CN117059796B - Sodium-electricity layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium-ion battery and electric equipment - Google Patents
Sodium-electricity layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium-ion battery and electric equipment Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 98
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 53
- 239000010949 copper Substances 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- 239000011734 sodium Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 34
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 33
- 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 32
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000010406 cathode material Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000011572 manganese Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011163 secondary particle Substances 0.000 description 5
- -1 NaOH Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/48—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
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/20—Two-dimensional structures
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/12—Surface area
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a sodium-electricity layered oxide positive electrode material, a preparation method thereof, a positive electrode plate, a sodium ion battery and electric equipment. The chemical general formula of the sodium-electricity layered oxide positive electrode material is NaNi 0.22+ x Fe y Mn z Cu 0.11‑x O 2 The method comprises the steps of carrying out a first treatment on the surface of the The sodium-electricity layered oxide anode material is mainly prepared by sintering a mixture containing a precursor material, a copper source and a sodium source; the tap density of the precursor material is more than or equal to 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the D50 median particle diameter d=3 to 10 μm of copper source; the sintering temperature T, the D50 median particle diameter D of the copper source and the molar ratio (0.11-x) of the copper source to the precursor material satisfy the following relationship: t= -20D/log (0.11-x) +850. The sintering temperature of the positive electrode material is low, the morphology of a large sheet layer of the positive electrode material is improved, and the energy density of the battery is improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium-electricity layered oxide positive electrode material, a preparation method thereof, a positive electrode plate, a sodium ion battery and electric equipment.
Background
Sodium ion batteries are secondary rechargeable batteries that use sodium as the negative electrode material and different positive electrode materials (e.g., carbon, oxides, etc.). Compared with a sodium ion battery, the sodium ion battery has the advantages of low cost, high safety, good low-temperature performance and the like. The nickel-iron-manganese anode material has a good development prospect.
The prior sodic ferronickel manganese copper quaternary precursor material can not realize even co-precipitation with Cu in a ratio of 0.1-0.12, can only realize co-precipitation with Cu content lower than 0.07, and has a tap density lower than 1.3g/cm 3 This is very unfriendly to the capacity design of the sintering of the positive electrode material.
The ternary coprecipitation precursor of nickel, iron and manganese is relatively mature, and the tap density of the precursor can be 2.0g/cm 3 The above. However, a higher sintering temperature is generally required in the process of preparing the anode material by adopting the nickel-iron-manganese ternary precursor at present>Most of the equipment is difficult to meet the condition at 1000 ℃, and even if the condition is met, the damage to the equipment is serious at high temperature. Meanwhile, the nickel-iron-manganese ternary precursor mainly presents a large-sheet morphology after being prepared into the positive electrode material, and the morphology can lead to poor fluidity of the positive electrode material and low compaction of the rear end electrode core pole piece, so that the battery energy density is low.
Therefore, the method has important significance in reducing the sintering temperature of the positive electrode material and improving the morphology of the large sheet layer of the positive electrode material.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the invention is to provide a sodium-electricity layered oxide positive electrode material, which has low sintering temperature and improved large-sheet morphology by regulating and controlling the molar ratio of a copper source to a precursor material and the D50 median particle diameter of the copper source raw material and satisfying a relational expression. The problems that the traditional preparation of the nickel-iron-manganese anode material needs higher sintering temperature, so that most of equipment is difficult to meet the conditions or the equipment is seriously damaged even if the conditions are met are solved; and solves the problem that the traditional nickel-iron-manganese precursor presents a large-sheet morphology after being prepared into the anode material.
The second object of the invention is to provide a preparation method of a sodium-electricity layered oxide positive electrode material, which has low sintering temperature, low requirements on sintering equipment, easy preparation, and capability of obviously improving the morphology of a large sheet layer of the positive electrode material, thereby improving the energy density of the positive electrode material.
A third object of the present invention is to provide a positive electrode sheet having a high energy density.
A fourth object of the present invention is to provide a sodium ion battery having excellent electrochemical properties.
