CN117594778A - Sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN117594778A CN117594778A CN202410075143.2A CN202410075143A CN117594778A CN 117594778 A CN117594778 A CN 117594778A CN 202410075143 A CN202410075143 A CN 202410075143A CN 117594778 A CN117594778 A CN 117594778A
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- Prior art keywords
- sodium ion
- positive electrode
- ion battery
- phosphate
- borate
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 94
- 239000007774 positive electrode material Substances 0.000 title claims description 38
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract description 30
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 19
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 17
- 229910021538 borax Inorganic materials 0.000 claims description 16
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 12
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 6
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 6
- 235000011010 calcium phosphates Nutrition 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- LOCZQLKNTOXJDV-UHFFFAOYSA-N magnesium;oxido(oxo)borane Chemical compound [Mg+2].[O-]B=O.[O-]B=O LOCZQLKNTOXJDV-UHFFFAOYSA-N 0.000 claims description 6
- RHJYKEDKMHDZBL-UHFFFAOYSA-L metaphosphoric acid (hpo3), magnesium salt Chemical compound [Mg+2].[O-]P(=O)=O.[O-]P(=O)=O RHJYKEDKMHDZBL-UHFFFAOYSA-L 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910001467 sodium calcium phosphate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 6
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
- 239000010405 anode material Substances 0.000 abstract description 17
- 239000003513 alkali Substances 0.000 abstract description 16
- 238000007086 side reaction Methods 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 21
- 229910016569 AlF 3 Inorganic materials 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000010416 ion conductor Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- H—ELECTRICITY
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Chemical & Material Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery anode material and a preparation method and application thereof. The sodium ion battery anode material comprises a sodium ion layered oxide and a coating layer coated on the surface of the sodium ion layered oxide; the coating comprises a co-sintered product of aluminum fluoride and a compound X comprising at least one of an oxide, a phosphate, boric acid, or a borate; is prepared by mixing sodium ion layered oxide with aluminum fluoride and compound X, grinding and sintering. According to the invention, the coating layer is arranged on the outer surface of the sodium ion layered oxide, the sodium ion layered oxide is isolated from air, the side reaction of the sodium ion battery anode material in the air is reduced, the side reaction of HF in the electrolyte can be effectively reduced by the coating layer material, the ion transmission of the surface of the anode material is effectively enhanced, and the residual alkali on the surface is relieved, so that the electrochemical performance of the sodium ion battery anode material is improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery anode material and a preparation method and application thereof.
Background
The layered compound sodium ion battery anode material has the advantages of higher theoretical capacity, small internal resistance, large voltage interval, high charge and discharge efficiency, good cycle performance, lower cost, simple maintenance, environmental friendliness and the like, is widely popularized and applied in the field of sodium ion battery manufacturing, but the layered compound sodium ion battery anode still has the problem of poor cycle stability, and is easy to react with electrolyte to cause the reduction of the cycle stability.
Chinese patent application No. CN202110089509.8 discloses a method for reducing the concentration of surface residual alkali and forming sodium salt with high ionic conductivity by sufficiently reacting boric acid solution, phosphoric acid solution or metaaluminate solution with the surface residual alkali of the positive electrode material. However, the method involves a wet process, and a series of problems such as waste liquid treatment and the like are unavoidable, which is not beneficial to large-scale production.
The chinese patent application publication No. CN112456567a discloses a method for coating a layered anode with an oxide by using a wet method, and as a result, a better coating effect is obtained, but the problems of wet coating are also brought.
The problem of surface residual alkali can be removed to a certain extent by the traditional coating of oxide, phosphate and borate, the interface stability of the anode is improved, and the surface lattice oxygen escape phenomenon still exists.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a sodium ion battery positive electrode material, wherein a coating layer is arranged on the outer surface of a sodium ion layered oxide, so that the sodium ion layered oxide is isolated from air, the side reaction of the sodium ion battery positive electrode material in the air is reduced, the side reaction of HF in an electrolyte can be effectively reduced by the coating layer material, the ion transmission of the surface of the positive electrode material is effectively enhanced, and the residual alkali on the surface is relieved, so that the electrochemical performance of the sodium ion battery positive electrode material is improved.
