CN117393748A - Layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment - Google Patents
Layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment Download PDFInfo
- Publication number
- CN117393748A CN117393748A CN202311555407.6A CN202311555407A CN117393748A CN 117393748 A CN117393748 A CN 117393748A CN 202311555407 A CN202311555407 A CN 202311555407A CN 117393748 A CN117393748 A CN 117393748A
- Authority
- CN
- China
- Prior art keywords
- layered oxide
- sodium
- cathode material
- positive electrode
- oxide cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 95
- 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 87
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 87
- 239000002243 precursor Substances 0.000 claims abstract description 64
- 238000005245 sintering Methods 0.000 claims abstract description 45
- -1 nickel-copper-iron-manganese hydroxide Chemical compound 0.000 claims abstract description 25
- 239000002019 doping agent Substances 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 4
- 239000010406 cathode material Substances 0.000 claims description 74
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 239000010949 copper Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing 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
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a layered oxide positive electrode material, a preparation method thereof, a positive electrode plate, a sodium ion battery and electric equipment. The layered oxide anode material is mainly prepared by sintering a nickel-copper-iron-manganese hydroxide precursor, a sodium source and a doping agent; the ratio of the mass of the doping element in the doping agent to the sum of the mass of the nickel-copper-iron-manganese hydroxide precursor and the mass of the sodium source is alpha, and alpha is more than or equal to 0.001 and less than or equal to 0.02; and the sintering temperature Y satisfies y=750 to 50×lgα±10℃. The layered oxide positive electrode material has small specific surface area, good cycle performance and high capacity.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a layered oxide positive electrode material, a preparation method thereof, a positive electrode plate, a sodium ion battery and electric equipment.
Background
In recent years, sodium ion batteries are rapidly developed, and are considered as one of the best choices of a large-scale energy storage system because of the abundant sodium content, easy availability and low cost. Therefore, development of a sodium battery electrode material having good electrochemical properties has been an important point of attention. Sodium ion battery cathode material research has focused mainly on several systems: polyanions, layered oxides, prussian blue and other systems. In the systems, the layered oxide has the advantages of convenient synthesis, simple structure, wide raw material sources and the like, and is easy to realize large-scale continuous industrial production.
The polycrystalline material in the layered oxide has higher capacity and rate capability, but when the polycrystalline material of the positive electrode of the sodium ion battery has higher copper content, the polycrystalline material has larger specific surface, and more side reactions are generated in circulation, so that the cycle performance of the battery is influenced.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a layered oxide cathode material, in which the specific surface area of the layered oxide cathode material can be reduced by controlling the amount of doping elements and controlling the sintering temperature. The problem of the polycrystalline material ratio table great in the prior art lead to battery cycle performance decline is solved.
The second object of the present invention is to provide a method for preparing a layered oxide cathode material, which has the advantages of simple operation, wide raw material source, suitability for mass production, etc.
The third object of the invention is to provide a positive electrode plate containing the layered oxide positive electrode material, and a sodium ion battery prepared from the positive electrode plate has good cycle performance.
A fourth object of the present invention is to provide a sodium ion battery which is excellent in cycle performance.
A fifth object of the present invention is to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a layered oxide anode material, which is prepared by sintering a nickel-copper-iron-manganese hydroxide precursor, a sodium source and a doping agent;
wherein the ratio of the mass of the doping element in the doping agent to the sum of the mass of the nickel-copper-iron-manganese hydroxide precursor and the mass of the sodium source is alpha, and alpha is more than or equal to 0.001 and less than or equal to 0.02;
and the sintering temperature Y satisfies y=750 to 50×lgα±10℃.
Preferably, the chemical formula of the nickel copper iron manganese hydroxide precursor is Ni 1-x-y-z Cu x Fe y Mn z (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.03 and less than or equal to 1/9,0.31, y is more than or equal to 0.35,0.31 and z is more than or equal to 0.35.
Preferably, the doping element in the dopant includes at least one of Al, ca, zr, co and Mg element.
Preferably, the molar ratio of sodium element in the sodium source to the nickel copper iron manganese hydroxide precursor is R, wherein R is 0.9< 1.0.
