CN117457888A - Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof - Google Patents
Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN117457888A CN117457888A CN202311775208.6A CN202311775208A CN117457888A CN 117457888 A CN117457888 A CN 117457888A CN 202311775208 A CN202311775208 A CN 202311775208A CN 117457888 A CN117457888 A CN 117457888A
- Authority
- CN
- China
- Prior art keywords
- ion battery
- sodium ion
- positive electrode
- single crystal
- electrode material
- 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.)
- Withdrawn
Links
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 76
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000013078 crystal Substances 0.000 title claims abstract description 59
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000002019 doping agent Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000012216 screening Methods 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 239000006012 monoammonium phosphate Substances 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 15
- 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 abstract description 11
- 238000005056 compaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000005303 weighing Methods 0.000 abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 125000004436 sodium atom Chemical group 0.000 description 6
- 229910006404 SnO 2 Inorganic materials 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
- C30B9/12—Salt solvents, e.g. flux growth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a layered oxide single crystal positive electrode material of a sodium ion battery and a preparation method thereof, and relates to the technical field of new energy batteries. The invention comprises the following steps: weighing a sodium ion battery anode material precursor, a sodium compound, a fluxing agent and a doping agent according to a certain proportion, and uniformly mixing; and (3) sintering, crushing, screening and coating the mixture at a high temperature, and then sintering, crushing and screening the mixture for the second time to finally prepare the finished product of the layered oxide single crystal positive electrode material of the sodium ion battery. According to the invention, the fluxing agent and the doping agent are added in the synthesis process of the sodium ion battery anode material, so that the sodium ion battery anode material is formed into uniform and dispersed monocrystal particle morphology, more sodium ions can be promoted to be embedded into the lattice of the sodium ion battery anode material by using the doping agent, the content of free sodium is reduced, the discharge capacity, the cycle characteristic and the pole piece compaction density are obviously improved, and the sodium ion battery has a better application prospect.
Description
Technical Field
The invention relates to the technical field of new energy batteries, in particular to a layered oxide single crystal positive electrode material of a sodium ion battery and a preparation method thereof.
Background
Along with the rapid development of new energy automobiles, new energy batteries are also under continuous research and development innovation. From a classification, new energy batteries include lithium ion batteries, sodium ion batteries, lead acid batteries, hydrogen fuel cells, and the like. The lithium ion battery gradually becomes a main part of a modern new energy battery due to great advantages in battery capacity, service life, safety performance, charge and discharge speed, green environmental protection and the like, but other new energy batteries still have a certain market prospect.
Sodium ion batteries mainly rely on sodium ions to move between a positive electrode and a negative electrode to work, and are similar to the working principle of lithium ion batteries, but the sodium ion batteries have the advantages of excellent low-temperature performance, high safety, quick charge and low cost, so that the development of the sodium ion batteries is a favorable supplement and replacement for lithium iron phosphate lithium ion batteries and ternary lithium ion batteries. Due to the inherent advantages of the sodium ion battery, the sodium ion battery can be widely applied to the fields of electric tools, small energy storage, large energy storage, passenger cars and the like, and the cost of the sodium ion battery is continuously reduced in the future, so that the sodium ion battery is a necessary trend to replace lead-acid batteries used in the fields of two-wheeled vehicles, low-speed vehicles and the like.
At present, the sodium ion battery has the defects of low pole piece compaction density, low discharge capacity, high gas production and poor cycle performance, so that the market application of the sodium ion battery is slow, and one of the reasons is that most of layered oxides used for the sodium ion battery are polycrystalline secondary sphere anode materials or monocrystal-like (primary particles are agglomerates with more than 1 mu m) anode materials. Because the polycrystalline secondary spheres or the monocrystal-like cathode material have crystal boundaries, the crystal boundaries can crack in the pole piece rolling or repeated circulation process, and particles are broken and pulverized, so that side reactions of active substances and electrolyte are further aggravated, the interface of the cathode material is lost in electrochemical activity and gas production is increased, and finally the cycle life of the sodium ion battery is reduced. In addition, although the single crystal positive electrode material can improve sodium ionsPole piece compaction density, gas production and cycle performance of the battery, however, the layered oxide positive electrode material of the sodium ion battery is difficult to synthesize single crystal materials with dispersed particles due to larger interfacial energy, and especially the pole piece compaction density is 3.5g/cm 3 The synthesis method of the single crystal positive electrode material is not yet disclosed and reported at present. Therefore, the preparation of the layered oxide single crystal positive electrode material of the sodium ion battery is a critical technical problem.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a layered oxide single crystal positive electrode material of a sodium ion battery and a preparation method thereof, wherein a fluxing agent is added in the sintering process to reduce the interfacial energy potential of the particle surface, so that the single crystal positive electrode material with high compaction density is synthesized, and meanwhile, bulk doping and surface nano coating are carried out on the positive electrode material to inhibit the internal phase transition of the single crystal material and stabilize the electrochemical active interface of the single crystal material, so that the volume energy density, gas production and cycle life of the sodium ion battery can be improved.
