CN116895753A - Positive electrode material of single crystal sodium ion battery, sodium ion battery and preparation method - Google Patents
Positive electrode material of single crystal sodium ion battery, sodium ion battery and preparation method Download PDFInfo
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- CN116895753A CN116895753A CN202311153359.8A CN202311153359A CN116895753A CN 116895753 A CN116895753 A CN 116895753A CN 202311153359 A CN202311153359 A CN 202311153359A CN 116895753 A CN116895753 A CN 116895753A
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- ion battery
- sodium ion
- sodium
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 56
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000011734 sodium Substances 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000002228 NASICON Substances 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000010416 ion conductor Substances 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 239000011572 manganese Substances 0.000 claims description 46
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 15
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004327 boric acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 8
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000007873 sieving Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/128—Borates containing plural metal or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
-
- 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
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- 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
Abstract
The application discloses a single crystal sodium ion battery positive electrode material, a sodium ion battery and a preparation method thereof, wherein the single crystal sodium ion battery positive electrode material has a core-shell structure, a layered oxide is adopted as an inner core, a coating material is adopted as an outer shell, and the layered oxide is Na of O3 phase x Ni a Fe b Mn c M1 d O 2 The space group is R-3m; m1 is one or more elements in Cu, zn, ti, ca, al, B, sr; the coating material is a sodium super ion conductor material with a NASICON structure, and the chemical composition is Na y M2 n+ e (PO4) m M2 is a metal element, including Ti, zr, zn, sn, Y, la; n is the valence of the metal M2; wherein the stoichiometry of each element satisfies the charge neutrality principle, i.e. y+n×e=3m. Compared with the uncoated sodium ion layered oxide anode material, the air stability, the cyclic charge and discharge stability and the multiplying power performance of the application are improved; the sintering cladding can be realized once, the secondary sintering step is reduced, and the energy conservation and the synergy can be realized.
Description
Technical Field
The application relates to the technical field of sodium ion batteries, in particular to a single crystal sodium ion battery anode material, a sodium ion battery and a preparation method.
Background
At present, the synthesis process for preparing the layered oxide of the sodium ion battery comprises the following steps:
and (2) mixing 2 or more raw materials and additives in a sodium source, an iron source, a nickel source and a manganese source at a high speed, and then sintering at a high temperature to obtain the sodium ion layered oxide.
And 2, mixing a sodium source and a spherical hydroxide precursor, and then sintering at high temperature to obtain the sodium ion layered oxide.
Compared with lithium, sodium has higher abundance and wider distribution in geology, so the sodium ion battery has great application prospect in the field of large-scale energy storage. Among various sodium-electric positive electrode materials, sodium-ion layered oxide positive electrode materials have been receiving attention and research due to their diversity of components and characteristics of easy mass production. However, the sodium-ion layered oxide cathode material still has some challenges in practical production and application, such as poor stability of the layered oxide material when exposed to air, and problems of moisture absorption, precipitation of sodium in the structure, high residual alkali on the surface of the material, and the like. The common strategy for improving air stability of the sodium ion layered oxide cathode material is surface coating, however, the conventional coating layer can only play a role of isolating the internal active material from air, and secondary sintering is usually required, and secondary sintering coating also means that higher energy consumption is required, namely, the economy of material production and preparation can be reduced.
The strategy for improving the air stability of the sodium ion layered oxide anode material is used for surface coating, and the strategy has the defects that; the coating material generally has a single function (only isolating air from direct contact with the inner sodium layered oxide) and generally requires a two-firing treatment for surface coating, which reduces the economy of material production and preparation.
Disclosure of Invention
The application provides a single crystal sodium ion battery anode material and a preparation method thereof, which aims to solve one of the technical problems that: the existing NASICON material needs to be sintered for the second time when being coated, so that the technical problem of higher energy consumption is caused.
In view of the foregoing problems of the prior art, according to one aspect of the disclosure, the present application adopts the following technical solutions:
a single crystal sodium ion battery positive electrode material is of a core-shell structure, wherein an inner core is a layered oxide, and an outer shell is a coating material;
na of which the layered oxide is O3 phase x Ni a Fe b Mn c M1 d O 2 The space group is R-3m; wherein x is more than or equal to 0.90 and less than or equal to 1.20,0 and less than or equal to a and less than or equal to 0.80,0 and less than or equal to b and less than or equal to 0.40,0 and less than or equal to c and less than or equal to 0.6,0 and less than or equal to d and less than or equal to 0.10; m1 is one or more elements in Cu, zn, ti, ca, al, B, sr;
the coating material is a sodium super ion conductor material with a NASICON structure, and the chemical composition is Na y M2 n+ e (PO4) m M2 is a metal element, including Ti, zr, zn, sn, Y, la; n is the valence of the metal M2; the stoichiometry of each element satisfies the charge neutrality principle, that is, y+n=3m.