The second aim of the invention is to provide a preparation method of the positive electrode material of the sodium ion battery, which is solid-phase coating, and has the characteristics of simple synthesis process, high production efficiency and the like, and the prepared positive electrode material has better uniformity.
A third object of the present invention is to provide a positive electrode sheet comprising the sodium ion battery positive electrode material as described above.
A fourth object of the present invention is to provide a sodium ion battery comprising the positive electrode sheet as described above.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
a positive electrode material of a sodium ion battery comprises a sodium ion layered oxide and a coating layer coated on the surface of the sodium ion layered oxide;
the coating comprises a co-sintered product of aluminum fluoride and a compound X comprising at least one of an oxide, phosphate, boric acid, or borate.
Preferably, the oxide comprises B 2 O 3 、TiO 2 、MgO、SnO 2 Or Al 2 O 3 At least one of them.
Preferably, the phosphate comprises at least one of diammonium phosphate, monoammonium phosphate, magnesium metaphosphate, aluminum phosphate, sodium phosphate, or calcium phosphate.
Preferably, the borate comprises at least one of sodium borate, magnesium metaborate, aluminum borate, calcium borate or zinc borate.
Preferably, the sodium ion layered oxide has a chemical formula of Na x MO 2 Of which 0.67<x is less than or equal to 1, and M comprises at least one of Ni, mn, fe, cu, ti, sn, mg, al, zr, zn or Co.
The preparation method of the sodium ion battery anode material comprises the following steps:
mixing sodium ion layered oxide with aluminum fluoride and a compound X, and grinding and sintering;
wherein the compound X comprises at least one of an oxide, a phosphate, boric acid or a borate.
Preferably, the oxide comprises B 2 O 3 、TiO 2 、MgO、SnO 2 Or Al 2 O 3 At least one of them.
Preferably, the phosphate comprises at least one of diammonium phosphate, monoammonium phosphate, magnesium metaphosphate, aluminum phosphate, sodium phosphate, or calcium phosphate.
Preferably, the borate comprises at least one of sodium borate, magnesium metaborate, aluminum borate, calcium borate or zinc borate.
Preferably, the sodium ion layered oxide has a chemical formula of Na x MO 2 Of which 0.67<x is less than or equal to 1, and M comprises at least one of Ni, mn, fe, cu, ti, sn, mg, al, zr, zn or Co.
Preferably, the mass percentage of the aluminum fluoride to the sodium ion layered oxide is 0.25-3 wt%.
Preferably, the mass percentage of the compound X in the sodium ion layered oxide is 0.25-3 wt%.
Preferably, the particle size of the sodium ion layered oxide before grinding is 1-20 μm.
Preferably, the particle size of the aluminum fluoride before grinding is 50 nm-3 μm.
Preferably, the particle size of the compound X before grinding is 50 nm-3 μm.
Preferably, the grinding is ball milling, the rotating speed of the ball milling is 150-450 rpm, and the time of the ball milling is 1-5 h.
Preferably, the sintering temperature is 180-800 ℃, and the sintering time is 4-10 hours.
A positive electrode sheet comprising a sodium ion battery positive electrode material as described above.
A sodium ion battery comprising a positive electrode sheet as described above.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the sodium ion battery anode material provided by the invention, the coating layer is arranged on the outer surface of the sodium ion layered oxide, so that the sodium ion layered oxide can be isolated from air, and the side reaction of the sodium ion battery anode material in the air is reduced; the coating comprises a co-sintered product of aluminum fluoride and a compound X, wherein the compound X comprises at least one of an oxide, phosphate, boric acid, or borate, alF 3 The addition of the catalyst can effectively reduce the side reaction of HF in the electrolyte, reduce the surface oxygen activity and inhibit the dissolution of transition metal; the ion conductor formed by the compound X can effectively enhance the ion transmission of the surface of the material and relieve the residual alkali on the surface, so that the electrochemical performance of the sodium ion positive electrode material is improved, and the sodium ion battery positive electrode material provided by the invention has good cycle stability.