According to the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment of the invention, the chemical formula is Na a Ni x Fe y Mn z M 1-x-y-z O 2 Wherein a is more than or equal to 0.50 and less than or equal to 1.20,0 and less than or equal to x and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and M= Ba, mg, ca, zn, B, al, zr, ti, sb, Y, cu, K, li, cs, W, mo, P, sn, ce, la, comprising the following steps:
s1: precursor Ni x Fe y Mn z M 1-x-y-z (OH) 2 Or Ni x Fe y Mn z M 1-x-y-z CO 3 Weighing the Na compound according to the proportion of metal molar weight of 1:0.5-1.2, adding one or more than two of fluxing agent Cs, W, B, mo, P, sn, ce, la and doping agent Ba, mg, ca, zn, al, zr, ti, sb, Y, cu, K, li, and uniformly mixing in a high-speed mixer;
s2: sintering the mixture at 850-1000 ℃ for 6-20h, crushing and screening, adding M compound into a coating machine for coating, then sintering for 3-10h at 400-800 ℃ for secondary heat preservation, crushing and screening, and finally obtaining the sodium ion battery layered oxide single crystal positive electrode material finished product.
Preferably, the sodium compound in the step S1 is one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.
Further, the fluxing agent added in the step S1 is one or more of cesium oxide, tungsten oxide, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, boron oxide, boric acid, molybdenum oxide, ammonium molybdate, phosphorus oxide, monoammonium phosphate, diammonium phosphate, tin oxide, cerium oxide and lanthanum oxide.
Preferably, the mass ratio of the total elements of the fluxing agent Cs, W, B, mo, P, sn, ce, la in the step S1 is 0.02-1%.
Further, the total element mass ratio of the doping agent Ba, mg, ca, zn, al, zr, ti, sb, Y, cu, K, li in the step S1 is 0.02-8%.
Further, the element of the coating agent M in the step S2 is one or more of B, al, zr, ti, ce, sn, sb, Y, cu, W, P, mo.
Preferably, in the step S2, the mass ratio of M total elements is 0.05-1%.
Further, the sintering atmosphere in the steps S1 and S2 is air, oxygen or a mixed gas with an oxygen concentration of 10% or more.
Preferably, d50=2.5-10 μm of the layered oxide single crystal positive electrode material of the sodium ion battery in the steps S1 and S2.
The invention also provides a layered oxide single crystal positive electrode material of the sodium ion battery, which is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
fluxing agents, also known as flux or molten salt methods, refer to substances capable of reducing the softening, melting or liquefying temperature of a crystalline material, and generally should have a liquid network structure and a small viscosity, which is conducive to heat and solute transfer; at the same time should have a low melting point and a boiling point as high as possible in order to have a broad temperature growth range, such as Bi 2 O、B 2 O 3 、LiOH·H 2 O and Na 2 CO 3 . The main principle of the fluxing agent is that the components of the crystal are dissolved in the liquid phase of the low-melting point fluxing agent at high temperature to form saturated melt, and supersaturated melt can be generated in the cooling process to separate out the crystal. The diffusion speed of substances in the molten salt liquid phase medium is higher than that of solid phase reaction, so that the fluxing agent serving as a reaction medium can reduce the reaction temperature and the reaction time for nucleation of crystals in the molten salt process. Meanwhile, the surface energy and interface energy of reactants and the flux can be reduced by adjusting the types, the addition amount, the reaction temperature and the reaction time of the flux, so that the size and the morphological characteristics of the crystal grain are changed. Since the reaction system of the flux method is a liquid phase, the infiltrated particles cannot be connected with each other, so that the synthesized crystal composition is uniform and has no segregation.