A fifth object of the present invention is to provide an electric device using the above sodium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a sodium-electricity layered oxide positive electrode material, which has a chemical general formula of NaNi 0.22+x Fe y Mn z Cu 0.11-x O 2 Wherein 0 is<x is less than or equal to 0.1; y is more than or equal to 0.32 and less than or equal to 0.36,0.31, z is more than or equal to 0.35, and y+z=0.67;
the sodium-electricity layered oxide anode material is mainly prepared by sintering a mixture containing a precursor material, a copper source and a sodium source; wherein the tap density of the precursor material is more than or equal to 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The D50 median particle diameter D=3-10 mu m of the copper source; and the sintering temperature T, the D50 median particle diameter D of the copper source, and the molar ratio (0.11-x) of the copper source to the precursor material satisfy the following relation: t= -20D/log (0.11-x) +850.
According to the invention, by regulating and controlling the molar ratio of the copper source to the precursor material and the D50 median particle diameter of the copper source raw material and satisfying the relation, the sintering temperature of the sodium-electricity layered oxide positive electrode material is reduced, the morphology of a large sheet layer of the positive electrode material is improved, and the energy density of a battery prepared from the positive electrode material is improved. The method solves the problems that the traditional preparation of the nickel-iron-manganese anode material needs higher sintering temperature, so that most of equipment is difficult to meet the conditions, or the equipment is seriously damaged even if the conditions are met; but also solves the problem that the traditional nickel-iron-manganese precursor presents a large-sheet morphology after being prepared into the anode material.
Further, the chemical formula of the precursor material is Ni u Fe v Mn w (OH) 2 Wherein u is more than or equal to 0.24 and less than or equal to 0.33,0.32, v is more than or equal to 0.41,0.31 and w is more than or equal to 0.40, and u+v+w=1.
Further, the specific surface area BET of the precursor material is 5m 2 /g<BET<50m 2 /g。
Further, the D50 median particle size of the sodium-electricity layered oxide positive electrode material is 5-20 mu m.
Further, the dullness P of the sodium-electricity layered oxide positive electrode material is 0.6-1.0.
Further, the first coulomb efficiency of the sodium-electricity layered oxide positive electrode material is more than or equal to 92%.
Further, the average specific discharge capacity of the sodium-electricity layered oxide positive electrode material is more than or equal to 133mAh/g after 3 weeks of circulation at 0.1 ℃.
Further, the average specific discharge capacity of the sodium-electricity layered oxide positive electrode material is more than or equal to 126mAh/g after 3 weeks of circulation at 0.5 ℃.
Further, the average specific discharge capacity of the sodium-electricity layered oxide positive electrode material is more than or equal to 120mAh/g after 3 weeks of circulation at 1C.
The invention further provides a preparation method of the sodium-electricity layered oxide anode material, which comprises the following steps:
and mixing the precursor material, the copper source and the sodium source, and then sintering to obtain the sodium-electricity layered oxide anode material.
Further, the sintering heat preservation time is 8-24 hours.
Further, the sintering is performed in an oxygen-containing atmosphere comprising an air atmosphere and/or an oxygen atmosphere.
Further, the chemical formula of the precursor material is Ni u Fe v Mn w (OH) 2 Wherein u is more than or equal to 0.24 and less than or equal to 0.33,0.32, v is more than or equal to 0.41,0.31 and w is more than or equal to 0.40, and u+v+w=1.
The invention also provides a positive plate which comprises the sodium-electricity layered oxide positive electrode material.
The invention also provides a sodium ion battery which comprises the positive plate.
The invention also provides electric equipment, which comprises the sodium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the sodium-ion battery layered oxide anode material provided by the invention, the molar ratio of the copper source to the precursor material and the D50 median particle size of the copper source raw material are regulated and controlled, and the relational expression is satisfied, so that on one hand, the sintering temperature of the sodium-ion battery layered oxide anode material is remarkably reduced, on the other hand, the morphology of a large sheet layer of the anode material is remarkably improved, and the energy density of the battery is improved.
(2) The secondary particle shape of the layered oxide positive electrode material of the sodium ion battery provided by the invention is similar to a sphere, and the obtained sodium ion battery has high capacity and first coulomb efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of a sodium electric layered oxide positive electrode material provided in example 2 of the present invention;
FIG. 2 is an SEM image of a sodium electric layered oxide positive electrode material provided in example 5 of the present invention;
FIG. 3 is an SEM image of a sodium electric layered oxide positive electrode material provided in comparative example 1 of the present invention;
FIG. 4 is an SEM image of a sodium electric layered oxide positive electrode material provided in comparative example 3 of the present invention;
fig. 5 is an SEM image of the sodium electric layered oxide positive electrode material provided in comparative example 5 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a sodium-electric (i.e., sodium ion battery) layered oxide cathode material having a chemical formula of NaNi 0.22+x Fe y Mn z Cu 0.11-x O 2 Wherein 0 is<x is less than or equal to 0.1; y is more than or equal to 0.32 and less than or equal to 0.36,0.31, z is more than or equal to 0.35, and y+z=0.67.