(2) The method is solid-phase coating, has the characteristics of simple synthesis process, high production efficiency and the like, and provides a positive electrode material with better uniformity; the invention has the advantages of easily available raw materials, no toxicity, low cost, compatibility with the existing production equipment and suitability for large-scale production.
(3) The fluoride and ion conductor layer is formed on the surface of the prepared material, and the film forming uniformity and compactness of CEI can be effectively improved, so that dissolution of transition metal, decomposition of electrolyte, gas production and the like are inhibited.
(4) The aluminum fluoride and the surface residual alkali adopted by the invention have eutectic phenomena, on one hand, conditions are provided for uniform coating of the coating layer, on the other hand, the residual alkali can be effectively consumed through the reaction of the compound X and the residual alkali, so that the residual alkali is converted into the ion conductor material, the characteristic of poor electric conduction/ion conduction of the aluminum fluoride is overcome, and the resistance of the material is effectively reduced.
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 XRD result pattern of the positive electrode active material provided in example 1 of the present application;
fig. 2 is a graph of specific capacity test results of a battery provided in example 1 of the present application, containing the positive electrode active material of the present application;
fig. 3 is a graph showing the results of the cycle performance test of the battery containing the positive electrode active material according to example 1 of the present application.
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.
The first aspect of the invention provides a sodium ion battery anode material, which comprises a sodium ion layered oxide and a coating layer coated on the surface of the sodium ion layered oxide;
the coating comprises a co-sintered product of aluminum fluoride comprising anhydrous aluminum fluoride and/or a hydrate of aluminum fluoride and a compound X comprising at least one of an oxide, phosphate, boric acid, or borate.
According to the sodium ion battery anode material provided by the invention, the coating layer formed by the co-sintered product of aluminum fluoride and the compound X is arranged on the outer surface of the sodium ion layered oxide, so that the sodium ion layered oxide can be isolated from air, and the side reaction of the sodium ion anode material in the air can be reduced; alF (AlF) 3 The addition of the compound can effectively reduce the side reaction of HF in the electrolyte, reduce the surface oxygen activity, inhibit the dissolution of transition metal, the compound X comprises at least one of oxide, phosphate, boric acid or borate, and the ion conductor formed by the compound X can effectively enhance the ion transmission of the surface of the material and relieve the residual alkali on the surface, so that the electrochemical performance of the positive electrode material of the sodium ion battery is improved, and the positive electrode material of the sodium ion battery provided by the invention has good cycle stability.
In some embodiments of the invention, the oxide comprises B 2 O 3 、TiO 2 、MgO、SnO 2 Or Al 2 O 3 At least one of them.
In some embodiments of the invention, the phosphate salt comprises at least one of diammonium phosphate, monoammonium phosphate, magnesium metaphosphate, aluminum phosphate, sodium phosphate, or calcium phosphate.
In some embodiments of the invention, the borate comprises at least one of sodium borate, magnesium metaborate, aluminum borate, calcium borate, or zinc borate, the sodium borate comprising anhydrous sodium borate and/or a hydrate of sodium borate, such as sodium tetraborate or borax.
In some embodiments of the invention, the sodium ion layered oxideHas a chemical general formula of Na x MO 2 Of which 0.67<x is less than or equal to 1, and M comprises at least one of Ni, mn, fe, cu, ti, sn, mg, al, zr, zn or Co.
The second aspect of the invention provides a preparation method of the sodium ion battery anode material, which comprises the following steps:
mixing sodium ion layered oxide with aluminum fluoride and a compound X, and grinding and sintering;
the compound X comprises at least one of oxide, phosphate, boric acid or borate, wherein the aluminum fluoride is anhydrous aluminum fluoride and/or hydrate of aluminum fluoride.
