preferably by a coprecipitation method; the coprecipitation method for preparing Ni x Fe y Mn z (OH) 2 Preferably comprising the steps of:
mixing nickel salt, ferrous salt, manganese salt, precipitant and complexing agent to perform coprecipitation reaction to obtain Ni x Fe y Mn z (OH) 2 。
In the present invention, the nickel salt preferably includes nickel sulfate; the ferrous salt preferably comprises ferrous sulfate; the manganese salt preferably comprises manganese sulfate; the precipitant preferably comprises sodium hydroxide solution; the complexing agent is preferably an aqueous ammonia solution.
In the invention, the molar ratio of Ni in the nickel salt, fe in the ferrous salt and Mn in the manganese salt is x:z, 0 < x < 0.5,0 < y < 0.33,0 < z < 0.5, and x+y+z=1.
In the present invention, the aqueous ammonia solution is preferably used in an amount sufficient for NH in the reaction system 3 The concentration is preferably 5-10 g/L; the amount of the precipitant is preferably such that the pH of the reaction system is maintained at 10 to 12.
In the present invention, the coprecipitation reaction is preferably carried out at 50 to 65℃and the time of the coprecipitation reaction is not particularly limited, and the Ni is used x Fe y Mn z (OH) 2 The particle diameter D50 of (2) is preferably 5 to 15. Mu.m, more preferably 10. Mu.m.
After the coprecipitation reaction is completed, the obtained product is preferably subjected to ageing, washing, filtering, drying and crushing in sequence to obtain the Ni x Fe y Mn z (OH) 2 。
In the present invention, the Ni x Fe y Mn z (OH) 2 The porosity of (2) is preferably 5 to 15%, more preferably 10 to 13%. In the present invention, the Ni x Fe y Mn z (OH) 2 The morphology of the particles is a spheroid secondary particle containing a pore structure, and the particles consist of nano-sheets extending outwards from the center of the particles.
In the present invention, the sodium source is preferably one or more of sodium hydroxide, sodium carbonate, sodium oxalate, sodium chloride and sodium nitrate. In the present invention, na and Ni in the sodium source x Fe y Mn z (OH) 2 The molar ratio of (2) is 0.98-1.03:1, preferably 0.99-1.02:1, more preferably 1.00-1.01: 1.
in the present invention, the thickener solution is preferably used in an amount such that the solid content of the precursor slurry is 30 to 80%, more preferably 40 to 70%, still more preferably 50 to 60%.
In the present invention, the mixing preferably includes one or more of mechanical stirring, ball milling and grinding.
In the present invention, the viscosity of the precursor slurry is preferably 1000 to 10000 mPas, more preferably 3000 to 8000 mPas, and even more preferably 5000 to 6000 mPas.
After the precursor slurry is obtained, the precursor slurry is dried and calcined in sequence, so that the nickel-iron-manganese layered oxide is obtained.
In the invention, the drying can be any drying mode, and the moisture of the dried material is less than 1 percent. After drying, ni x Fe y Mn z (OH) 2 Part of the pores on the surface of the particles are filled with a sodium source and a thickener, and the porosity is 1-10%.
The dried precursor is preferably crushed before the calcination. The invention has no special requirement on the crushing process, and the conventional crushing process is adopted.
In the present invention, the calcination temperature is 600 to 850 ℃, preferably 650 to 800 ℃, more preferably 700 to 750 ℃; the heat-retaining time for the calcination is preferably 6 to 15 hours, more preferably 8 to 13 hours, and still more preferably 10 to 11 hours. In the present invention, the calcination is preferably performed under an air atmosphere or an oxygen atmosphere.
In the calcination process, the sodium source enters Ni x Fe y Mn z (OH) 2 Inside, form a compound of the chemical formula NaNi x Fe y Mn z O 2 Nickel-iron-manganese layered oxide. Filled in Ni x Fe y Mn z (OH) 2 The thickener in the pores of the particles only has partial carbon remained after calcination, so that on one hand, the conductivity of the material can be increased, and on the other hand, the thickener plays a supporting role on the physical structure of the particles, and the structural stability of the material is enhanced.