Therefore, a certain amount of fluxing agent is added in the solid phase synthesis of the positive electrode material of the sodium ion battery, so that the formation of the morphology of the single crystal of the positive electrode material particle of the sodium ion battery is facilitated. In the preparation process of the positive electrode material, the primary particles of the positive electrode can be dissolved in the liquid-phase fluxing agent by controlling the dosage and the variety of the fluxing agent, the single crystal reaction temperature and the reaction time, and the elements of the positive electrode material can be uniformly distributed in the fluxing agent phase, so that the positive electrode material of the sodium ion battery with high-strength single crystal appearance is finally formed by cooling. The surface of the positive electrode material particles of the sodium ion battery can generate interface side reaction with electrolyte in the charge-discharge cycle process to generate CO 2 、CO、H 2 、CH 4 Waiting for gas; meanwhile, in the high-voltage charging process of more than 4.0V, the iron element in the metal layer in the particle is migrated to the sodium metal layer, so that O3-P3 phase transformation and lattice oxygen release are generated. The phase transition causes the volume expansion of particles to generate cracks and lattice collapse, thereby causing the migration resistance of sodium ions to increase, resulting in the decrease of charge-discharge capacity. And oxygen release enables the electrolyte to be oxidized to produce a gas. Therefore, a doping technology is generally used for inhibiting migration of iron element and inhibiting phase transformation, so that the aim of improving circulation is fulfilled, and meanwhile, a surface coating technology is adopted for reducing interface side reaction to reduce gas production of the sodium ion battery. Sodium ion battery single crystal mentioned in the present inventionIn the synthesis of the positive electrode material, the doping agent and the coating agent are added, so that the problems of high gas production, low pole piece compaction density and poor cycle performance of the sodium ion battery can be effectively solved, and the sodium ion battery has better application prospect.
Drawings
FIG. 1 is an SEM image of a layered oxide single crystal positive electrode material of a sodium ion battery of example 1; wherein fig. 1 (a) is a partially enlarged view of fig. 1 (b), and fig. 1 (b) is a partially enlarged view of fig. 1 (c);
FIG. 2 is an SEM image of a layered oxide polycrystalline cathode material of a sodium ion battery of comparative example 1; wherein fig. 2 (a) is a partially enlarged view of fig. 2 (b), and fig. 2 (b) is a partially enlarged view of fig. 2 (c);
FIG. 3 is a graph showing the comparison of the compacted densities of the positive electrode sheet materials of layered oxides of sodium ion batteries in example 1 and comparative example 1;
fig. 4 is a graph of capacity of layered oxide cathode materials of sodium ion batteries of example 1 and comparative example 1;
fig. 5 is a graph of cycling of layered oxide cathode materials for sodium ion batteries of example 1 and comparative example 1.
Detailed Description
The technical scheme in the patent of the invention is further described below with reference to the accompanying drawings and examples.
Example 1:
the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment comprises the following steps:
(1) According to formula Na 0.5-1.10 Ni 0.25 Fe 0.35 Mn 0.40 5 μm precursor Ni 0.25 Fe 0.35 Mn 0.40 (OH) 2 With Na and Na 2 CO 3 Weighing according to the molar ratio of total metal atoms to sodium atoms of 1:0.8, and simultaneously adding Cs with the mass ratio of 0.02 percent of Cs 2 O fluxing agent and 8% of ZnO doping agent in mass ratio of Zn are mixed uniformly in a high-speed mixer.
(2) Sintering the mixture in 900 deg.c air atmosphere for 10 hr, crushing, sieving and coating with 0.3 wt% H 28 N 6 O 41 W 12 And 0.1% Ti of TiO 2 Then sintering and preserving heat for 5 hours at 550 ℃, and finally obtaining the finished product of the layered oxide single crystal positive electrode material of the 5 mu m sodium ion battery after crushing and screening.
Example 2:
the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment comprises the following steps:
(1) According to formula Na 0.5-1.10 Ni 0.40 Fe 0.20 Mn 0.40 2.5 μm precursor Ni 0.40 Fe 0.20 Mn 0.40 CO 3 With NaHCO 3 Weighing according to the molar ratio of total metal atoms to sodium atoms of 1:1.2, and simultaneously adding Cs in a mass ratio of 1% Cs 2 O fluxing agent and ZnO doping agent with the mass ratio of 0.02 percent of Zn are mixed uniformly in a high-speed mixer.