NaNi of the above formula 0.22+x Fe y Mn z Cu 0.11-x O 2 X includes, but is not limited to, a point value of any one of 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 or a range value therebetween; y includes, but is not limited to, a point value of any one of 0.32, 0.33, 0.34, 0.35, 0.36 or a range value therebetween; z includes, but is not limited to, a point value of any one of 0.31, 0.32, 0.33, 0.34, 0.35, or a range value therebetween.
The sodium-electricity layered oxide anode material is mainly prepared by sintering a mixture containing a precursor material, a copper source and a sodium source.
It will be appreciated that the sintering described above is the main step in preparing the sodium-electrical layered oxide cathode material, but is not the only step, and may include other steps such as mixing, crushing, sieving, etc.
Wherein the tap density of the precursor material is more than or equal to 1.6g/cm 3 Including but not limited to 1.6g/cm 3 、1.7g/cm 3 、1.8g/cm 3 、1.9g/cm 3 、2.0g/cm 3 、2.1g/cm 3 、2.2g/cm 3 Any one of the point values or a range value between any two.
The D50 median particle diameter d=3 to 10 μm of the copper source includes, but is not limited to, a dot value of any one of 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or a range value between any two.
And, the sintering temperature T, the D50 median particle diameter D of the copper source, and the molar ratio (0.11-x) of the copper source to the precursor material satisfy the following relation: t= -20D/log (0.11-x) +850. Wherein the sintering temperature T is expressed in degrees Celsius, and the D50 median diameter D of the copper source is expressed in μm.
It will be appreciated that the molar ratio (0.11-x) of the copper source to the precursor material is the stoichiometric ratio of the copper source to the precursor material, and is also of the general formula NaNi 0.22+x Fe y Mn z Cu 0.11-x O 2 Subscript of medium Cu, 0<x≤0.1。
According to the sodium ion battery layered oxide positive electrode material provided by the invention, the molar ratio of the copper source to the precursor material and the D50 median particle size of the copper source raw material are regulated and controlled, and the relational expression is satisfied, so that the sintering temperature of the sodium ion battery layered oxide positive electrode material can be remarkably reduced, large-scale sintering is possible, the morphology of a large sheet of the positive electrode material can be remarkably improved, the morphology of secondary particles of the positive electrode material is more round and more spherical or olive-shaped, and the energy density of the battery is further improved.
In some embodiments, the precursor material has the chemical formula Ni u Fe v Mn w (OH) 2 . Wherein u is more than or equal to 0.24 and less than or equal to 0.33,0.32, v is more than or equal to 0.41,0.31 and w is more than or equal to 0.40, and u+v+w=1.
Ni of the above general formula u Fe v Mn w (OH) 2 U includes, but is not limited to, a point value of any one of 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33 or a range value therebetween; v includes, but is not limited to, a dot value of any one of 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41 or between any twoA range value; w includes, but is not limited to, a point value of any one of 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, or a range value therebetween.
The chemical composition of the precursor material is controlled, so that the chemical composition of the obtained sodium-electricity layered oxide anode material is controlled, the sintering temperature is reduced, and the problem of morphology of a large sheet of the anode material is solved.
The precursor material adopts the D50 median particle size in the range, which is beneficial to reducing the sintering temperature and improving the morphology of a large sheet layer of the positive electrode material, so that the positive electrode material is more round and more blunt, and the energy density is further improved.
In some embodiments, the precursor material has a specific surface area BET of 5m 2 /g<BET<50m 2 And/g. Wherein the specific surface area BET includes, but is not limited to, 5.5m 2 /g、6m 2 /g、8m 2 /g、10m 2 /g、12m 2 /g、15m 2 /g、18m 2 /g、20m 2 /g、25m 2 /g、29m 2 /g、30m 2 /g、35m 2 /g、39m 2 /g、40m 2 /g、45m 2 /g、48m 2 A point value of any one of/g or a range value between any two.