According to the invention, aluminum fluoride and a compound X are adopted to carry out co-cladding on the sodium ion layered oxide, so that an ion conductor can be constructed on the surface of the positive electrode material, and the problem of residual alkali on the surface can be relieved in the mode; the method has the advantages that the surface is modified by introducing aluminum fluoride, on one hand, the extremely strong electronegativity of fluorine ions is utilized, the surface oxygen activity is reduced, the dissolution of transition metal is inhibited, on the other hand, aluminum fluoride is prevented from being corroded by hydrogen fluoride, on the basis of eutectic phenomenon of aluminum fluoride and surface residual alkali, on the other hand, conditions are provided for uniform coating of a coating layer, on the other hand, the residual alkali can be effectively consumed through the reaction of the compound X and the residual alkali, so that the residual alkali is converted into an ion conductor material, the ion transmission of the surface of the material can be effectively enhanced, the poor electric conduction/ion conduction characteristics of the aluminum fluoride are overcome, the material resistance is effectively reduced, and the electrochemical performance of the positive electrode material of the sodium ion battery is improved.
The sodium ion layered oxide, aluminum fluoride and a compound X are mixed and sintered, a film is formed on the surface of the sodium ion layered oxide in the sintering process, and the film can isolate the sodium ion layered oxide from air, so that side reaction of the sodium ion anode material in the air is reduced; the fluoride and ion conductor layer is formed on the surface of the prepared material, so that the film forming uniformity and compactness of CEI can be effectively improved, and the dissolution of transition metal, the decomposition of electrolyte, gas production and the like are inhibited.
The method is solid-phase coating, has the characteristics of simple synthesis process, high production efficiency and the like, and the prepared anode material has good uniformity; the raw materials are easy to obtain, nontoxic and low in cost, can be compatible with the existing production equipment, and is suitable for large-scale production.
In some embodiments of the invention, the oxide comprises B 2 O 3 、TiO 2 、MgO、SnO 2 Or Al 2 O 3 At least one of them.
In some embodiments of the invention, the phosphate salt comprises at least one of diammonium phosphate, monoammonium phosphate, magnesium metaphosphate, aluminum phosphate, sodium phosphate, or calcium phosphate.
In some embodiments of the invention, the borate comprises at least one of sodium borate, magnesium metaborate, aluminum borate, calcium borate, or zinc borate, wherein the sodium borate is anhydrous sodium borate and/or a hydrate of sodium borate, such as sodium tetraborate or borax.
In some embodiments of the present invention, the sodium ion layered oxide has the chemical formula Na x MO 2 Of which 0.67<x is less than or equal to 1, and M comprises at least one of Ni, mn, fe, cu, ti, sn, mg, al, zr, zn or Co.
In some embodiments of the invention, the mass percentage of aluminum fluoride to the sodium ion layered oxide is 0.25wt% to 3wt%, for example, 0.25wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt% of any point value or range of values consisting of any two point values.
In some embodiments of the invention, the mass percentage of the compound X in the sodium ion layered oxide is 0.25wt% to 3wt%, for example, any point value or a range of values consisting of any two point values of 0.25wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%.
In some embodiments of the present invention, the particle size of the sodium ion layered oxide before the grinding is 1 to 20 μm, for example, any one point value or any two point values of 1 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 15 μm, 20 μm.
In some embodiments of the invention, the particle size of the aluminum fluoride before the grinding is 50nm to 3 μm, for example, any one point value or a range value composed of any two point values of 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 1 μm, 2 μm, 3 μm.
In some embodiments of the present invention, the particle size of the compound X before the grinding is 50nm to 3 μm, for example, any one point value or a range value composed of any two point values of 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 1 μm, 2 μm, 3 μm.
In some preferred embodiments of the present invention, the particle sizes of the sodium ion layered oxide 1-20 μm, the aluminum fluoride and the compound X before the grinding are all 50 nm-3 μm, and controlling the particle sizes of the three substances within the above range is advantageous for uniformly coating the surface of the sodium ion layered oxide with the coating.
In some embodiments of the present invention, the grinding may be manual grinding and/or ball milling, which not only can mix the reaction raw materials uniformly, but also can inhibit particle agglomeration, thereby facilitating full coating of the sodium ion layered oxide after sintering.