Preferably, the sintering temperature y=820 to 920 ℃.
Preferably, the sodium source comprises at least one of sodium carbonate and sodium hydroxide, wherein the mass of the sodium carbonate is less than 10% of the total mass of the sodium source.
Preferably, the specific surface area of the layered oxide cathode material is less than or equal to 0.5m 2 /g。
Preferably, the layered oxide cathode material has a median particle diameter of 4 to 20 μm.
Preferably, the layered oxide cathode material has a polycrystalline morphology.
The invention further provides a preparation method of the layered oxide cathode material, which comprises the following steps:
and mixing and sintering the nickel-copper-iron-manganese hydroxide precursor, the sodium source and the doping agent to obtain the layered oxide cathode material.
Preferably, the sintering time is 8-30 hours.
Preferably, the temperature rising rate in the sintering process is 1-10 ℃/min.
The invention also provides a positive electrode plate which comprises the layered oxide positive electrode material.
The invention further provides a sodium ion battery, which comprises the positive electrode 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:
according to the layered oxide positive electrode material provided by the invention, the mass of the doping element is controlled to occupy the mass sum of the precursor and the sodium source, the sintering temperature is regulated and controlled to meet Y=750-50 xlgalpha+/-10 ℃, the rapid growth of primary particles of the precursor is prevented, and the gaps generated by the rapid growth of the primary particles at high temperature are reduced, so that the layered oxide positive electrode material has the advantages of small specific surface area, good cycle performance and high capacity.
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 layered oxide cathode material prepared in example 7 provided by the present invention;
fig. 2 is an SEM image of the layered oxide cathode material prepared in comparative example 3 provided in the present invention;
fig. 3 is an SEM image of the layered oxide cathode material prepared in comparative example 4 provided by 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 the present invention, unless specifically stated otherwise, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity or as implicitly indicating the importance or quantity of the indicated technical feature. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the present invention, "one or more" or "at least one" means any one, any two or more of the listed items unless specifically stated otherwise. Wherein "several" means any two or more.
In a first aspect, the invention provides a layered oxide cathode material, which is prepared mainly by mixing and sintering a nickel-copper-iron-manganese hydroxide precursor, a sodium source and a dopant.
Wherein the ratio of the mass of the doping element in the doping agent to the sum of the mass of the nickel-copper-iron-manganese hydroxide precursor and the mass of the sodium source is alpha, and alpha is more than or equal to 0.001 and less than or equal to 0.02. Where α includes, but is not limited to, a point value of any one of 0.001, 0.003, 0.005, 0.008, 0.01, 0.012, 0.015, 0.018, 0.02 or a range value therebetween.
And the sintering temperature Y satisfies y=750 to 50×lgα±10℃. It is understood that the unit of Y is in degrees Celsius.
Wherein "±" indicates an error in sintering temperature, that is, y=750 to 50×lgα -10 to 750 to 50×lgα+10. For example, when α=0.001, y=890 to 910 ℃.
According to the invention, the mass of the doping element is controlled to occupy the mass sum of the precursor and the sodium source, the sintering temperature is regulated to be within the range of Y=750-50 xlgalpha + -10 ℃, the rapid growth of primary particles of the precursor can be prevented, the gaps generated by the rapid growth of the primary particles at high temperature are reduced, and finally the polycrystalline layered oxide anode material with small specific surface area, good cycle performance and high capacity is formed.
In some embodiments, the nickel copper iron manganese hydroxide precursor has the chemical formula Ni 1-x-y- z Cu x Fe y Mn z (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.03 and less than or equal to 1/9,0.31, y is more than or equal to 0.35,0.31 and z is more than or equal to 0.35.
Chemical Ni 1-x-y-z Cu x Fe y Mn z (OH) 2 X includes, but is not limited to, a point value of any one of 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 1/9 or a range value therebetween; y 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; 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 nickel-copper-iron-manganese hydroxide precursor may be prepared by any method commonly used in the art, such as a coprecipitation method, a hydrothermal method, a sol-gel method, an oxide mixing method, and the like, but is not limited thereto. The nickel copper iron manganese hydroxide precursor may also be a commercially available precursor material, as the present invention is not limited in this regard.