The precursor material adopts the specific surface area in the range, so that the sintering temperature can be further reduced, and the morphology of a large sheet layer of the positive electrode material can be improved.
In some embodiments, the sodium source comprises a sodium-containing compound, such as NaOH, na 2 CO 3 、NaHCO 3 And NaNO 3 One or more of the above, but not limited thereto.
In some embodiments, the copper source includes a copper-containing compound, such as, but not limited to, copper oxide, copper hydroxide, or copper carbonate.
In some specific embodiments, the D50 median particle size of the sodium-electricity layered oxide positive electrode material is 5-20 μm; including but not limited to a dot value of any one of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, or a range value between any two.
The invention is beneficial to ensuring the yield of the product and avoiding the capacity hard to be exerted due to material agglomeration by controlling the D50 median particle diameter of the sodium-electricity layered oxide anode material.
In some specific embodiments, the dullness P of the sodium-electric layered oxide positive electrode material is 0.6 to 1.0; including but not limited to a point value of any one of 0.6, 0.7, 0.8, 0.91.0 or a range value therebetween.
The dullness P of the sodium-electricity layered oxide positive electrode material provided by the invention is 0.6-1.0, which indicates that the positive electrode material is round and spherical rather than sharp sheet-shaped.
The blunting degree P is tested by a granularity particle shape instrument, 100 pictures are analyzed by the device, and the result of the blunting degree P can be obtained by intelligent statistical calculation of big data. In popular terms, the nearest circle is taken as denominator, the actual numerator is taken, if the circle is relatively sharp, the blunt value P is close to 0, and if the circle is relatively smooth, the blunt value P is close to 1.
In some specific embodiments, the first coulombic efficiency of the sodium-electric layered oxide positive electrode material is greater than or equal to 92%; including but not limited to any one of the dot values or range values between any two of 92.0%, 92.1%, 92.2%, 92.3%, 92.4%, 92.5%, 92.6%, 92.7%, 92.8%, 92.9%, 93.0%, 93.5%, 94.0%.
In some specific embodiments, the sodium-electric layered oxide positive electrode material has an average specific discharge capacity (i.e., an average specific discharge capacity of 3 weeks) of not less than 133mAh/g at 0.1C for 3 weeks; including but not limited to a point value of any one of 133mAh/g, 134mAh/g, 135mAh/g, 136mAh/g, 137mAh/g, 138mAh/g, 139mAh/g, 140mAh/g, or a range value therebetween.
In some specific embodiments, the average specific discharge capacity of the sodium-electricity layered oxide positive electrode material is greater than or equal to 126mAh/g after 3 weeks of circulation at 0.5 ℃; including but not limited to a point value of any one of 126mAh/g, 127mAh/g, 128mAh/g, 129mAh/g, 130mAh/g, 131mAh/g, 132mAh/g, 133mAh/g, or a range value therebetween.
In some specific embodiments, the average specific discharge capacity of the sodium-electricity layered oxide positive electrode material is greater than or equal to 120mAh/g after 3 weeks of circulation at 1C; including but not limited to a point value of any one of 120mAh/g, 121mAh/g, 122mAh/g, 123mAh/g, 124mAh/g, 125mAh/g, 126mAh/g, 127mAh/g, 128mAh/g, 129mAh/g, 130mAh/g, or a range value therebetween.
It is understood that each of the above electrochemical performance parameters refers to the electrochemical performance of a sodium ion battery made from the sodium-electric layered oxide cathode material provided by the present invention.
It can be seen that the sodium ion battery prepared from the sodium-electricity layered oxide positive electrode material provided by the invention has excellent electrochemical performance.
In a second aspect, the present invention provides a method for preparing the sodium-electric layered oxide cathode material as described above, comprising the steps of:
and mixing the precursor material, the copper source and the sodium source, sintering, and cooling to obtain the sodium-electricity layered oxide anode material.
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the invention has the advantages of lower sintering temperature, low requirements on sintering equipment, adoption of most of sintering devices, and obvious improvement of the morphology of a large sheet layer of the positive electrode material, and the obtained secondary particles are more round in morphology, so that the energy density of the sodium battery prepared by the method is improved.
In some specific embodiments, the sintering temperature is 700-1200 ℃. It is understood that the specific sintering temperature T satisfies the relation t= -20D/log (0.11-x) +850.