In some embodiments of the invention, the milling is ball milling at a rotational speed of 150 to 450rpm, for example, any one point value or a range of any two point values of 150rpm, 200rpm, 250rpm, 300rpm, 350rpm, 400rpm, 450 rpm; the ball milling time is 1-5 h, for example, any one point value or a range value formed by any two point values in 1h, 2h, 3h, 4h and 5h.
The rotating speed and time of ball milling are reasonably controlled, the uniformity of mixing of the reaction raw materials can be improved, and meanwhile, the reaction raw materials can be ensured to have proper particle size.
In some embodiments of the invention, the sintering temperature is 180-800 ℃, such as 180 ℃, 200 ℃, 300 ℃, 400 ℃, 450 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃ or any two point values in the range of values; the sintering time is 4-10 h, for example, any one point value or any range value composed of two point values in 4h, 5h, 6h, 7h, 8h, 9h and 10h, the sintering temperature is too low, film formation is not easy to occur, coating is uneven, impedance is increased, the sintering temperature is too high, the anode raw material is changed, performance is reduced, and therefore the sintering temperature needs to be reasonably controlled.
A third aspect of the invention provides a positive electrode sheet comprising a sodium ion battery positive electrode material as described above.
A fourth aspect of the invention provides a sodium ion battery comprising a positive electrode sheet as described above.
Some embodiments of the invention are described in detail below in connection with specific application examples. The starting materials used in the examples, such as those not specifically described, are commercially available.
Example 1
Preparation of NaNi 1/3 Mn 1/3 Fe 1/3 O 2 @AlF 3 -Na 2 B 4 O 7 Layered positive electrode material:
(S1) weighing 0.0105 mmolNa 2 CO 3 、0 .01 mmol NiO、0 .01 mmol MnO 2 、0 .005mmol Fe 2 O 3 And ethanol with the same total mass as the materials is mixed and placed in a ball milling tank, and the ball-material ratio is controlled to be 15:1, setting the rotating speed of the ball mill to 600rpm, performing ball milling for 10 hours in a positive and negative rotation mode, drying and grinding in an oven, and then transferring to a vacuum oven for preservation.
(S2) placing the dried precursor into a muffle furnace for calcination, heating at a speed of 5 ℃/min to 900 ℃, preserving heat for 15 hours, and cooling to room temperature to obtain the NaNi 1/3 Mn 1/3 Fe 1/3 O 2 Layered positive electrode material (sodium ion layered oxide).
(S3) weighing a certain amount of NaNi 1/3 Mn 1/3 Fe 1/3 O 2 Sodium ion layered oxide, 0.5wt% AlF was added 3 1wt% Na 2 B 4 O 7 ·10H 2 O, where NaNi 1/3 Mn 1/3 Fe 1/3 O 2 Particle diameter of positive electrode6 μm AlF 3 With Na and Na 2 B 4 O 7 ·10H 2 Mixing the materials in a ball mill with the particle size of O of 300nm, and setting the procedure to 300 rpm-300 min to obtain a material to be burned; the materials are put into a muffle furnace again for high-temperature fusion, the sintering temperature is 600 ℃, and 5h is sintered to obtain NaNi 1/3 Mn 1/3 Fe 1/ 3 O 2 @AlF 3 -Na 2 B 4 O 7 And transferring the layered anode material to a hand box for standby.
Preparing a positive plate:
the obtained NaNi 1/3 Mn 1/3 Fe 1/3 O 2 @AlF 3 -Na 2 B 4 O 7 The laminar positive electrode material, the conductive additive SP and the binder PVDF are mixed according to 80 parts by weight, 10 parts by weight and 10 parts by weight, dissolved in a solvent NMP, stirred to obtain uniform slurry, then the slurry is uniformly coated on a carbon-coated aluminum foil by using a 100 mu m scraper, dried and sliced to obtain the positive electrode plate.
Example 2
Example 2 is similar to example 1, except that: alF with coating material changed to 1wt% 3 1wt% of B 2 O 3 The other conditions were the same as in example 1.