As an example, the method for preparing nickel copper iron manganese hydroxide precursor by adopting the coprecipitation method comprises the following steps: according to Ni: cu: fe: mn molar ratio is used for preparing quaternary metal salt solution as raw material, quaternary metal salt solution, liquid alkali, ammonia water and nitrogen are added into a reaction kettle for coprecipitation reaction, and the reaction process is controlled by controlling the reaction rotating speed, temperature, pH value and ammonia value, so that the purpose of preparing nickel-copper-iron-manganese hydroxide precursor slurry is achieved. The nickel-copper-iron-manganese hydroxide precursor slurry is subjected to washing and dehydration procedures by a centrifuge or a filter press, and finally is subjected to drying, mixing, sieving and packaging procedures to prepare a nickel-copper-iron-manganese hydroxide precursor finished product.
In some specific embodiments, the doping elements in the dopant include at least one of Al, ca, zr, co and Mg, and any two, three or four of them may be selected.
The doping element can limit the growth of primary particles, reduce gaps among particles, reduce specific surface area and improve electrochemical performance.
In some embodiments, the dopant is a compound containing a doping element, and by way of example, the dopant includes an oxide containing a doping element and/or a carbonate containing a doping element, but is not limited thereto.
In some specific embodiments, the molar ratio of the sodium element in the sodium source to the nickel copper iron manganese hydroxide precursor is R, and R satisfies 0.9< R.ltoreq.1.0. Wherein R includes, but is not limited to, a dot value of any one of 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.0 or a range value therebetween.
By using the R value in the above range, the capacity of the polycrystalline material can be exhibited.
In some specific embodiments, the ratio of the molar amount of doping element in the dopant to the molar amount of the nickel copper iron manganese hydroxide precursor is Q, Q satisfying 0.001+.q <0.1; wherein Q includes, but is not limited to, a dot value of any one of 0.001, 0.002, 0.003, 0.005, 0.008, 0.01, 0.03, 0.05, 0.07, 0.09, or a range value therebetween.
In some specific embodiments, the sintering temperature y=820 to 920 ℃, including, but not limited to, any one of 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃ or a range of values between any two.
In the sintering temperature range, the polycrystalline material with smaller primary particles and lower specific surface area can be produced.
It is understood that the raw material sodium source used for preparing the layered oxide cathode material can be any sodium-containing compound commonly used in the art, and the layered oxide cathode material with a relatively low specific surface area can be obtained.
In some specific embodiments, in order to further reduce the specific surface area of the layered oxide cathode material and improve the capacity and cycle performance of the layered oxide cathode material, the invention optimizes the composition and the proportion of the sodium source in order to avoid the reduction of the capacity and cycle performance of the material caused by insufficient reaction of high-melting sodium carbonate at a lower polycrystalline sintering temperature. Wherein the sodium source comprises at least one of sodium carbonate and sodium hydroxide, preferably contains both sodium carbonate and sodium hydroxide, wherein the mass of sodium carbonate is less than 10% of the total mass of the sodium source, including but not limited to a point value of any one of 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 1%, or a range value between any two.
In some specific embodiments, the specific surface area of the layered oxide cathode material is less than or equal to 0.5m 2 /g; including but not limited to 0.5m 2 /g、0.48m 2 /g、0.45m 2 /g、0.43m 2 /g、0.41m 2 /g、0.4m 2 /g、0.39m 2 /g、0.38m 2 /g、0.36m 2 /g、0.35m 2 /g、0.33m 2 /g、0.3m 2 A point value of any one of/g or a range value between any two.
The layered oxide positive electrode material prepared by the invention has small specific surface area, less electrolyte is consumed in the charge and discharge process, side reaction is reduced, and the cycle performance of the battery is further improved.
In some specific embodiments, the layered oxide cathode material has a median particle size of 4 to 20 μm; including but not limited to a dot value of any one of 4 μm, 5 μm, 7 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, or a range value between any two.