In some specific embodiments, the sintering heat preservation time is 8-24 hours; including but not limited to a point value of any one of 8h, 10h, 12h, 14h, 15h, 18h, 20h, 22h, 24h or a range value therebetween.
In some specific embodiments, the temperature rising rate of the sintering is 1-10 ℃/min; including but not limited to a point value of any one of 1 deg.c/min, 3 deg.c/min, 5 deg.c/min, 8 deg.c/min, 10 deg.c/min, or a range value between any two.
In some embodiments, the sintering is performed in an oxygen-containing atmosphere.
In some embodiments, the oxygen-containing atmosphere comprises an air atmosphere and/or an oxygen atmosphere.
In some specific embodiments, the materials are calculated and weighed according to the chemical formula of the sodium-electricity layered oxide positive electrode material, and are mixed at a high speed to uniformly mix the materials.
In some embodiments, after the sintering, the steps of crushing and sieving are further included.
In some embodiments, the precursor material has the chemical formula Ni u Fe v Mn w (OH) 2 Wherein u is more than or equal to 0.24 and less than or equal to 0.33,0.32, v is more than or equal to 0.41,0.31 and w is more than or equal to 0.40, and u+v+w=1.
In some embodiments, the precursor material has a content of each impurity element of no more than 5000ppm, such as Na, S, ca, mg, al, zn, co, and Li element content of less than 5000ppm.
In some embodiments, the sodium source is a sodium-containing compound including, but not limited to, naOH, na 2 CO 3 、NaHCO 3 And NaNO 3 One or more of them.
In some embodiments, the copper source is a copper-containing compound including, but not limited to, one or more of copper oxide, copper hydroxide, copper carbonate, and copper nitrate.
In a third aspect, the present invention provides a sodium ion battery positive electrode sheet (i.e., positive electrode sheet) comprising a sodium-oxide layered oxide positive electrode material as described above.
In some specific embodiments, the positive electrode sheet comprises a current collector and a positive electrode material coated on the current collector, wherein the positive electrode material is mainly prepared from the sodium-electric layered oxide positive electrode material.
Optionally, a binder and/or a conductive agent is also included in the positive electrode material.
Among them, any conventional, commercially available binder for positive electrode sheets, such as polyvinylidene fluoride (PVDF), or a binder prepared according to the prior art may be used, but is not limited thereto.
The conductive agent may be any commercially available conductive agent for battery such as carbon black, graphite, conductive polymer, etc., but is not limited thereto.
In a fourth aspect, the present invention provides a sodium ion battery comprising a positive electrode sheet as described above.
In some embodiments, the sodium ion battery further comprises a negative electrode sheet, a separator, and an electrolyte.
The negative electrode sheet, the diaphragm and the electrolyte can be any commercially available negative electrode sheet, diaphragm and electrolyte, or any negative electrode sheet, diaphragm and electrolyte prepared by the prior art, and the invention is not limited thereto.
In a fifth aspect, the present invention provides a powered device comprising a sodium ion battery as described above.
It is understood that the above-mentioned electric equipment includes any equipment, device or system using the above-mentioned sodium ion battery, and is applied to the fields of vehicles, electronic products, aerospace, medical and energy storage, etc.
The electric equipment is not limited to electric vehicles, electric motorcycles, electric bicycles, electric tools, energy storage systems, electronic products or office equipment, and the like.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
NaHCO employed in the following examples of the invention 3 The purity of (2) was 99.84%, the purity of NaOH was 99.30%, and the purity of Na 2 CO 3 Has a purity of 99.76%, naNO 3 The purity of (2) was 99.20% and the purity of CuO was 99.46%.
Example 1
The chemical general formula of the sodium-electricity layered oxide positive electrode material provided in the embodiment is NaCu 0.1 Mn 0.33 Ni 0.23 Fe 0.34 O 2 。
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the embodiment comprises the following steps: weigh 1.061kg NaHCO 3 0.056kg NaOH, 2kg precursor Mn 0.367 Ni 0.256 Fe 0.377 (OH) 2 And 0.112kg of CuO (namely copper source) are uniformly mixed at a high speed to obtain a mixture, the mixture is sintered at a high temperature for 12 hours in an air atmosphere at 910 ℃, wherein the heating rate is 10 ℃/min, and after cooling, the sintered material is crushed and screened to obtain the D50 median particle diameter=8 mu m sodium electric layered oxide positive electrode material.