The invention provides the nickel-iron-manganese layered oxide prepared by the preparation method, which has the chemical composition shown in the formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
According to the invention, the nickel-iron-manganese layered oxide is mixed with sodium by a liquid phase method, so that sodium elements are uniformly distributed on precursor particles, and enter the material more easily in a calcination stage, thereby being beneficial to reducing the calcination temperature and shortening the calcination time, reducing the loss of sodium elements at high temperature, avoiding adding a large amount of excessive sodium salt and reducing the residual alkali content on the surface of the nickel-iron-manganese layered oxide; the thickener is introduced, so that the aggregation and sedimentation of particles in the slurry in the drying process can be prevented, and a better effect of fixing a sodium source is achieved; filled in the precursor Ni x Fe y Mn z (OH) 2 The thickener in the pores of the particles only has partial carbon remained after calcination, so that on one hand, the conductivity of the material can be increased, and on the other hand, the thickener plays a supporting role on the physical structure of the particles, and the structural stability of the material is enhanced. With the inventionThe sodium ion battery prepared by taking the nickel-iron-manganese layered oxide as the positive electrode material has high specific capacity and good cycling stability.
The invention provides application of the nickel-iron-manganese layered oxide as a positive electrode material in a sodium ion battery.
The nickel-iron-manganese layered oxide, the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The chemical formula for preparing the nickel-iron-manganese layered oxide is NaNi 0.4 Fe 0.2 Mn 0.4 O 2 The preparation method comprises the following steps:
1) Nickel sulfate, ferrous sulfate and manganese sulfate are selected as reaction raw materials, a sodium hydroxide solution is selected as a precipitator according to the molar ratio of Ni, fe and Mn being 4:2:4, an ammonia water solution is selected as a complexing agent, a coprecipitation reaction is carried out in a coprecipitation reaction kettle, the reaction temperature is 60 ℃, the pH is controlled to be 10.5, the ammonia concentration is controlled to be 8g/L, the feeding is stopped when the particle size grows to 10 mu m, and Ni is obtained through ageing, washing, filtering, drying and crushing 0.4 Fe 0.2 Mn 0.4 (OH) 2 ；
2) The thickener is carboxymethyl cellulose, the solvent is water, and the thickener solution with the mass fraction of 5% of the carboxymethyl cellulose is prepared;
3) According to sodium and Ni in sodium source 0.4 Fe 0.2 Mn 0.4 (OH) 2 The molar ratio of (2) is 1.01:1, and sodium carbonate and Ni are weighed 0.4 Fe 0.2 Mn 0.4 (OH) 2 Adding the thickener solution in the step 2), mechanically stirring to form precursor slurry, wherein the solid content of the slurry is 65%, and the viscosity of the slurry is 8300 mPa.s;
4) Drying and crushing the precursor slurry in the step 3), and then calcining in a blast box type atmosphere furnace at 800 ℃ for 10 hours, and naturally cooling to room temperature to obtain NaNi 0.4 Fe 0.2 Mn 0.4 O 2 Layered oxide positive electrode materials.
Through detection, ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The porosity of the particles was 13.6%, the porosity of the particles after filling with sodium source and thickener was 3.0%, ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The compressive strength of the granules was 17.6MPa, and the compressive strength of the granules after calcination was 78.4MPa.