In some embodiments, the layered oxide cathode material has a polycrystalline morphology.
In some embodiments, the layered oxide cathode material has the general formula Na m Ni 1-x-y- z Cu x Fe y Mn z M a O 2 Wherein 0.9<m≤1.0，0.03≤x≤1/9，0.31≤y≤0.35，0.31≤z≤0.35，0.001≤a<0.1, M is selected from one or more of Al, ca, zr, co and Mg elements.
In some specific embodiments, the first discharge capacity of a sodium ion battery containing the layered oxide cathode material at 0.1C is greater than or equal to 139mAh/g, including, but not limited to, a point value of any one of 139mAh/g, 140mAh/g, 141mAh/g, 142mAh/g, 143mAh/g, 144mAh/g, 145mAh/g, or a range value therebetween.
In some embodiments, the first coulombic efficiency of a sodium ion battery containing the layered oxide cathode material is greater than or equal to 92% at 0.1C, including, but not limited to, a point value of any one of 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, or a range of values between any two.
In some embodiments, the capacity retention of a sodium ion battery containing the layered oxide cathode material after 50 cycles at 1C is greater than or equal to 93%, including, but not limited to, any one of 93%, 93.5%, 94%, 94.5%, 95% spot value or a range of values between any two.
In a second aspect, the present invention provides a method for preparing a layered oxide cathode material, comprising the steps of:
and (3) mixing the nickel-copper-iron-manganese hydroxide precursor, a sodium source and a doping agent at a high speed according to a stoichiometric ratio, sintering, and cooling to obtain the layered oxide cathode material.
The method can reduce the specific surface area of the layered oxide cathode material and improve the capacity and the cycle performance of the layered oxide cathode material.
In addition, the method has the advantages of simple operation, wide raw material sources, suitability for mass production and the like.
In some specific embodiments, the sintering time is 8 to 30 hours; including but not limited to a point value of any one of 8h, 10h, 12h, 15h, 18h, 20h, 24h, 28h, 30h, or a range value therebetween.
In some specific embodiments, the temperature rise rate during the sintering process is 1-10 ℃/min, including but not limited to a point value of any one of 1 ℃/min, 3 ℃/min, 5 ℃/min, 7 ℃/min, 8 ℃/min, 10 ℃/min, or a range value between any two.
In some embodiments, the atmosphere of sintering comprises an air atmosphere or an oxygen atmosphere.
In a third aspect, the present invention provides a positive electrode sheet, including the layered oxide positive electrode material.
The sodium ion battery prepared from the positive plate has good cycle performance and high capacity.
In some specific embodiments, the positive electrode sheet includes a current collector and a composite layer disposed on the current collector, the composite layer being made primarily of the layered oxide positive electrode material.
Preferably, the composite layer is mainly made of the layered oxide cathode material, a binder, and a conductive agent.
The binder includes any binder material commonly used in the art, and as an example, the binder includes polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene, sodium carboxymethyl cellulose, etc., but is not limited thereto.
The conductive agent includes any conductive material commonly used in the art, and as an example, the conductive agent includes conductive graphite, acetylene black, carbon nanotubes, nano-powder, graphene, and the like, but is not limited thereto.
In a fourth aspect, the invention provides a sodium ion battery, comprising the positive electrode plate.
The sodium ion battery has good cycle performance and high capacity.
In some embodiments, the sodium ion battery further comprises a negative electrode tab, an electrolyte, and a separator.
The negative electrode plate can be any negative electrode plate commonly used in the field, and the negative electrode active material in the negative electrode plate comprises any negative electrode active material sold in the market or prepared according to the prior art. For example, the anode active material may be natural graphite, artificial graphite, mesophase micro carbon spheres, hard carbon, soft carbon, silicon-based material, tin-based material, or the like, but is not limited thereto.
The separator and the electrolyte may be any commercially available separator and electrolyte, or may be prepared according to any prior art, and the present invention is not limited thereto.
In a fifth aspect, the present invention provides an electrical device, including the sodium ion battery.