Example 3
Example 3 is similar to example 1, except that: alF with coating material changed to 1wt% 3 1wt% Na 3 PO 4 The other conditions were the same as in example 1.
Example 4
Example 4 is similar to example 1, except that: alF with coating material changed to 1wt% 3 1wt% of Al 2 O 3 The other conditions were the same as in example 1.
Example 5
Example 5 is similar to example 1, except that: the sintering conditions were changed to 450-6 h, and the other conditions were the same as in example 1.
Example 6
Example 6 is similar to example 1, except that: the sintering conditions were changed to 400-8 h, and the other conditions were the same as in example 1.
Example 7
Example 7 is similar to example 1, except that: the sintering conditions were changed to 800-4 h, and the other conditions were the same as in example 1.
Example 8
Example 8 is similar to example 1, except that: the coating material is changed to 0.5wt percent AlF 3 0.5wt% of Mg 2 B 2 O 4 The other conditions were the same as in example 1.
Example 9
Example 9 is similar to example 1, except that: the coating material is changed to 0.5wt percent AlF 3 0.5wt% of Mg 3 (PO 4 ) 2 The other conditions were the same as in example 1.
Example 10
Example 10 is similar to example 1, except that: the coating material is changed to 0.5wt percent AlF 3 0.5wt% AlPO 4 The other conditions were the same as in example 1.
Comparative example 1
Comparative example 1 is similar to example 1, except that: the coating material is changed to 0.5 weight percent AlF 3 The other conditions were the same as in example 1.
Comparative example 2
Comparative example 2 is similar to example 1, except that: changing the coating material to 1wt% Na 2 B 4 O 7 ·10H 2 O, the other conditions were the same as in example 1.
Comparative example 3
Comparative example 3 is similar to example 2, except that: changing the coating material to 1wt% of B 2 O 3 The other conditions were the same as in example 2.
Comparative example 4
Comparative example 4 is similar to example 3, except that: changing the coating material to 1wt% Na 3 PO 4 The other conditions were the same as in example 3.
Comparative example 5
Comparative example 5 is similar to example 4, except that: changing the coating material to 1wt% Al 2 O 3 The other conditions are the same as in the examples4。
Comparative example 6
Comparative example 6 is similar to example 1, except that: the sintering temperature was 600-2 h, and the other conditions were the same as in example 1.
Comparative example 7
Comparative example 7 is similar to example 1, except that: the sintering temperature was 600-15. 15 h, and the other conditions were the same as in example 1.
Comparative example 8
Comparative example 8 the procedure was the same as in example 1, except that comparative example 8 was free of coating material, and the remaining conditions were the same as in example 1.
Experimental example
The positive electrode sheet and the sodium sheet obtained in each example and each comparative example are assembled into a half cell, and the electrolyte used is 1M NaClO 4 in PC+5 vol% FEC; electrochemical testing was performed after assembly. The positive electrode was activated for 3 cycles at a current density of 0.1C and then charge-discharge cycled at a current density of 1C in a voltage interval of 2.0-4.1V, and the test results are shown in table 1.
TABLE 1
As can be seen from fig. 1, the layered structure of the O3 positive electrode is not changed by the artificially designed coating, and the coating can still be classified into a P3/mmc type space group. From the test results of the half cells of each example in the half cells of table 1, it can be seen that: after the coating material coats the layered positive electrode material, the initial discharge specific capacity of the sodium battery is slightly reduced, because the coating layer is an inactive material and cannot provide capacity, but the capacity retention rate of the coated material is remarkably improved. For example, in example 1, the reversible discharge specific capacity after 200 cycles still has 128.6 mAh/g, while in comparative example 8 without coating, the reversible discharge specific capacity is only 71.06 mAh/g, and the cycling stability of the sodium ion battery is obviously improved after the co-coating in example 1; as shown in fig. 2, the specific capacity of the battery obtained after co-coating in example 1 was 136.9mAh/g, and was not significantly changed as compared with the uncoated battery; as shown in fig. 3, the battery containing the positive electrode material of the sodium ion battery in example 1 of the present application has good cycle stability. In addition, by comparison with comparative examples 1-5, the co-coating has a more pronounced improvement in the long cycle performance of the layered cathode material and less capacity reduction than the simple oxide, phosphate, borate or fluoride coating. By comparison with comparative examples 6 to 7, short-time sintering may result in insufficient material reaction, long-time sintering may result in the original structure of the raw material being destroyed, both of which are manifested as capacity reduction and cycle reduction.