(2) Sintering and preserving the temperature of the mixture for 20 hours in an oxygen atmosphere at 850 ℃, crushing, screening, and coating H with the mass ratio of 0.3% W in a coating machine 28 N 6 O 41 W 12 And 0.1% Ti by mass of TiO 2 Then sintering and preserving heat for 3 hours at 800 ℃, and finally obtaining the finished product of the layered oxide single crystal positive electrode material of the sodium ion battery with the thickness of 2.5 mu m after crushing and screening.
Example 3:
the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment comprises the following steps:
(1) According to formula Na 0.5-1.10 Ni 0.33 Fe 0.33 Mn 0.34 7 μm precursor Ni 0.33 Fe 0.33 Mn 0.34 (OH) 2 With Na and Na 2 CO 3 The mixture is weighed according to the molar ratio of total metal atoms to sodium atoms of 1:0.5, and CeO and WO with the mass ratio of 0.5 percent (Ce+W+B+Mo) are added simultaneously 3 、B 2 O 3 And MoO 3 Four fluxing agents and 4% (Sb+Y+Cu+K+Li) mass ratio of Sb 2 O 3 、Y 2 O 3 CuO, KOH and LiOH.H 2 The O five dopants are then mixed uniformly in a high-speed mixer.
(2) Oxygen at 1000deg.CSintering and preserving heat for 6h in a mixed atmosphere with the content of 10 percent, crushing and screening, and coating Al with the mass ratio of 1 percent (Al+Zr+Ti+Ce) in a coating machine 2 O 3 、Zr 2 O 3 、TiO 2 And CeO 2 The four coating agents are sintered for the second time at 400 ℃ and kept for 10 hours, and after crushing and screening, the 7 mu m sodium ion battery layered oxide single crystal positive electrode material finished product is finally prepared.
Example 4:
the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment comprises the following steps:
(1) According to formula Na 0.5-1.10 Ni 0.25 Fe 0.35 Mn 0.40 10 mu m of precursor Ni 0.25 Fe 0.35 Mn 0.40 (OH) 2 Weighing NaOH according to the molar ratio of total metal atoms to sodium atoms of 1:1, and simultaneously adding 0.5% (P+Sn+Ce+La) of NH by mass 4 H 2 PO 4 、SnO 2 、CeO 2 And La (La) 2 O 3 Four fluxing agents and 5% (Al+Zr+Ti+Sb) of Al by mass ratio 2 O 3 、ZrO 2 、TiO 2 And SnO 2 The five dopants are then mixed uniformly in a high-speed mixer.
(2) Sintering and preserving the temperature of the mixture for 10 hours in a mixed atmosphere with the oxygen content of 50% at 960 ℃, crushing, screening, and coating SnO with the mass ratio of 0.5 percent (Sn+Sb+Y+Cu) in a coating machine 2 、SnO 2 、Y 2 O 3 And four coating agents of CuO, then sintering and preserving heat for 5 hours at 600 ℃, and finally obtaining the finished product of the layered oxide single crystal positive electrode material of the 10 mu m sodium ion battery after crushing and screening.
Example 5:
the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment comprises the following steps:
(1) According to formula Na 0.5-1.10 Ni 0.33 Fe 0.33 Mn 0.34 4 mu m precursor Ni 0.33 Fe 0.33 Mn 0.34 CO 3 With NaHCO 3 According to the total metal atoms and sodium atoms of 1:0.9Is added with a molar ratio of 0.08% (Mo+P+Sn) by mass ratio of (NH) 4 ) 2 MoO 4 、(NH 4 ) 2 HPO 4 And SnO 2 Three fluxing agents, four BaO, mgO, caO doping agents with the mass ratio of 1 percent (Ba+Mg+Ca+Zn) and four doping agents with ZnO are mixed uniformly in a high-speed mixer.
(2) Sintering and preserving the temperature of the mixture for 15 hours at 880 ℃ in an air atmosphere, crushing, screening, and coating H with the mass ratio of 0.3 percent (W+P+Mo) in a coating machine 28 N 6 O 41 W 12 、NH 4 H 2 PO 4 And (NH) 4 ) 2 MoO 4 The three coating agents are sintered for the second time at 500 ℃ and kept for 10 hours, and after crushing and screening, the finished product of the layered oxide single crystal positive electrode material of the 4 mu m sodium ion battery is finally prepared.