Example 2
The chemical formula for preparing the nickel-iron-manganese layered oxide is NaNi 0.33 Fe 0.33 Mn 0.33 O 2 The preparation method comprises the following steps:
1) Nickel sulfate, ferrous sulfate and manganese sulfate are selected as reaction raw materials, the molar ratio of Ni, fe and Mn is 1:1:1, a precipitator is sodium hydroxide solution, a complexing agent is ammonia water solution, a coprecipitation reaction is carried out in a coprecipitation reaction kettle, the reaction temperature is 60 ℃, the pH is controlled to be 10.2, the ammonia concentration is controlled to be 8g/L, when the particle size grows to 10 mu m, the feeding is stopped, and the Ni is obtained through ageing, washing, filtering, drying and crushing 0.33 Fe 0.33 Mn 0.33 (OH) 2 ；
2) The thickener is carboxymethyl cellulose, the solvent is water, and the thickener solution with the mass fraction of 5% of the carboxymethyl cellulose is prepared;
3) Weighing a certain amount of sodium carbonate and Ni according to the molar ratio of sodium in a sodium source to a precursor of 1.01:1 0.33 Fe 0.33 Mn 0.33 (OH) 2 Adding the mixed solution into the step 2), mechanically stirring to form precursor slurry, wherein the solid content of the slurry is 60%, and the viscosity of the slurry is 7100 mPa.s;
4) Drying and crushing the precursor slurry in the step 3, and then placing the dried and crushed precursor slurry in a blast box type atmosphere furnace for calcination, wherein the calcination temperature is 800 ℃, the calcination time is 10 hours, and naturally cooling to room temperature to obtain NaNi 0.33 Fe 0.33 Mn 0.33 O 2 Layered oxide positive electrode materials.
Through detection, ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The porosity of the particles was 12.3%, the porosity of the particles after filling with sodium source and thickener was 2.1%, ni 0.33 Fe 0.33 Mn 0.33 (OH) 2 The compressive strength of the granules was 21.5MPa, and the compressive strength of the granules after calcination was 83.8MPa.
Example 3
Preparation of NaNi according to the procedure of example 1 0.4 Fe 0.2 Mn 0.4 O 2 The difference is that the thickener in step 2) is selected to be glucose, the mass fraction of glucose in the thickener solution is 10%, the solid content of the precursor slurry in step 3) is 80%, and the viscosity of the slurry is 6700 mPa.s.
The test shows that the porosity of the particles after filling with sodium source and thickener in example 3 is 1.4%, and the compressive strength of the particles after calcination is 92.4Mpa.
Example 4
Preparation of NaNi according to the procedure of example 1 0.4 Fe 0.2 Mn 0.4 O 2 The difference is that the solvent in the step 2) is selected as a mixed solution of water and ethanol, the volume ratio is 95:5, and the viscosity of the precursor slurry obtained in the step 3) is 6600 mPas.
The test shows that the porosity of the particles after filling with sodium source and thickener in example 4 is 1.1% and the compressive strength of the particles after calcination is 102.1Mpa.
Comparative example 1
The chemical formula for preparing the nickel-iron-manganese layered oxide is NaNi 0.4 Fe 0.2 Mn 0.4 O 2 The preparation method differs from example 1 in that: the sodium source and Ni are mixed in a solid manner 0.4 Fe 0.2 Mn 0.4 (OH) 2 Mixing, i.e. according to sodium and Ni in a sodium source 0.4 Fe 0.2 Mn 0.4 (OH) 2 The molar ratio of (2) is 1.01:1, and sodium carbonate and Ni are weighed 0.4 Fe 0.2 Mn 0.4 (OH) 2 The mixture was mixed in a high-speed mixer and calcined in a box-type atmosphere furnace, and the subsequent steps were the same as in example 1.
Comparative example 1 was tested on sodium source and Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The porosity of the mixed particles was 12.7%, and the compressive strength of the calcined particles was 47.8MPa.
Comparative example 2
Preparation of NaNi according to the procedure of example 1 0.4 Fe 0.2 Mn 0.4 O 2 Except that step 2) does not add a thickener, i.e. sodium carbonate and Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The subsequent steps were carried out in the same manner as in example 1.
Experimental procedure found Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 Delamination was seen soon after the mixing and stirring with the sodium source in water ceased. Comparative example 2 was tested on sodium source and Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The porosity of the mixed particles was 10.8% and the compressive strength of the calcined particles was 56.7MPa.
Comparative example 3
Preparation of NaNi according to the procedure of example 1 0.4 Fe 0.2 Mn 0.4 O 2 Except that sodium carbonate and Ni added in step 3) are reduced 0.4 Fe 0.2 Mn 0.4 (OH) 2 The quality of the precursor slurry, i.e., the solid content, was reduced to 20%, and the subsequent steps were identical to those of example 1.