In order to better realize the application, the further technical scheme is as follows:
further, the coating material accounts for 0.03-30% of the total mass of the coating material.
A preparation method of a single crystal sodium ion battery positive electrode material comprises the following steps:
weighing two or more of a sodium source, an iron source, a nickel source and a manganese source, and uniformly mixing with an M1 source, an M2 source and a phosphorus source according to a designed stoichiometric ratio;
sintering for 8-24 h in a furnace at 850-1100 ℃;
and after the sintering temperature is reduced to room temperature, crushing the obtained material to obtain the sodium-ion layered oxide anode material coated by the NASICON structural material.
Further, according to the stoichiometric ratio of Na to Ni to Fe to Mn to B to Zn to P= (1.02-1.1): 0.33 to 0.33, (0.03-0.05): 0.08-0.1): 0.06-0.15, a certain amount of sodium carbonate, nickel iron manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate are weighed and evenly mixed.
Further, weighing a certain amount of sodium carbonate, nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate according to the stoichiometric ratio of Na to Fe to Mn to B to Zn to P=1.02 to 0.33 to 0.05 to 0.08, and uniformly mixing.
Further, weighing a certain amount of sodium carbonate, nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate according to a stoichiometric ratio of Na to Ni to Fe to Mn to Cu to La to P=1.1 to 0.33 to 0.03 to 0.06, and uniformly mixing.
Further, a certain amount of sodium carbonate, nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate are weighed according to the stoichiometric ratio of Na to Fe to Mn to Al to Zr to P=1.07 to 0.33 to 0.03 to 0.1 to 0.15 and are uniformly mixed.
Further, the molar ratio of Ni to Fe to Mn in the nickel-iron-manganese hydroxide precursor is 0.33:0.33:0.33.
Further, during sintering, the temperature rise rate was 3 ℃/min.
A sodium ion battery is prepared by adopting the positive electrode material of the single crystal sodium ion battery.
Compared with the prior art, the application has one of the following beneficial effects:
according to the single crystal sodium ion battery positive electrode material, the sodium ion battery and the preparation method, 1) compared with the uncoated sodium ion layered oxide positive electrode material, the sodium ion layered oxide positive electrode material coated by the NASICON structure material has improved air stability, stable cyclic charge and discharge and rate capability; 2) The sintering cladding can be realized once, the secondary sintering step is reduced, and the energy-saving and efficiency-increasing advantages are realized.
Drawings
For a clearer description of embodiments of the present application or of solutions in the prior art, reference will be made below to the accompanying drawings, which are used in the description of embodiments or of the prior art, it being obvious that the drawings in the description below are only references to some embodiments of the present application, from which other drawings can be obtained, without inventive effort, for a person skilled in the art.
Fig. 1 and 2 are SEM schematic views of a positive electrode material according to example 1 of the present application.
Fig. 3 is a schematic charge-discharge curve of example 1 of the present application.
FIG. 4 is a graph showing the cycle stability curve of example 1 of the present application.
FIG. 5 is a schematic view of the rate capability of the present application.
Fig. 6 and 7 are SEM schematic views of comparative example 1.
Fig. 8 is a schematic diagram of the charge-discharge curve of comparative example 1.
FIG. 9 is a schematic of the cycle stability of comparative example 1.
Detailed Description
The present application will be described in further detail with reference to examples, but embodiments of the present application are not limited thereto.
The application provides a strategy for forming a sodium super ion conductor (NASICON) structure type coating material on the surface of a sodium ion layered oxide in situ, which can effectively improve the air stability of a sodium ion layered oxide anode material and enhance the rapid charge and discharge capacity of the material, and the specific principle is as follows:
1) The NASICON material has excellent stability (the existence of a firm P-O bond in the structure) in water and air, so that the NASICON material coated on the surface of the sodium ion layered oxide can effectively isolate air/water from contacting with internal materials, thereby improving the air stability of the material;
2) The NASICON material is of an open 3D network structure, wherein sodium ions are located at gap positions of a 3D network formed by P-O and M-O, and the NASICON material has excellent sodium ion conductivity due to the special structure. Therefore, the NASICON coating layer is formed on the surface of the sodium ion layered oxide anode material, so that the diffusion kinetics of sodium ions can be improved, and the rate capability of the material is improved.