Example 2
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this example is the same as that of example 1.
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the embodiment comprises the following steps: weigh 1.178kg NaHCO 3 2kg of precursor Mn 0.367 Ni 0.256 Fe 0.378 (OH) 2 And 0.112kg of CuO are uniformly mixed at a high speed to obtain a mixture, the mixture is sintered at a high temperature for 12 hours in an air atmosphere at 950 ℃, wherein the heating rate is 10 ℃/min, and after cooling, the sintered material is crushed and screened to obtain the D50 median particle size=10 mu m sodium electric layered oxide positive electrode material.
Example 3
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this example is the same as that of example 1.
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the embodiment comprises the following steps: weigh 0.745kg Na 2 CO 3 2kg of precursor Mn 0.367 Ni 0.256 Fe 0.378 (OH) 2 And 0.112kg of CuO are uniformly mixed at a high speed to obtain a mixture, the mixture is sintered at a high temperature for 12 hours in an air atmosphere at 1050 ℃, wherein the heating rate is 10 ℃/min, and after cooling, the sintered material is crushed and screened to obtain the D50 median particle diameter=20 mu m sodium electric layered oxide positive electrode material.
Example 4
The chemical general formula of the sodium-electricity layered oxide positive electrode material provided in the embodiment is NaCu 0.01 Mn 0.33 Ni 0.32 Fe 0.34 O 2 。
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the embodiment comprises the following steps: weigh 1.06kg NaHCO 3 、0.120kg NaNO 3 2kg of precursor Mn 0.333 Ni 0.324 Fe 0.343 (OH) 2 And 0.011kg of CuO are uniformly mixed at a high speed to obtain a mixture, and the mixture is sintered at a high temperature for 12 hours in an air atmosphere at 950 ℃, wherein the heating rate is 10 ℃/min, and after cooling, the sintered material is crushed and screened to obtain the D50 median particle diameter=5 mu m sodium electric layered oxide positive electrode material.
Example 5
The chemical general formula of the sodium-electricity layered oxide positive electrode material provided in the embodiment is NaCu 0.1 Mn 0.31 Ni 0.23 Fe 0.36 O 2 。
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the embodiment comprises the following steps: weighing 0.564kg of NaOH and 2kg of precursor Mn 0.344 Ni 0.256 Fe 0.4 (OH) 2 (tap Density of precursor TD=1.7 g/cm) 3 ) And 0.112kg of CuO are uniformly mixed at a high speed to obtain a mixture, the mixture is sintered at a high temperature for 12 hours in an air atmosphere at 910 ℃, wherein the heating rate is 10 ℃/min, and after cooling, the sintered material is crushed and screened to obtain the D50 median particle size=8 mu m sodium electric layered oxide positive electrode material.
Example 6
The chemical general formula of the sodium-electricity layered oxide positive electrode material provided in the embodiment is NaCu 0.1 Mn 0.35 Ni 0.23 Fe 0.32 O 2 。
The preparation method of the sodium-electricity layered oxide positive electrode material provided by the embodiment comprises the following steps: weigh 0.236kg NaHCO 3 、0.595kg Na 2 CO 3 2kg of precursor Mn 0.389 Ni 0.256 Fe 0.355 (OH) 2 And 0.112And (3) uniformly mixing kg of CuO at a high speed to obtain a mixture, sintering the mixture at a high temperature under an air atmosphere at 970 ℃ for 12 hours, wherein the heating rate is 10 ℃/min, cooling, and then crushing and screening the sintered material to obtain the D50 median particle diameter=15 mu m sodium-electricity layered oxide anode material.
Comparative example 1
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this comparative example is the same as that of example 1.
The preparation method of the sodium electric layered oxide cathode material provided in this comparative example is basically the same as that of example 1, except that the D50 median particle diameter D of CuO (i.e., copper source) is replaced with 2 μm.
Comparative example 2
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this comparative example is the same as that of example 2.
The preparation method of the sodium electric layered oxide cathode material provided in this comparative example is basically the same as that of example 2, except that the D50 median particle diameter D of CuO (i.e., copper source) is replaced with 11 μm.
Comparative example 3
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this comparative example is the same as that of example 2.