Example 6:
the preparation method of the layered oxide single crystal positive electrode material of the sodium ion battery in the embodiment comprises the following steps:
(1) According to formula Na 0.5-1.10 Ni 0.33 Fe 0.33 Mn 0.34 7 μm precursor Ni 0.33 Fe 0.33 Mn 0.34 (OH) 2 With Na and Na 2 CO 3 The molar ratio of total metal atoms to sodium atoms is 1:0.6, and simultaneously 0.5 percent (P+Sn+Ce+La) of NH is added 4 HPO 4 、SnO 2 、CeO 2 And La (La) 2 O 3 Four fluxing agents and 0.5 percent (Al+Zr+Ti+Sb) of Al by mass ratio 2 O 3 、ZrO 2 、TiO 2 And Sb (Sb) 2 O 3 The four dopants are then mixed uniformly in a high-speed mixer.
(2) Sintering and preserving the temperature of the mixture for 16 hours in a mixed atmosphere with the oxygen content of 50% at 960 ℃, crushing, screening, and cladding H with the mass ratio of 0.05% B in a cladding machine 3 BO 3 And (3) the coating agent is sintered for the second time at 300 ℃ and is preserved for 5 hours, and after crushing and screening, the 7 mu m sodium ion battery layered oxide single crystal positive electrode material finished product is finally prepared.
Comparative example 1:
this comparative example uses the same sodium ion positive electrode material precursor Ni as in example 1 0.25 Fe 0.35 Mn 0.40 (OH) 2 The remainder was the same as in example 1, except that no flux and no dopant were added during the synthesis of the positive electrode material.
Comparative example 2:
this comparative example uses the same sodalime precursor Ni as in example 1 0.25 Fe 0.35 Mn 0.40 (OH) 2 The other portions were the same as in example 1 except that no dopant was added during the synthesis of the positive electrode material.
In the examples of the present invention, the sodium ion layered oxide single crystal positive electrode material products obtained in the above examples and comparative examples were subjected to performance test by the following methods:
the free sodium or residual alkali is used by an automatic potentiometric titrator, model: METTLETOLIDOG 20, weighing 5g of sample solvent in 40mL of water solution, performing ultrasonic treatment for 2min, filtering, shaking up in a volumetric flask with volume of 100mL, standing, and collecting clear liquid for testing.
The electrochemical cycle performance was tested using the following method: mixing the sodium-electricity anode material, conductive carbon black and a binder PVDF according to the mass ratio of 80:10:10, adding NMP to prepare uniform slurry, coating the slurry on an aluminum foil, drying, rolling and pressing, and cutting into round pole pieces with the diameter of 14 mm. Assembled into a sodium ion battery by using a CR2032 button battery, wherein a diaphragm is made of glass fiber, and an electrolyte is NaPF with a solvent of 1mol/L of EC/PC/DEC 6 The solution, the negative plate is sodium plate.
The sodium ion battery test conditions were: the temperature is 25+/-1 ℃, the voltage range of charge-discharge cycle is 3.0V-4.0V, the current is 0.1C (150 mAh/g), and the cycle test is carried out according to 0.5C charge-1℃ discharge.
The test results are shown in table 1:
as can be seen from Table 1, the sodium-electricity positive materials prepared in examples 1 to 6 are excellent in discharge capacity, cycle, free sodium and compacted density of the pole pieceFor example, the 50-week cycle retention rate is 93% or more, and the positive electrode sheet compacted density is 3.40g/cm 3 The above.
The samples obtained in example 1 and comparative example 1 were also observed for surface morphology and particle size by using a Hitachi SU5000 scanning electron microscope, respectively. FIG. 1 shows that the sodium electric positive material in the embodiment 1 has a flaky single crystal morphology, and single crystal particles are relatively dispersed and have a relatively smooth surface. Because CeO is used in the synthesis process of the sodium-electricity positive material 2 The addition of the flux (melting point 490 c) results in a decrease in the surface energy and interfacial energy of the precursor particles, so that the primary particles readily dissolve in each other during high temperature sintering to eventually form single crystal particles. Thus, the free sodium in example 1 is lower and the discharge capacity and cycle are higher. FIG. 2 shows the morphology of the sample of comparative example 1, in which the free sodium is higher (5.247%) and the pole piece compaction density is low (3.10 g/cm) because no flux is added during the synthesis of the positive material of the sodium ion battery to form secondary spherical polycrystalline particles 3 ) The method comprises the steps of carrying out a first treatment on the surface of the On the other hand, the failure to add the dopant does not inhibit the phase transition caused by migration of the iron element to the sodium metal layer, resulting in lower capacity and poorer circulation. Comparative example 2 although the addition of the flux formed a single crystal morphology, the compacted density of the sodium electric positive electrode sheet was increased (3.40 g/cm) 3 ) And the free sodium content was reduced (1.362%), but the improvement in discharge capacity and cycle was not significant due to the non-addition of the dopant.