The strategy provided by the application not only improves the air stability and the multiplying power performance of the material, but also can realize the coating by primary sintering, reduces the secondary sintering step and has the advantages of energy conservation and efficiency improvement.
Specifically, the single crystal sodium ion battery anode material is of a core-shell structure, wherein an inner core is a layered oxide, and an outer shell is a coating material;
na of which the layered oxide is O3 phase x Ni a Fe b Mn c M1 d O 2 The space group is R-3m; wherein x is more than or equal to 0.90 and less than or equal to 1.20,0 and less than or equal to a and less than or equal to 0.80,0 and less than or equal to b and less than or equal to 0.40,0 and less than or equal to c and less than or equal to 0.6,0 and less than or equal to d and less than or equal to 0.10; m1 is one or more elements in Cu, zn, ti, ca, al, B, sr;
the coating material is a sodium super ion conductor material with a NASICON structure, and the chemical composition is Na y M2 n+ e (PO4) m M2 is a metal element, including Ti, zr, zn, sn, Y, la; n is the valence of the metal M2; the stoichiometry of each element satisfies the charge neutrality principle, that is, y+n=3m.
The coating material accounts for 0.03-30% of the total mass of the coating material.
A method of preparing the single crystal sodium ion battery positive electrode material of the above embodiment, comprising:
weighing two or more of a sodium source, an iron source, a nickel source and a manganese source, and uniformly mixing with an M1 source, an M2 source and a phosphorus source according to a designed stoichiometric ratio; wherein, the stoichiometric ratio can be Na, ni, fe, mn, M1, M2, P= (1.02-1.1), 0.33, (0.03-0.05), 0.08-0.1, 0.06-0.15;
sintering for 8-24 h in a furnace at 850-1100 ℃; the sintering can be carried out in equipment such as an air atmosphere furnace, a box furnace and the like;
and after the sintering temperature is reduced to room temperature, crushing and storing the obtained material to obtain the sodium-ion layered oxide anode material coated by the NASICON structural material.
Example 1: the embodiment provides a sodium ion layered oxide positive electrode material coated by a NASICON structure material and a one-step synthesis method thereof. The preparation method comprises the following steps:
weighing a certain amount of sodium carbonate, nickel-iron-manganese hydroxide precursor (the molar ratio of Na to Ni to Mn is 0.33:0.33:0.33:0.05:0.08:0.08), boric acid, zinc oxide and sodium metaphosphate according to the stoichiometric ratio of Na to Fe to Mn to B to Zn, uniformly mixing the raw materials by a high-speed mixer, placing the obtained powder into a box-type furnace, sintering for 14h at 950 ℃, and heating up at a rate of 3 ℃/min. Cooling to room temperature, pulverizing and sieving the sintered powder, wherein the sieving material is marked as NaZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 . As shown in FIGS. 1 and 2, the morphology of the NaZnPO product is compared with that of the product of comparative example 1 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The surface forms a uniform coating.
Taking a certain mass of NaZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 This was placed in a glove box, and the relative humidity in the glove box was kept at 20% ± 3%. The moisture content and the surface residual alkali (sodium carbonate and sodium hydroxide) in the powder detection material with constant quality are taken every 4 hours. The method used for detecting the moisture content is a Karl Fischer moisture test method, the residual alkali is an automatic potentiometric titration method, and the moisture content and the surface residual alkali detection result are shown in Table 1.
TABLE 1 summary of moisture content and residual alkali detection results
As can be seen from table 1: compared with NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 In terms of NaZnPO after in-situ coating 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The water absorbability of the anode of the lithium ion battery is obviously improved, and sodium precipitation in a material system to form residual alkali is also obviously inhibited.
The NaZnPO obtained above is mixed with 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The active material serving as the positive electrode material of the sodium ion battery is used for preparing the sodium ion battery, and the specific preparation steps are as follows: naZnPO is added with 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Mixing Super P and polyvinylidene fluoride (PVDF) according to the mass ratio of 9:0.5:0.5, adding proper amount of N-methyl pyrrolidone (NMP), stirring to form slurry, uniformly coating the slurry on clean aluminum foil, drying for 8 hours (100 ℃) in a vacuum drying box, punching a round grade sheet with a die with the diameter of 14mm after passing through a cold press pair roller, vacuum baking for 2 hours, transferring into a glove box protected by Ar atmosphere for battery assembly, taking glass fiber as a diaphragm, and taking 1 mol/L NaPF (sodium silicate fiber) 6 Propylene carbonate solution of (a) as an electrolyte. And using a Xinwei battery test system to perform charge and discharge tests in a cross-flow charge and discharge mode, wherein a test voltage window is 2.0-4.0V.
NaZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The first-week charge-discharge curve of the prepared button cell is shown in fig. 3, and the first-week discharge capacity is 125.7 mAh/g and the coulomb efficiency is 92.9% under the charge-discharge rate of 0.1C. Further to NaZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The cyclic charge and discharge test was performed, and the test results are shown in fig. 4: the discharge capacity is still close to 103 mAh/g after 100 weeks of cyclic charge and discharge, and the capacity retention rate is 82.06%. In addition, for NaZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The prepared button cell is subjected to charge and discharge tests under different multiplying powers and is compared with uncoated materials, as shown in FIG. 5, naZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Is superior to NaNi in multiplying power performance 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 A kind of electronic device.
Example 2: the embodiment provides a sodium ion layered oxide positive electrode material coated by a NASICON structure material and a one-step synthesis method thereof. The preparation method comprises the following steps:
according to the stoichiometric ratio of Na to Ni to Fe to Mn to Cu to La to P=1.1 to 0.33 to 0.03 to 0.06, a certain amount of sodium carbonate, nickel iron manganese hydroxide precursor (the molar ratio of Ni to Fe to Mn is 0.33 to 0.33), copper oxide, lanthanum oxide and monoammonium phosphate are weighed, the raw materials are uniformly mixed by a high-speed mixer, the obtained powder is placed in a box furnace, sintering is carried out for 10 hours at 900 ℃, and the heating rate is 3 ℃/min. Cooling to room temperature, pulverizing and sieving the sintered powder, wherein the sieving material is marked as Na 3 La(PO 4 ) 2 @NaNi 0.33 Cu 0.03 Fe 0.33 Mn 0.33 O 2 。
Example 3: the embodiment provides a sodium ion layered oxide positive electrode material coated by a NASICON structure material and a one-step synthesis method thereof. The preparation method comprises the following steps:
according to the stoichiometric ratio of Na to Ni to Fe to Mn to Al to Zr to P=1.07:0.33:0.33:0.03:0.03:0.1:0.15, a certain amount of sodium carbonate, nickel iron manganese hydroxide precursor (the molar ratio of Ni to Fe to Mn is 0.33:0.33), zinc oxide, zirconium dioxide and ammonium dihydrogen phosphate are weighed, the raw materials are uniformly mixed by a high-speed mixer, the obtained powder is placed in a box furnace, sintering is carried out for 14 hours at 1100 ℃, and the heating rate is 3 ℃/min. Cooling to room temperature, pulverizing and sieving the sintered powder, wherein the sieving material is marked as NaZr 2 (PO 4 ) 3 @NaNi 0.33 Al 0.06 Fe 0.33 Mn 0.33 O 2 。
Comparative example 1: according to the stoichiometric ratio of Na to Ni to Fe to Mn to B=102:0.33:0.33:0.33:0.05, a certain amount of sodium carbonate, nickel-iron-manganese hydroxide precursor (the molar ratio of Ni to Fe to Mn is 0.33:0.33) and boric acid are weighed, the raw materials are uniformly mixed by a high-speed mixer, the obtained powder is placed in a box furnace, and sintered for 14 hours at 950 ℃, and the heating rate is 3 ℃/min. Cooling to room temperature, pulverizing and sieving the sintered powder, wherein the sieving material is marked as NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 . The morphology of the particles was observed by a scanning electron microscope and is shown in fig. 6 and 7, and the particle surfaces were smooth.
NaNi was tested by the same test method as in example 1 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The relationship between the moisture content and the residual alkali on the surface with time is shown in Table 1.
Further processing NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Assembled into button cell for testing. The charge-discharge curve is shown in FIG. 8, and the initial discharge capacity is 130.2 mAh/g and the coulombic efficiency is 92.2% at a charge-discharge rate of 0.1C. Further to NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The cyclic charge and discharge test was performed, and the test results are shown in fig. 9: after 100 weeks of cyclic charge and discharge, the discharge capacity was 91.9 mAh/g, and the capacity retention rate was 71.7%. In contrast, naZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Is superior to NaNi in cyclic charge and discharge stability 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Is a cyclic charge-discharge stability of (c). In addition, for NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 The prepared button cell is subjected to charge and discharge tests under different multiplying powers, and compared with the coated material, as shown in FIG. 5, naNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Rate capability is higher than NaZnPO 4 @NaNi 0.33 Fe 0.33 Mn 0.33 B 0.05 O 2 Is poor in rate performance.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described by a difference from other embodiments, and identical and similar parts between the embodiments are mutually referred.