Comparative example 3 was tested on sodium source and Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The porosity of the mixed particles was 4.3% and the compressive strength of the calcined particles was 51.6MPa.
Comparative example 4
Preparation of NaNi according to the procedure of example 1 0.4 Fe 0.2 Mn 0.4 O 2 The post procedure was as in example 1 except that the molar ratio of sodium to precursor in the sodium source was 1.05:1.
Comparative example 4 was tested on sodium source and Ni 0.4 Fe 0.2 Mn 0.4 (OH) 2 The porosity of the mixed particles was 2.7%, and the compressive strength of the calcined particles was 81.3MPa.
Ni obtained in step 1) of example 1 was subjected to a field emission Scanning Electron Microscope (SEM) (JSM-7800F) 0.4 Fe 0.2 Mn 0.4 (OH) 2 Particles obtained by crushing the precursor slurry obtained in the step 3) and NaNi obtained in the step 4) 0.4 Fe 0.2 Mn 0.4 O 2 The particles and surface morphology of the layered oxide were examined as shown in fig. 1 to 4. It can be seen that Ni obtained in example 1 0.4 Fe 0.2 Mn 0.4 (OH) 2 The porous structure of the spheroid secondary particles is characterized in that the morphology of the primary particles is flaky, the pores among the primary particles are covered after being filled by a sodium source and a thickener, and the spheroid with a polycrystalline structure is obtained after calcination, so that the particle size distribution is uniform.
For NaNi prepared in comparative example 1 0.4 Fe 0.2 Mn 0.4 O 2 SEM characterization is carried out on the particle surfaces of the layered oxide, and as shown in fig. 6, the secondary particles have no specific morphology, and the particle structure collapses, which is detrimental to the processing performance of the material.
NaNi obtained in example 1 and comparative example 1 was subjected to XRD diffractometer (Panalytical X' PERT PRO MPD, netherlands) 0.4 Fe 0.2 Mn 0.4 O 2 The phase structure of the layered oxide cathode material was examined, and as shown in fig. 5 and 7, the XRD pattern of the material prepared in example 1 showed that it had higher crystallinity, no impurity phase, and the same crystal form as the target product, whereas the XRD pattern of the material prepared in comparative example 1 had poor crystallinity and had a plurality of impurity phases.
The nickel-iron-manganese layered oxides prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to sodium content detection using a German Stek ICP-OES plasma emission spectrometer GREEN, and the loss amount of sodium was obtained, and the results are shown in Table 1.
Table 1 sodium loss rates for examples and comparative examples
| Category(s) | Sodium content/Atom% | Sodium loss rate/% |
| Example 1 | 25.03 | 0.22％ |
| Example 2 | 25.12 | 0.13％ |
| Example 3 | 24.99 | 0.26％ |
| Example 4 | 25.06 | 0.19％ |
| Comparative example 1 | 23.04 | 2.21％ |
| Comparative example 2 | 23.47 | 1.78％ |
| Comparative example 3 | 24.67 | 0.58％ |
| Comparative example 4 | 26.06 | 0.19％ |
As can be seen from Table 1, the material calcined by the technical scheme of the invention has relatively higher sodium content, can reduce the loss of sodium element, and is compared with the material calcined by solidMixing the sodium source and the precursor Ni x Fe y Mn z (OH) 2 The mixing can better optimize the proportioning and the calcining process.