FIG. 3 is a comparison of the compacted densities of the positive electrode material of sodium ion battery of example 1 and comparative example 1, it is apparent that the compacted density of single crystals (3.55 g/cm 3 ) Higher than the compaction density of the polycrystal (3.10 g/cm) 3 ）。
In addition, the samples of example 1 and comparative example 1 were subjected to discharge capacity and cycle performance comparison tests, respectively, and the data were made into fig. 4 and 5. As can be seen from fig. 4 and 5, na in example 1 0.7-1.10 Ni 0.25 Fe 0.35 Mn 0.40 The first discharge capacity of the catalyst is 139mAh/g, and the cycle retention rate of 50 weeks is 94%; the first capacity in comparative example 1 is only 131mAh/g, and the 50-week cycle retention rate is 88%, further illustrating the positive electrode of the sodium ion battery with single crystal morphologyThe cycling performance is better, and the doping agent can promote more sodium ions to enter the sodium-electricity positive material crystal, so the discharge capacity is higher and the free sodium content on the particle surface is less.
Claims (8)
1. Preparation method of layered oxide single crystal positive electrode material of sodium ion battery, and chemical formula of the material is Na a Ni x Fe y Mn z M 1-x-y- z O 2 Wherein a is more than or equal to 0.50 and less than or equal to 1.20,0 and less than or equal to x and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and M= Ba, mg, ca, zn, B, al, zr, ti, sb, Y, cu, K, li, cs, W, mo, P, sn, ce, and is characterized by comprising the following steps:
s1: precursor Ni x Fe y Mn z M 1-x-y-z (OH) 2 Or Ni x Fe y Mn z M 1-x-y-z CO 3 And Na in the molar ratio of 1:0.5-1.2, and adding fluxing agent and doping agent, wherein the cosolvent comprises one or more of Cs, W, B, mo, P, sn, ce, la compounds, the doping agent comprises one or more of Ba, mg, ca, zn, B, al, zr, ti, sb, Y, cu, K, li compounds, and then mixing uniformly in a high-speed mixer;
s2: sintering the mixture at 850-1000 ℃ for 6-20h, crushing and screening, adding M compound into a coating machine for coating, then sintering for 3-10h at 400-800 ℃ for secondary heat preservation, crushing and screening, and finally obtaining the sodium ion battery layered oxide single crystal positive electrode material finished product.
2. The method for preparing the layered oxide single crystal positive electrode material of the sodium ion battery as claimed in claim 1, wherein the method comprises the following steps: the sodium compound in the step S1 is one or more of sodium carbonate, sodium bicarbonate and sodium hydroxide.
3. The method for preparing the layered oxide single crystal positive electrode material of the sodium ion battery as claimed in claim 1, wherein the method comprises the following steps: the fluxing agent in the step S1 comprises one or more of cesium oxide, tungsten oxide, ammonium tungstate, ammonium metatungstate and ammonium paratungstate, one or two of boron oxide and boric acid, one or more of molybdenum oxide and ammonium molybdate, one or more of phosphorus oxide, monoammonium phosphate and diammonium phosphate, and one or more of tin oxide, cerium oxide and lanthanum oxide; the mass ratio of Cs, W, B, mo, P, sn, ce, la elements in the fluxing agent is 0.02-1%.
4. The method for preparing the layered oxide single crystal positive electrode material of the sodium ion battery as claimed in claim 1, wherein the method comprises the following steps: the dopant in the step S1 has one or more of Ba, mg, ca, zn, al, zr, ti, cu, K, li elements, and the total mass ratio of Ba, mg, ca, zn, al, zr, ti, cu, K, li elements in the dopant is 0.02-8%.