The electric equipment comprises any device, system or equipment containing the sodium ion battery, such as an electric automobile, an electric motorcycle, an electric bicycle, an electric tool, an energy storage system, an electronic product, office equipment and the like, but is not limited to the device, the system or the equipment.
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.
Example 1
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 1/3-0.03 Cu 0.03 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 0.96, the sodium source is a mixture of sodium hydroxide and sodium carbonate, the mass of the sodium carbonate accounts for 10 percent of the total mass of the sodium source, and the mass of the metal element accounts for alpha = of the total mass of the precursor and the sodium source0.001 alumina. And (3) mixing the precursor, the sodium source and the alumina at a high speed, sintering for 12 hours at 910 ℃, wherein the heating rate is 3 ℃/min, and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 0.96 Ni 1/3-0.03 Cu 0.03 Fe 1/3 Mn 1/ 3 Al 0.005 O 2 。
Example 2
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 1/3-0.03 Cu 0.03 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 0.96, the sodium source is a mixture of sodium hydroxide and sodium carbonate, the mass of the sodium carbonate accounts for 10% of the total mass of the sodium source, and zirconium oxide with the mass of metal element accounting for alpha=0.001 of the total mass of the precursor and the sodium source is weighed. And (3) mixing the precursor, the sodium source and the zirconia at a high speed, sintering for 15 hours at 890 ℃, wherein the heating rate is 2 ℃/min, and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 0.96 Ni 1/3-0.03 Cu 0.03 Fe 1/3 Mn 1/ 3 Zr 0.001 O 2 。
Example 3
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 2/9 Cu 1/9 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 0.95, the sodium source is a mixture of sodium hydroxide and sodium carbonate, the mass of the sodium carbonate accounts for 10% of the total mass of the sodium source, and calcium oxide with the mass of metal element accounting for alpha=0.02 of the total mass of the precursor and the sodium source is weighed. Mixing the precursor, sodium source and calcium oxide at high speed, sintering at 835 deg.C for 15 hr at a heating rate of 2 deg.C/min,and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 0.95 Ni 2/9 Cu 1/9 Fe 1/3 Mn 1/ 3 Ca 0.07 O 2 。
Example 4
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 1/3-0.05 Cu 0.05 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 0.96, the sodium source is a mixture of sodium hydroxide and sodium carbonate, the mass of the sodium carbonate accounts for 10% of the total mass of the sodium source, and alumina and zirconia, the mass of which accounts for alpha=0.02 of the total mass of the precursor and the sodium source, are weighed (wherein the aluminum element and the zirconium element respectively account for 0.01 of the total mass of the precursor and the sodium source). And (3) mixing the precursor, the sodium source, the alumina and the zirconia at a high speed, sintering for 15 hours at 835 ℃, heating at a rate of 2 ℃/min, and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 0.96 Ni 1/3-0.05 Cu 0.05 Fe 1/3 Mn 1/ 3 Al 0.05 Zr 0.015 O 2 。
Example 5
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 1/3-0.07 Cu 0.07 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 0.96, the sodium source is a mixture of sodium hydroxide and sodium carbonate, the mass of the sodium carbonate accounts for 10% of the total mass of the sodium source, and aluminum oxide and calcium oxide, the mass of which accounts for alpha=0.016 of the total mass of the precursor and the sodium source, are weighed (wherein the aluminum element and the calcium element respectively account for 0.008 of the total mass of the precursor and the sodium source). Precursor, sodium source, alumina and oxygenAnd (3) after mixing the calcium oxide at a high speed, sintering for 15 hours at 840 ℃, wherein the heating rate is 2 ℃/min, and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 0.96 Ni 1/3-0.07 Cu 0.07 Fe 1/3 Mn 1/ 3 Al 0.04 Ca 0.028 O 2 。
Example 6