The nickel-iron-manganese layered oxides prepared in examples 1-4 and comparative examples 1-4 are used as positive electrode materials of sodium ion batteries, are respectively mixed with SP and PVDF in a dry room with humidity less than 10% according to a mass ratio of 85:10:5, homogenized, coated on an aluminum foil current collector with solid content of 45%, vacuum baked at 110 ℃ for 8 hours, and rolled and punched to prepare positive electrode plates of sodium ion batteries. The button half cell is assembled in a glove box filled with argon, a counter electrode is a metal sodium sheet, a used diaphragm is a PE diaphragm, and an electrolyte is NaPF of 1mol/L 6 EC/DMC (volume ratio 1:1). The button cell test equipment was a commercial LAND cell test system from blue electric electronics Inc. of Wuhan, at a test temperature of 25 ℃. The charge and discharge test is carried out on the button cell, the 0.1C capacity test flow is that the 0.1C constant current and constant voltage charge is carried out to 4.0V, the 0.1C constant current and constant voltage discharge is carried out to 2.0V, the first charge and discharge curve of the material is measured, the 1C cycle test flow is that the 1C constant current and constant voltage charge is carried out to 4.0V, the 1C constant current and constant voltage charge is carried out to 2.0V, and the cycle is carried out for 100 times, thus obtaining the cycle life curve. The results of the 0.1C capacity test and the 1C cycle 100 capacity retention test are shown in table 2, and the 1C cycle test life curve of the positive electrode material prepared in example 1 is shown in fig. 7.
Table 2 results of capacity test and cyclic capacity retention test of examples and comparative examples
As can be seen from Table 2, the positive electrode material of the sodium ion battery prepared by the technical scheme of the invention has higher specific capacity and cycle capacity retention rate. From the results of morphology and XRD characterization of example 1 and comparative example, the compressive strength of the particles after calcination of comparative example 1 was significantly reduced, the structure collapsed, the crystallinity was poor, and a plurality of impurity phases appeared, so that the electrochemical properties thereof were significantly reduced. Comparative example 2 the porosity of the particles after drying the precursor slurry was slightly reduced from the precursor particles without introducing a thickener, and more sodium remained on the surface of the material after calcination without entering the interior of the crystal, forming an impurity phase. The slurry in comparative example 3 had a reduced solids content to 20% and a low viscosity resulted in settling of the precursor during drying of the slurry and uneven sodium distribution on the surface of the precursor, again forming a more impurity phase. Comparative example 4 sodium source was added in excess and calcined to form residual alkali, resulting in poor processability of the material and poor cycling stability of the late battery.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the nickel-iron-manganese layered oxide is characterized by comprising the following steps of:
dissolving a thickener into a solvent to obtain a thickener solution;
ni is added with x Fe y Mn z (OH) 2 Mixing a sodium source with the thickener solution to obtain precursor slurry; na and Ni in the sodium source x Fe y Mn z (OH) 2 The molar ratio of (2) is 0.98-1.03:1;
sequentially drying and calcining the precursor slurry to obtain the nickel-iron-manganese layered oxide; the calcining temperature is 600-850 ℃, and the heat preservation time is 6-15 h;
the chemical composition of the nickel-iron-manganese layered oxide is shown in formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
2. The method of claim 1, wherein the thickener is one or more of citric acid, glucose, sucrose, carboxymethyl cellulose, acrylic acid, polyacrylate, and polyurethane.
3. The preparation method according to claim 1, wherein the solvent is water or a water-ethanol mixed solvent, and the volume content of ethanol in the water-ethanol mixed solvent is 20% or less.
4. The method according to claim 1, wherein the Ni x Fe y Mn z (OH) 2 Is prepared by a coprecipitation method.
5. The method of claim 1, wherein the sodium source is one or more of sodium hydroxide, sodium carbonate, sodium oxalate, sodium chloride, and sodium nitrate.
6. The preparation method according to claim 1, wherein the calcination is performed under an air atmosphere or an oxygen atmosphere.
7. A method of preparation according to any one of claims 1 to 3, wherein the thickener solution has a mass concentration of 1 to 10%.
8. The method according to any one of claims 1 to 5, wherein the precursor slurry has a solid content of 30 to 80% and a viscosity of 1000 to 10000 mPa-s.
9. The nickel-iron-manganese layered oxide prepared by the preparation method of any one of claims 1 to 8, having a chemical composition represented by formula 1: naNi x Fe y Mn z O 2 Formula 1; in the formula 1, x is more than 0 and less than 0.5, y is more than 0 and less than 0.33,0, z is more than 0.5, and x+y+z=1.
10. The use of the nickel-iron-manganese layered oxide according to claim 9 as a positive electrode material in sodium ion batteries.
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