5. The method for preparing the layered oxide single crystal positive electrode material of the sodium ion battery as claimed in claim 1, wherein the method comprises the following steps: the element of the coating agent M in the step S2 is one or more of B, al, zr, ti, ce, sn, sb, Y, cu, W, P, mo, and the mass ratio of the total element M is 0.05-1%.
6. The method for preparing the layered oxide single crystal positive electrode material of the sodium ion battery as claimed in claim 1, wherein the method comprises the following steps: the sintering atmosphere in the steps S1 and S2 is air, oxygen or mixed gas with the oxygen concentration of more than 10%.
7. The method for preparing the layered oxide single crystal positive electrode material of the sodium ion battery as claimed in claim 1, wherein the method comprises the following steps: d50=2.5-10 μm of the layered oxide single crystal positive electrode material of the sodium ion battery in the steps S1 and S2.
8. A layered oxide single crystal positive electrode material of a sodium ion battery is characterized in that: a method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311775208.6A CN117457888A (en) | 2023-12-22 | 2023-12-22 | Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311775208.6A CN117457888A (en) | 2023-12-22 | 2023-12-22 | Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117457888A true CN117457888A (en) | 2024-01-26 |
Family
ID=89591482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311775208.6A Withdrawn CN117457888A (en) | 2023-12-22 | 2023-12-22 | Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117457888A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118398796A (en) * | 2024-05-23 | 2024-07-26 | 成都碳合利科技有限公司 | Sodium ion battery layered oxide positive electrode material with low residual alkali content and preparation method thereof |
| CN118658997A (en) * | 2024-08-20 | 2024-09-17 | 天津国安盟固利新材料科技股份有限公司 | Sodium ion battery layered oxide positive electrode material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
| CN108878859A (en) * | 2018-06-07 | 2018-11-23 | 中航锂电（洛阳）有限公司 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof, lithium ion battery |
| CN111354926A (en) * | 2018-12-22 | 2020-06-30 | 中天新兴材料有限公司 | Nickel cobalt lithium manganate composite material and preparation method thereof |
| CN114645314A (en) * | 2022-03-09 | 2022-06-21 | 中南大学 | Preparation method of single crystal morphology ternary cathode material |
| CN114940519A (en) * | 2022-06-20 | 2022-08-26 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material |
| CN115275134A (en) * | 2022-07-18 | 2022-11-01 | 贵州振华新材料有限公司 | Single crystal sodium ion battery anode material and preparation method and application thereof |
| CN115763799A (en) * | 2022-10-18 | 2023-03-07 | 桂林理工大学 | Method for improving electrochemical performance of single crystal type high-nickel ternary positive electrode material through fluoride coating modification |
| CN115881920A (en) * | 2022-12-14 | 2023-03-31 | 中国科学技术大学 | Multi-strategy modified cobalt-doped cladding type monocrystal layered oxide sodium ion battery positive electrode material |
| CN116979059A (en) * | 2023-08-08 | 2023-10-31 | 溧阳中科海钠科技有限责任公司 | Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment |
| CN117133893A (en) * | 2023-08-25 | 2023-11-28 | 美钠(无锡)能源科技有限公司 | Sodium-electricity positive electrode material and synthesis method thereof |
-
2023
- 2023-12-22 CN CN202311775208.6A patent/CN117457888A/en not_active Withdrawn
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159251A (en) * | 2015-03-31 | 2016-11-23 | 河南科隆新能源有限公司 | One kind monocrystalline lithium battery tertiary cathode material and preparation method thereof |
| CN108878859A (en) * | 2018-06-07 | 2018-11-23 | 中航锂电（洛阳）有限公司 | A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof, lithium ion battery |
| CN111354926A (en) * | 2018-12-22 | 2020-06-30 | 中天新兴材料有限公司 | Nickel cobalt lithium manganate composite material and preparation method thereof |
| CN114645314A (en) * | 2022-03-09 | 2022-06-21 | 中南大学 | Preparation method of single crystal morphology ternary cathode material |
| CN114940519A (en) * | 2022-06-20 | 2022-08-26 | 泾河新城陕煤技术研究院新能源材料有限公司 | Preparation method of high-nickel monocrystal nickel cobalt lithium manganate ternary cathode material |
| CN115275134A (en) * | 2022-07-18 | 2022-11-01 | 贵州振华新材料有限公司 | Single crystal sodium ion battery anode material and preparation method and application thereof |