The preparation method of the sodium-electric layered oxide cathode material provided in this comparative example is basically the same as that of example 2, except that the sintering temperature T is replaced with 930 ℃.
Comparative example 4
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this comparative example is the same as that of example 2.
The preparation method of the sodium electric layered oxide cathode material provided in this comparative example was substantially the same as in example 2, except that the sintering temperature T was replaced with 970 ℃.
Comparative example 5
The chemical general formula of the sodium-electricity layered oxide cathode material provided in this comparative example is the same as that of example 5.
The preparation method of the sodium-electricity layered oxide cathode material provided in this comparative example is basically the same as that of example 5, except that the tap density TD of the precursor is replaced with 1.5g +.cm 3 。
In each of the above examples and comparative examples, the tap density TD, the D50 median particle diameter of the precursor used and the specific surface area BET thereof, the D50 median particle diameter D of the copper source used, the molar ratio of the copper source used to the precursor used, the sintering temperature T during the production process, the D50 median particle diameter of the obtained sodium electric layered oxide cathode material product and the dullness P thereof are shown in table 1.
The testing method of the bluff degree P comprises the following steps: and carrying out the statistical analysis of the granularity and the particle shape of 100-20000 particles by adopting a rice spectrum technology W-3000 granularity and particle shape instrument. The blunting degree refers to aerodynamics for a blunting model in a wind tunnel experiment. The front section of the blunt model is a small arc, the rear section is a cylinder, and an arch section is connected between the rear section and the front section. The arch segment is tangential to the front portion. Blunt = tip arc diameter +.post cylinder diameter x 100%. Generally, the diameter of the rear cylinder is fixed, and the diameter of the top circular arc is changed to study the blunt effect.
Table 1 performance index of raw materials and products, sintering temperature:
experimental example electrochemical performance test:
positive electrode materials prepared in each example and each comparative example were used as active materials to prepare positive electrode sheets and sodium ion batteries, and electrochemical performance tests were performed on each sodium ion battery, and the results are shown in table 2.
The battery assembly and electrochemical performance test method comprises the following steps: the positive electrode materials prepared in each example and each comparative example are respectively used as active substances, the active substances are mixed according to the mass ratio of SP to PVDF of 90:5:5, NMP is added to prepare adhesive glue solution, the adhesive glue solution is coated on aluminum foil, and the aluminum foil is baked for 12 hours at 120 ℃ in a vacuum drying oven, so that the positive electrode plate is obtained. Sodium metal sheet is used as counter electrode, glass fiber (Waterman) is used as diaphragm, 1mol/L NaPF 6 EC/dmc=1:1 (Alfa) as electrolyte, 2032 coin cell was assembled in an Ar protection glove box. The battery is tested in a voltage range of 2.5-4.0V, and the battery is circulated for 3 weeks at 0.1C and circulated at 0.5CThe specific discharge capacity of each cell was recorded for 3 weeks at 3 weeks, 1C cycle, and 3 weeks on average at 0.1C, 0.5C and 1C, respectively, with the corresponding first effect (first coulombic efficiency).
Table 2 electrochemical performance test results:
as can be seen from comparison of the bluff property data and the electrical property data of example 1 and comparative example 1, and example 2 and comparative example 2, the D50 median particle diameter D of the copper source is in the range of 3 to 10 μm, and the bluff property of the positive electrode material is not less than 0.6 and approximately 1.0 while the positive electrode material exhibits a high capacity.
As can be seen from comparing the dullness data and the electrical property data of example 2 and comparative examples 3 to 4, T satisfies the formula T= -20D/log (0.11-x) +850, and the dullness of the positive electrode material is more than or equal to 0.6 and is close to 1.0 on the basis of exerting high capacity.
As can be seen from comparing the dullness data and the electrical property data of example 5 and comparative example 5, the tap density TD of the precursor was controlled to be 1.6g/cm or more 3 The passivation degree is more than or equal to 0.6 and is close to 1.0 on the basis of the high capacity of the positive electrode material.
Further, as shown in fig. 1, an SEM image of the sodium electric layered oxide cathode material prepared in example 2 is shown; FIG. 2 is an SEM image of a sodium electric layered oxide positive electrode material prepared in example 5; FIG. 3 is an SEM image of the sodium electric layered oxide positive electrode material prepared in comparative example 1; FIG. 4 is an SEM image of a sodium electric layered oxide positive electrode material prepared in comparative example 3; fig. 5 is an SEM image of the sodium electric layered oxide positive electrode material prepared in comparative example 5.