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 2/9 Cu 1/9 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 0.98, the sodium source is a mixture of sodium hydroxide and sodium carbonate, the mass of the sodium carbonate accounts for 10% of the total mass of the sodium source, and calcium oxide and zirconium oxide, the mass of which accounts for alpha=0.012, are weighed, the mass of metal element accounts for the total mass of the precursor and the sodium source (wherein the calcium element and the zirconium element respectively account for 0.006) of the total mass of the precursor and the sodium source. And (3) mixing the precursor, the sodium source, the calcium oxide and the zirconium oxide at a high speed, sintering for 15h at 845 ℃, heating at a rate of 2 ℃/min, and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 0.98 Ni 2/9 Cu 1/9 Fe 1/3 Mn 1/ 3 Ca 0.02 Zr 0.009 O 2 。
Example 7
The preparation method of the layered oxide cathode material provided by the embodiment comprises the following steps:
weighing precursor Ni 1/3-0.03 Cu 0.03 Fe 1/3 Mn 1/3 (OH) 2 And a sodium source, wherein the molar ratio of sodium element in the sodium source to the precursor is 1.0, the sodium source is a mixture of sodium hydroxide and sodium carbonate, wherein the mass of the sodium carbonate accounts for 10 percent of the total mass of the sodium source, and aluminum oxide, calcium oxide and zirconium oxide (wherein aluminumThe elements of the precursor, the calcium element and the zirconium element respectively account for 0.005 of the total mass of the precursor and the sodium source). And (3) mixing the precursor, the sodium source, the aluminum oxide, the calcium oxide and the zirconium oxide at a high speed, sintering for 15 hours at 840 ℃, heating at a rate of 2 ℃/min, and crushing the sintered material to obtain the layered oxide cathode material.
The chemical formula of the layered oxide cathode material prepared in the embodiment is Na 1.0 Ni 1/3-0.03 Cu 0.03 Fe 1/3 Mn 1/ 3 Al 0.026 Ca 0.018 Zr 0.008 O 2 。
Example 8
The preparation method of the layered oxide cathode material provided in this example is basically the same as that in example 1, except that cobalt oxide, in which the mass of the metal element is α=0.001 of the total mass of the precursor and the sodium source, is weighed.
Example 9
The preparation method of the layered oxide cathode material provided in this example is basically the same as that of example 1, except that magnesium oxide, in which the mass of the metal element is α=0.001 of the total mass of the precursor and the sodium source, is weighed.
Example 10
The preparation method of the layered oxide cathode material provided in this example is basically the same as that of example 1, except that sodium carbonate accounts for 90% of the total mass of the sodium source.
Comparative example 1
The preparation method of the layered oxide cathode material provided in this comparative example is substantially the same as that of example 1, except that alumina is not added.
Comparative example 2
The preparation method of the layered oxide cathode material provided in this comparative example is substantially the same as that of example 3, except that no calcium oxide is added.
Comparative example 3
The preparation method of the layered oxide cathode material provided in this comparative example was substantially the same as in example 7, except that the sintering temperature was replaced with 810 ℃.
Comparative example 4
The preparation method of the layered oxide cathode material provided in this comparative example was substantially the same as in example 2, except that the sintering temperature was replaced with 930 ℃.
Comparative example 5
The preparation method of the layered oxide cathode material provided in this comparative example is basically the same as that of example 3, except that calcium oxide, in which the mass of the metal element is α=0.03, based on the total mass of the precursor and the sodium source, is weighed, and the sintering temperature is replaced with 817 ℃.
The alpha value, theoretical sintering temperature and actual sintering temperature in each of the above examples and each of the comparative examples are shown in table 1.
Experimental example
The layered oxide cathode materials prepared in the above examples and comparative examples were subjected to a morphology test, a specific surface area (abbreviated as BET) test, a median particle diameter D50 test, a first discharge capacity (abbreviated as first discharge) test, a first-cycle charge and discharge efficiency (abbreviated as first effect) test, and a capacity retention test after 50 cycles, respectively, wherein the test results are shown in table 1.
Wherein, morphology test: a Hitachi S-4800 type field emission scanning electron microscope is adopted, the accelerating voltage is 5kV, the amplification factor is 5k, and the shooting mode is SE. Specific surface area test: and testing by adopting a microscopic high-porosity specific surface area analyzer.