Reference throughout this specification to "one embodiment," "another embodiment," "an embodiment," etc., means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present application as broadly described. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with any embodiment, it is intended that such feature, structure, or characteristic be implemented within the scope of the application.
Although the application has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure. More specifically, various variations and modifications may be made to the component parts and/or arrangements of the subject combination arrangement within the scope of the disclosure and claims. In addition to variations and modifications in the component parts and/or arrangements, other uses will be apparent to those skilled in the art.
Claims (10)
1. The positive electrode material of the single crystal sodium ion battery is of a core-shell structure, wherein an inner core is a layered oxide, and an outer shell layer is a coating material, and is characterized in that:
na of which the layered oxide is O3 phase x Ni a Fe b Mn c M1 d O 2 The space group is R-3m; wherein x is more than or equal to 0.90 and less than or equal to 1.20,0 and less than or equal to a and less than or equal to 0.80,0 and less than or equal to b and less than or equal to 0.40,0 and less than or equal to c and less than or equal to 0.6,0 and less than or equal to d and less than or equal to 0.10; m1 is one or more elements in Cu, zn, ti, ca, al, B, sr;
the coating material is a sodium super ion conductor material with a NASICON structure, and the chemical composition is Na y M2 n+ e (PO4) m M2 is a metal element, including Ti, zr, zn, sn, Y, la; n is the valence of the metal M2; the stoichiometry of each element satisfies the charge neutrality principle, that is, y+n=3m.
2. The single crystal sodium ion battery positive electrode material according to claim 1, wherein the coating material accounts for 0.03-30% by mass.
3. A method for producing the single-crystal sodium ion battery positive electrode material according to claim 1 or 2, characterized by comprising:
weighing two or more of a sodium source, an iron source, a nickel source and a manganese source, and uniformly mixing with an M1 source, an M2 source and a phosphorus source according to a designed stoichiometric ratio;
sintering for 8-24 h in a furnace at 850-1100 ℃;
and after the sintering temperature is reduced to room temperature, crushing the obtained material to obtain the sodium-ion layered oxide anode material coated by the NASICON structural material.
4. The method for preparing the positive electrode material of the single crystal sodium ion battery according to claim 3, which is characterized in that sodium carbonate, nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate are weighed and uniformly mixed according to the stoichiometric ratio of Na, fe, mn, zn, P= (1.02-1.1), 0.33:0.33:0.33:0.33, (0.03-0.05), 0.08-0.1 and 0.06-0.15.
5. The method for preparing the positive electrode material of the single crystal sodium ion battery according to claim 4, which is characterized in that sodium carbonate, a nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate are weighed and uniformly mixed according to the stoichiometric ratio of Na to Ni to Fe to Mn to B to Zn to P=1.02 to 0.33 to 0.05 to 0.08.
6. The method for preparing the positive electrode material of the single crystal sodium ion battery according to claim 3, which is characterized in that sodium carbonate, a nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate are weighed and uniformly mixed according to the stoichiometric ratio of Na, ni, fe, mn, cu and La with P=1.1:0.33:0.33:0.33:0.03:0.03:0.06.
7. The method for preparing the positive electrode material of the single crystal sodium ion battery according to claim 3, which is characterized in that sodium carbonate, a nickel-iron-manganese hydroxide precursor, boric acid, zinc oxide and sodium metaphosphate are weighed according to a stoichiometric ratio of Na to Fe to Mn to Al to Zr to P=1.07 to 0.33 to 0.03 to 0.1 to 0.15 and are uniformly mixed.
8. The method for preparing a single crystal sodium ion battery positive electrode material according to any one of claims 4 to 7, characterized in that the molar ratio of Ni to Fe to Mn in the nickel-iron-manganese hydroxide precursor is 0.33:0.33:0.33.
9. The method for preparing a positive electrode material for a single crystal sodium ion battery according to claim 3, wherein the temperature rising rate is 3 ℃/min during the sintering process.
10. A sodium ion battery characterized by being prepared by using the single crystal sodium ion battery positive electrode material according to any one of claims 1 to 2.
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| CN117497746A (en) * | 2023-12-29 | 2024-02-02 | 宁波容百新能源科技股份有限公司 | Sodium-electricity layered anode material and preparation method and application thereof |
| CN117497746B (en) * | 2023-12-29 | 2024-05-14 | 宁波容百新能源科技股份有限公司 | Sodium-electricity layered anode material and preparation method and application thereof |
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