As can be seen from fig. 1 and fig. 2, the secondary particles of the sodium-electricity layered oxide positive electrode material prepared in the examples are in a sphere-like shape, and have a round appearance instead of a sheet shape. And the secondary particles of the sodium-electricity layered oxide positive electrode material prepared in the comparative example are in a large-sheet morphology.
In summary, according to the layered oxide positive electrode material for the sodium ion battery, provided by the invention, by controlling the molar ratio of the copper source to the precursor material and the D50 median particle size of the copper source raw material and satisfying the relational expression, the sintering temperature of the layered oxide positive electrode material for the sodium ion battery can be reduced, the morphology of a large sheet layer of the positive electrode material can be obviously improved, and the energy density of the sodium ion battery is further improved.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (10)
1. The sodium-electricity layered oxide positive electrode material is characterized in that the chemical general formula of the sodium-electricity layered oxide positive electrode material is NaNi 0.22+x Fe y Mn z Cu 0.11-x O 2 Wherein 0 is<x is less than or equal to 0.1; y is more than or equal to 0.32 and less than or equal to 0.36,0.31, z is more than or equal to 0.35, and y+z=0.67;
the sodium-electricity layered oxide anode material is mainly prepared by sintering a mixture containing a precursor material, a copper source and a sodium source; wherein the tap density of the precursor material is more than or equal to 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The D50 median particle diameter D=3-10 mu m of the copper source; and the sintering temperature T, the D50 median particle diameter D of the copper source, and the molar ratio (0.11-x) of the copper source to the precursor material satisfy the following relation: t= -20D/log (0.11-x) +850.
2. The sodium-electric layered oxide cathode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The chemical general formula of the precursor material is Ni u Fe v Mn w (OH) 2 Wherein 0.24U is more than or equal to 0.33,0.32, v is more than or equal to 0.41,0.31, w is more than or equal to 0.40, and u+v+w=1;
(2) The specific surface area BET of the precursor material is 5m 2 /g<BET<50m 2 /g。
3. The sodium-electric layered oxide cathode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The D50 median particle size of the sodium-electricity layered oxide positive electrode material is 5-20 mu m;
(2) The dullness P of the sodium-electricity layered oxide positive electrode material is 0.6-1.0.
4. The sodium-electric layered oxide cathode material according to claim 1, characterized by comprising at least one of the following features (1) to (4):
(1) The first coulomb efficiency of the sodium-electricity layered oxide positive electrode material is more than or equal to 92%;
(2) The average discharge specific capacity of the sodium-electricity layered oxide positive electrode material is more than or equal to 133mAh/g after 3 weeks of circulation at 0.1 ℃;
(3) The average discharge specific capacity of the sodium-electricity layered oxide anode material is more than or equal to 126mAh/g after 3 weeks of circulation at 0.5 ℃;
(4) The average specific discharge capacity of the sodium-electricity layered oxide positive electrode material is more than or equal to 120mAh/g after 3 weeks of circulation at 1C.
5. The method for preparing the sodium-electricity layered oxide positive electrode material according to any one of claims 1 to 4, comprising the steps of:
and mixing the precursor material, the copper source and the sodium source, and then sintering to obtain the sodium-electricity layered oxide anode material.
6. The method for producing a sodium-electric layered oxide positive electrode material according to claim 5, characterized by comprising at least one of the following features (1) to (2):
(1) The sintering heat preservation time is 8-24 hours;
(2) The sintering is performed in an oxygen-containing atmosphere comprising an air atmosphere and/or an oxygen atmosphere.
7. The method for preparing a sodium-electric layered oxide cathode material according to claim 5, wherein the precursor material has a chemical formula of Ni u Fe v Mn w (OH) 2 Wherein u is more than or equal to 0.24 and less than or equal to 0.33,0.32, v is more than or equal to 0.41,0.31 and w is more than or equal to 0.40, and u+v+w=1.
8. The positive electrode sheet, characterized by comprising the sodium-electrode layered oxide positive electrode material according to any one of claims 1 to 4.
9. A sodium ion battery comprising the positive electrode sheet according to claim 8.
10. A powered device comprising a sodium ion battery as defined in claim 9.
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