And (3) assembling a button cell: the layered oxide cathode material, the conductive agent Super P and the adhesive PVDF are mixed according to the mass ratio of 90:5:5 preparing positive electrode material slurry by using a deaeration machine, regulating the solid content of the slurry to 39% by adopting N-methyl pyrrolidone (NMP), coating the regulated slurry on aluminum foil by using an automatic coating machine, drying at 120 ℃ in a vacuum drying oven, rolling by a roll squeezer, performing button 2032 battery assembly in a glove box after punching by a slicer, and adopting NaPF with electrolyte of 1.2mol/L 6 Wherein the solvent is EC: PC: emc=1:1:1 (volume ratio), 2wt.% of FEC is additionally added, the separator is a glass fiber separator, and a metallic sodium sheet is used as a counter electrode.
Electrochemical testing: and (3) carrying out charge and discharge test on the button half battery on a Xinwei tester at a voltage interval of 2.5-4.05V. 0.1C was charged and discharged 3 times, and then 1C was subjected to a charge and discharge test for the first discharge capacity and the first-turn charge and discharge efficiency of 0.1C, and the capacity retention after 50 turns of 1C cycle.
Table 1 parameters for preparing and characterizing layered oxide cathode materials
Further, an SEM image of the layered oxide cathode material prepared in example 7 is shown in fig. 1. An SEM image of the layered oxide cathode material prepared in comparative example 3 is shown in fig. 2. An SEM image of the layered oxide cathode material prepared in comparative example 4 is shown in fig. 3.
Referring to table 1, the data of examples 1 to 10 demonstrate that the specific surface area of the layered oxide cathode material can be reduced and the capacity and cycle performance can be improved by controlling the amount of doping element and controlling the sintering temperature.
As can be seen from the comparison of example 1 with comparative example 1, example 3 with comparative example 2, the positive electrode material sintered by adding the dopant has smaller specific surface area and better capacity and cycle performance.
As can be seen from a comparison of example 7 and comparative example 3, the positive electrode material obtained in comparative example 3 was inferior in capacity and cycle performance after sintering at a temperature lower than the theoretical sintering temperature.
As can be seen from comparing example 2 with comparative example 4, after the actual sintering temperature is higher than the theoretical sintering temperature, the positive electrode material obtained in comparative example 4 has a morphology similar to that of a single crystal, and the capacity and the cycle performance are lower.
As can be seen from comparing the morphologies of example 7 and comparative example 3, the positive electrode material obtained in example 7 had a denser surface, whereas the positive electrode material obtained in comparative example 3 had a larger primary particle size and more gaps.
As can be seen from comparing example 3 with comparative example 5, the excessive amount of the doping element leads to a decrease in capacity and cycle performance of comparative example 5.
Further, as can be seen from a comparison of example 1 and example 10, example 10 caused insufficient sintering due to the excessive use of sodium carbonate, and further resulted in a lower capacity of the prepared positive electrode material and a decrease in cycle performance.
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 layered oxide anode material is characterized by being prepared by sintering a nickel-copper-iron-manganese hydroxide precursor, a sodium source and a doping agent;
wherein the ratio of the mass of the doping element in the doping agent to the sum of the mass of the nickel-copper-iron-manganese hydroxide precursor and the mass of the sodium source is alpha, and alpha is more than or equal to 0.001 and less than or equal to 0.02;
and the sintering temperature Y satisfies y=750 to 50×lgα±10℃.
2. The layered oxide cathode material according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) The chemical formula of the nickel-copper-iron-manganese hydroxide precursor is Ni 1-x-y-z Cu x Fe y Mn z (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is more than or equal to 0.03 and less than or equal to 1/9,0.31, y is more than or equal to 0.35,0.31 and z is more than or equal to 0.35;
(2) The doping element in the dopant comprises at least one of Al, ca, zr, co and Mg element;
(3) The molar ratio of the sodium element in the sodium source to the nickel-copper-iron-manganese hydroxide precursor is R, wherein R is 0.9< and less than or equal to 1.0.
3. The layered oxide cathode material according to claim 1, wherein the sintering temperature Y = 820-920 ℃.
4. The layered oxide cathode material of claim 1, wherein the sodium source comprises at least one of sodium carbonate and sodium hydroxide, wherein the mass of the sodium carbonate is less than 10% of the total mass of the sodium source.