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 positive electrode material of the sodium ion battery is characterized by comprising a sodium ion layered oxide and a coating layer coated on the surface of the sodium ion layered oxide;
the coating comprises a co-sintered product of aluminum fluoride and a compound X comprising at least one of an oxide, phosphate, boric acid, or borate.
2. The sodium ion battery cathode material of claim 1, comprising at least one of the following features (1) to (4):
(1) The oxide includes B 2 O 3 、TiO 2 、MgO、SnO 2 Or Al 2 O 3 At least one of (a) and (b);
(2) The phosphate comprises at least one of diammonium phosphate, monoammonium phosphate, magnesium metaphosphate, aluminum phosphate, sodium phosphate or calcium phosphate;
(3) The borate comprises at least one of sodium borate, magnesium metaborate, aluminum borate, calcium borate or zinc borate;
(4) The chemical general formula of the sodium ion layered oxide is Na x MO 2 Of which 0.67<x is less than or equal to 1, and M comprises at least one of Ni, mn, fe, cu, ti, sn, mg, al, zr, zn or Co.
3. The method for preparing the positive electrode material of the sodium ion battery as claimed in claim 1 or 2, comprising the following steps:
mixing sodium ion layered oxide with aluminum fluoride and a compound X, and grinding and sintering;
wherein the compound X comprises at least one of an oxide, a phosphate, boric acid or a borate.
4. The method for producing a sodium ion battery positive electrode material according to claim 3, characterized by comprising at least one of the following features (1) to (4):
(1) The oxide includes B 2 O 3 、TiO 2 、MgO、SnO 2 Or Al 2 O 3 At least one of (a) and (b);
(2) The phosphate comprises at least one of diammonium phosphate, monoammonium phosphate, magnesium metaphosphate, aluminum phosphate, sodium phosphate or calcium phosphate;
(3) The borate comprises at least one of sodium borate, magnesium metaborate, aluminum borate, calcium borate or zinc borate;
(4) The chemical general formula of the sodium ion layered oxide is Na x MO 2 Of which 0.67<x is less than or equal to 1, and M comprises at least one of Ni, mn, fe, cu, ti, sn, mg, al, zr, zn or Co.
5. The method for producing a sodium ion battery positive electrode material according to claim 3, characterized by comprising at least one of the following features (1) to (2):
(1) The mass percentage of the aluminum fluoride to the sodium ion layered oxide is 0.25-3 wt%;
(2) The mass percentage of the compound X in the sodium ion layered oxide is 0.25-3 wt%.
6. The method for preparing a positive electrode material for a sodium ion battery according to claim 3, wherein the particle size of the sodium ion layered oxide before the grinding is 1 to 20 μm;
and/or the particle size of the aluminum fluoride before grinding is 50 nm-3 mu m;
and/or the particle size of the compound X before grinding is 50 nm-3 mu m.
7. The method for preparing the positive electrode material of the sodium ion battery according to claim 3, wherein the grinding is ball milling, the rotational speed of the ball milling is 150-450 rpm, and the time of the ball milling is 1-5 h.
8. The method for preparing the positive electrode material of the sodium ion battery according to claim 3, wherein the sintering temperature is 180-800 ℃, and the sintering time is 4-10 h.
9. A positive electrode sheet, characterized by comprising the positive electrode material for a sodium ion battery according to claim 1 or 2 or a positive electrode material for a sodium ion battery prepared by the method for preparing a positive electrode material for a sodium ion battery according to any one of claims 3 to 8.
10. A sodium ion battery comprising the positive electrode sheet of claim 9.
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