| CN115763799A (en) * | 2022-10-18 | 2023-03-07 | 桂林理工大学 | Method for improving electrochemical performance of single crystal type high-nickel ternary positive electrode material through fluoride coating modification |
| CN115881920A (en) * | 2022-12-14 | 2023-03-31 | 中国科学技术大学 | Multi-strategy modified cobalt-doped cladding type monocrystal layered oxide sodium ion battery positive electrode material |
| CN116979059A (en) * | 2023-08-08 | 2023-10-31 | 溧阳中科海钠科技有限责任公司 | Sodium ion battery positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment |
| CN117133893A (en) * | 2023-08-25 | 2023-11-28 | 美钠(无锡)能源科技有限公司 | Sodium-electricity positive electrode material and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄华文 等: "层状氧化物正极材料晶体结构与储钠性能探究", 《广东化工》, vol. 50, no. 21, 30 November 2023 (2023-11-30), pages 1 - 4 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118398796A (en) * | 2024-05-23 | 2024-07-26 | 成都碳合利科技有限公司 | Sodium ion battery layered oxide positive electrode material with low residual alkali content and preparation method thereof |
| CN118658997A (en) * | 2024-08-20 | 2024-09-17 | 天津国安盟固利新材料科技股份有限公司 | Sodium ion battery layered oxide positive electrode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117457888A (en) | Sodium ion battery layered oxide single crystal positive electrode material and preparation method thereof | |
| JP2023534756A (en) | Lithium ion battery positive electrode lithium replenishment additive and its preparation method and lithium ion battery | |
| CN110233253A (en) | A kind of binary doped monocrystalline tertiary cathode material and preparation method thereof | |
| CN110600697B (en) | Sulfur positive electrode material with core-shell structure, preparation method of sulfur positive electrode material, lithium-sulfur battery positive electrode piece and lithium-sulfur battery | |
| KR20220155344A (en) | Silicon oxide composite negative electrode material and manufacturing method thereof, lithium ion battery | |
| CN110649230B (en) | Nanometer rivet core-shell structure anode material and preparation method thereof | |
| EP4343894A1 (en) | Lithium battery positive electrode material precursor, preparation method therefor and application thereof | |
| CN115939336A (en) | Positive electrode material of sodium ion battery, positive plate and secondary battery | |
| CN116504954B (en) | Positive electrode material, preparation method thereof and sodium ion battery | |
| CN114094078B (en) | Nitrogen-doped carbon-coated metal sulfide heterojunction material, preparation method and battery application | |
| CN116986649A (en) | Low-residual-alkali sodium-electricity positive electrode material, preparation method thereof and sodium-ion battery | |
| CN115395007A (en) | Layered-spinel composite phase monocrystal lithium-rich manganese-based positive electrode material and application thereof | |
| CN115571927A (en) | Composite in-situ coated high-nickel single crystal positive electrode material and preparation method thereof | |
| CN117913264A (en) | O3/P2 double-phase composite sodium ion positive electrode material and preparation method and application thereof | |
| CN116344775A (en) | Positive electrode material of sodium ion battery and sodium ion battery | |
| CN116031380A (en) | Polycrystalline sodium ion-like positive electrode material, and preparation method and application thereof | |
| CN117383627B (en) | Preparation method of sodium-electricity layered anode material | |
| CN114645314A (en) | Preparation method of single crystal morphology ternary cathode material | |
| CN113666424A (en) | Precursor of sodium ion battery anode material and preparation method thereof | |
| CN116495800A (en) | Method for reducing residual alkali content on surface of layered positive electrode material of sodium ion battery, positive electrode material of sodium ion battery and sodium ion battery | |
| CN114388779B (en) | Composite ternary positive electrode material, preparation method thereof and lithium ion battery | |
| CN116093298A (en) | Lithium cobalt oxide positive electrode material, preparation method thereof, lithium ion battery and application | |
| CN116053458A (en) | Doped NCM ternary positive electrode material, preparation method thereof, positive electrode and lithium ion battery | |
| CN115520911A (en) | Lithium-nickel composite oxide positive electrode material and preparation method thereof | |
| CN115663176A (en) | Lithium iron phosphate cathode material, preparation method and application thereof |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20240126 |