5. The layered oxide cathode material according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) The specific surface area of the layered oxide positive electrode material is less than or equal to 0.5m 2 /g；
(2) The median particle diameter of the layered oxide cathode material is 4-20 mu m;
(3) The layered oxide cathode material has a polycrystalline morphology.
6. The method for producing a layered oxide cathode material according to any one of claims 1 to 5, comprising the steps of:
and mixing and sintering the nickel-copper-iron-manganese hydroxide precursor, the sodium source and the doping agent to obtain the layered oxide cathode material.
7. The method for producing a layered oxide cathode material according to claim 6, wherein the sintering time is 8 to 30 hours;
and/or the temperature rising rate in the sintering process is 1-10 ℃/min.
8. A positive electrode sheet comprising the layered oxide positive electrode material according to any one of claims 1 to 5.
9. A sodium ion battery comprising the positive electrode sheet of claim 8.
10. A powered device comprising the sodium ion battery of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311555407.6A CN117393748A (en) | 2023-11-20 | 2023-11-20 | Layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311555407.6A CN117393748A (en) | 2023-11-20 | 2023-11-20 | Layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117393748A true CN117393748A (en) | 2024-01-12 |
Family
ID=89435778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311555407.6A Pending CN117393748A (en) | 2023-11-20 | 2023-11-20 | Layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117393748A (en) |
-
2023
- 2023-11-20 CN CN202311555407.6A patent/CN117393748A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| KR101562686B1 (en) | Oxycobalt hydroxide particulate powder and manufacturing method therefor, as well as lithium cobaltate particulate powder, manufacturing method therefor, and non-aqueous electrolyte secondary battery using the same | |
| CN110931768A (en) | Ternary positive electrode material of high-nickel monocrystal lithium ion battery and preparation method | |
| CN107482172B (en) | High-rate layered lithium-rich manganese-based cathode material and preparation method thereof | |
| CN110289408A (en) | Nano-silicon and silicon/carbon composite and preparation method and application based on cutting scrap silicon | |
| CN115763717A (en) | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery | |
| CN115732674A (en) | Sodium anode precursor material and preparation method and application thereof | |
| CN113113590A (en) | Single crystal anode material with core-shell structure and preparation method thereof | |
| CN115395007A (en) | Layered-spinel composite phase monocrystal lithium-rich manganese-based positive electrode material and application thereof | |
| CN113422039A (en) | Ternary composite oxide matrix material, ternary positive electrode material, preparation method and lithium ion battery prepared from ternary composite oxide matrix material and ternary positive electrode material | |
| CN115340134B (en) | Preparation method of nickel cobalt lithium manganate precursor with coating structure and lithium ion battery containing precursor | |
| CN115304104B (en) | Manganese series lithium supplementing additive, preparation method and application thereof | |
| CN116053458A (en) | Doped NCM ternary positive electrode material, preparation method thereof, positive electrode and lithium ion battery | |
| CN117393748A (en) | Layered oxide positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment | |
| CN112768686A (en) | Positive electrode material, positive plate and lithium ion battery | |
| CN114242982B (en) | Graphene-coated two-dimensional metal compound electrode material and preparation method and application thereof | |
| CN117276535B (en) | High-nickel positive electrode material, and preparation method and application thereof | |
| CN117558912B (en) | Positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment | |
| CN117525386B (en) | High-nickel positive electrode material, and preparation method and application thereof | |
| CN115472841A (en) | Positive active material and preparation method and application thereof | |
| CN118016870A (en) | Positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment | |
| CN117712340A (en) | Positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment | |
| CN116072858A (en) | Niobium-doped nickel-cobalt-manganese lithium aluminate quaternary material, preparation method thereof and lithium ion battery containing same | |
| CN116072857A (en) | Niobium-phosphorus co-doped nickel-cobalt-manganese lithium aluminate quaternary material, preparation method thereof and lithium ion battery containing same | |
| CN116062797A (en) | Positive electrode material and battery containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |