CN114853079A - Layered sodium ion positive electrode material and preparation method thereof - Google Patents
Layered sodium ion positive electrode material and preparation method thereof Download PDFInfo
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- CN114853079A CN114853079A CN202210625663.7A CN202210625663A CN114853079A CN 114853079 A CN114853079 A CN 114853079A CN 202210625663 A CN202210625663 A CN 202210625663A CN 114853079 A CN114853079 A CN 114853079A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 60
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 239000010406 cathode material Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
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Abstract
The invention relates to an ion battery, in particular to a layered sodium ion positive electrode material and a preparation method thereof. The preparation method of the sodium ion anode material comprises the steps of adding triethanolamine in the preparation process; the raw material of the sodium ion cathode material comprises Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 . The invention uses triethanolamine, the prepared material has a porous structure, and sodium ions in NaCu can be shortened x Fe y Mn z O 2 Migration distance in the/carbon composite; prepared NaCu x Fe y Mn z O 2 The/carbon composite material has higher gram capacity and rate capability, and the 0.2C discharge capacity is more than 115 mAh/g; the 10C discharge capacity is more than 106 mAh/g.
Description
Technical Field
The invention relates to an ion battery, in particular to a layered sodium ion positive electrode material and a preparation method thereof.
Background
Since the end of the 70's of the 20 th century, sodium ion battery research has been almost synchronized with lithium ion batteries. However, lithium ion batteries have received much attention due to the low energy density and cycle life variation of sodium ion batteries. In recent years, with the gradual exposure of problems such as scarcity and uneven distribution of lithium resources, sodium ion batteries with wide resource distribution are receiving renewed attention.
Sodium ion batteries can be classified as Na, according to the positive electrode material 3 V 2 (PO 4 ) 3 Layered NaNi x Fe y Mn z O 3 Or layered NaCu x Fe y Mn z O 2 Prussian blue three batteries; the layered sodium-ion battery has a specific Na ratio 3 V 2 (PO 4 ) 3 The sodium ion battery has higher energy density and longer cycle life than the Prussian blue sodium ion battery, and is favored by people.
Disclosure of Invention
In layered sodium ion batteries, NaCu x Fe y Mn z O 2 With NaNi x Fe y Mn z O 3 In contrast, the price of copper metal is much lower than that of nickel metal, and the distribution of copper metal is more extensive than that of nickel metal, and thus is receiving much attention. The inventor finds that NaCu in practice x Fe y Mn z O 2 Sodium ion batteries have the following drawbacks: with NaNi x Fe y Mn z O 3 In contrast, the divalent to trivalent copper conversion capacity is weaker than that of divalent to trivalent nickel, and thus NaCu x Fe y Mn z O 2 The multiplying power charge-discharge capacity of the prepared sodium ion battery is weaker than that of NaNi x Fe y Mn z O 3 The prepared sodium ion battery has charge and discharge capacity.
The present invention is directed to solving at least one of the above problems.
The embodiment of the invention provides a layered sodium ion positive electrode material and a preparation method thereof.
The inventors have surprisingly found that triethanolamine, which can be used as a reducing agent to add Mn to the raw material during the preparation of the sodium ion positive electrode material, can be used as a reducing agent 4+ Reduction to Mn 3+ The gas generated in the reduction process can form a porous structure, and the porous structure improves the NaCu x Fe y Mn z O 2 The surface area of the material is more beneficial to the sodium ions to enter and exit from the anode material; on the other hand, triethanolamine cracks and carbonizes to form carbon-coated NaCu x Fe y Mn z O 2 The positive electrode material further improves the conductivity of the sodium vanadium phosphate material.
The invention firstly provides a preparation method of a sodium ion anode material, which comprises the steps of adding triethanolamine in the preparation process; the raw material of the sodium ion cathode material comprises Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 。
In the present example, the triethanolamine was added in an amount of MnO 2 0.5-3 times of the material quality, and optionally 1.5-3 times of the material quality; specific examples thereof include 0.5 times, 0.8 times, 1 time, 1.5 times, 1.8 times and 3 times.
In the present example, triethanolamine was added together with a solvent, or after the triethanolamine was made into a solution.
In the embodiment of the present invention, the solvent is an organic solvent, and specifically may be one or more selected from methanol, ethanol, propanol, butanol, and isopropanol.
In the embodiment of the invention, the solvent is 60-80 wt% of the total weight of the raw materials for preparing the sodium ion cathode material.
In the examples of the present invention, Na is added 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Added according to the required stoichiometric ratio. Examples are Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 The stoichiometric ratio (molar ratio) of (A) to (B) is 10 (4-4.5):3 (0.95-4), specifically 10:4:3:1, 10:4.5:3:0.95, 10:4.5:3: 0.95.
In the examples of the present invention, the preparation method includes ball milling all the raw materials. The ball milling rotating speed is preferably 100-200 rpm; the ball milling time is preferably 8 to 16 hours.
In the embodiment of the invention, the preparation method comprises drying the ball-milled materials. Optionally, the drying temperature is 80-120 ℃; alternatively, the drying time is 1-2 hours. Drying to obtain the precursor of the finished product.
In an embodiment of the present invention, the preparation method includes sintering the dried precursor after ball milling. Optionally, the obtained precursor is sintered for 0.5-1 hour at a heating rate of 5-10 ℃/min to 350-500 ℃ under the protection of an inert atmosphere (such as nitrogen), and then is transferred to an air atmosphere to be sintered for 5-10 hours at 700-900 ℃. The sintered powder is the sodium ion anode material.
In an embodiment of the present invention, the preparation method comprises:
1) mixing Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Adding the mixture into a ball milling tank according to the required stoichiometric ratio, and then adding triethanolamine and ethanol (solvent), wherein the addition amount of the triethanolamine is MnO 2 0.5-3 times of the mass, and the total mass of the ethanol (solvent) is 60-80% of the total mass of the materials;
2) adding grinding balls (for example, the mass of the balls is one third to one half of the weight of the solid materials) into a ball milling tank; the ball milling speed is 100 and 200rpm, and the ball milling time is 8-16 hours;
3) drying the material obtained in the step 2) in a vacuum oven at the temperature of 80-120 ℃ for 1-2 hours; and obtaining the precursor of the finished product.
4) Under the protection of nitrogen, the precursor obtained in the step 3) is sintered for 0.5 to 1 hour at the temperature rising rate of 10 ℃/min to 350-DEG C and 500 ℃, then transferred to the air atmosphere and sintered for 5 to 10 hours at the temperature of 700-DEG C and 900 ℃, and the obtained powder is NaCu x Fe y Mn z O 2 the/C composite anode material is characterized in that x is more than 0 and less than or equal to 0.3; y is more than 0 and less than or equal to 0.5; 0 < z≤0.3。
In the embodiment of the invention, the sodium ion cathode material is NaCu x Fe y Mn z O 2 the/C composite anode material is characterized in that x is more than 0 and less than or equal to 0.3; y is more than 0 and less than or equal to 0.5; z is more than 0 and less than or equal to 0.3. In some examples, x is 0.225 or 0.3; y is 0.3; z is 0.475 or 0.5.
The invention also discloses the sodium ion cathode material prepared by the method.
In the embodiment of the invention, the sodium ion positive electrode material is a layered sodium ion positive electrode material.
The invention also provides application of the sodium ion positive electrode material in preparation of a sodium ion battery.
The invention also provides a sodium ion battery which comprises the sodium ion positive electrode material.
In the embodiment of the invention, the sodium ion battery is NaCu x Fe y Mn z O 2 A sodium ion battery.
In the embodiment of the invention, the sodium ion battery is made of NaCu x Fe y Mn z O 2 Is a positive electrode; optionally hard carbon or metallic sodium as the negative electrode.
The invention uses triethanolamine, the prepared material has a porous structure, and sodium ions in NaCu can be shortened x Fe y Mn z O 2 Migration distance in the/carbon composite; prepared NaCu x Fe y Mn z O 2 The/carbon composite material has higher gram capacity and rate capability, and the 0.2C discharge capacity is more than 115 mAh/g; the 10C discharge capacity is more than 106 mAh/g.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Example 1
The embodiment provides a sodium ion cathode material, and a preparation method thereof is as follows:
1) mixing Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Adding 10mol:4mol:3mol:1mol of triethanolamine and ethanol (solvent), wherein the adding amount of the triethanolamine is MnO 2 1.5 times of the mass, and the total mass of the ethanol (solvent) is 60 percent of the total mass of the materials;
2) adding grinding balls into the ball milling tank, wherein the mass of the balls is one half of the weight of the solid material; the ball milling speed is 130rpm, and the ball milling time is 12 hours;
3) drying the material obtained in the step 2) in a vacuum oven at 100 ℃ for 2 hours to obtain a precursor of a finished product;
4) sintering the precursor obtained in the step 3) at the temperature rising rate of 10 ℃/min to 450 ℃ for 1 hour under the protection of nitrogen, transferring to the air atmosphere, and sintering at 850 ℃ for 8 hours to obtain powder, namely NaCu 0.2 Fe 0.3 Mn 0.5 O 2 And C, a positive electrode material.
Example 2
The embodiment provides a sodium ion cathode material, and a preparation method thereof is as follows: 1) mixing Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Adding 10mol:4.5mol:3mol:0.95mol into a ball milling tank, then adding triethanolamine and ethanol (solvent), wherein the adding amount of the triethanolamine is MnO 2 1.8 times of the mass, and the total mass of the ethanol (solvent) is 65 percent of the total mass of the materials;
2) adding grinding balls into the ball milling tank, wherein the mass of the balls is one half of the weight of the solid material; the ball milling speed is 150rpm, and the ball milling time is 11 hours;
3) drying the material obtained in the step 2) in a vacuum oven at 100 ℃ for 2 hours to obtain a precursor of a finished product;
4) sintering the precursor obtained in the step 3) at a heating rate of 10 ℃/min to 500 ℃ for 1 hour under the protection of nitrogen, transferring to an air atmosphere, and sintering at 900 ℃ for 10 hours to obtain powder, namely NaCu 0.225 Fe 0.3 Mn 0.475 O 2 a/C isElectrode material
Example 3
The embodiment provides a sodium ion cathode material, and a preparation method thereof is as follows: 1) mixing Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Adding 10mol:4.5mol:3mol:0.95mol into a ball milling tank, then adding triethanolamine and ethanol (solvent), wherein the adding amount of the triethanolamine is MnO 2 3 times of the mass, and the total mass of the ethanol (solvent) is 65 percent of the total mass of the materials;
2) adding grinding balls into the ball milling tank, wherein the mass of the balls is one half of the weight of the solid material; the ball milling speed is 150rpm, and the ball milling time is 11 hours;
3) drying the material obtained in the step 2) in a vacuum oven at 100 ℃ for 2 hours to obtain a precursor of a finished product;
4) sintering the precursor obtained in the step 3) at a heating rate of 10 ℃/min to 500 ℃ for 1 hour under the protection of nitrogen, transferring to an air atmosphere, and sintering at 900 ℃ for 10 hours to obtain powder, namely NaCu 0.225 Fe 0.3 Mn 0.475 O 2 a/C positive electrode material.
Comparative example 1
The comparative example provides a sodium ion positive electrode material, and the preparation method thereof is as follows:
1) mixing Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Adding 10mol:4mol:3mol:1mol of the raw materials into a ball milling tank, and then adding ethanol (solvent), wherein the total mass of the ethanol (solvent) is 60% of the total mass of the raw materials;
2) adding grinding balls into the ball milling tank, wherein the mass of the balls is one half of the weight of the solid material; the ball milling speed is 130rpm, and the ball milling time is 12 hours;
3) drying the material obtained in the step 2) in a vacuum oven at 100 ℃ for 2 hours; obtaining a precursor of a finished product;
4) sintering the precursor obtained in the step 3) for 8 hours at 850 ℃ in air atmosphere to obtain powder, namely NaCu 0.2 Fe 0.3 Mn 0.5 O 2 And (3) a positive electrode material.
Examples of the experiments
Preparing a half cell: NaCu prepared in examples 1-3 and comparative example 1 x Fe y Mn z O 2 Composite material of/C or NaCu x Fe y Mn z O 2 As the positive electrode, metal sodium is used as the negative electrode, a 20 mu mPP/PE/PP diaphragm and NaPF 6 The Ethylene Carbonate (EC)/dimethyl carbonate (DEC) solution is used as an electrolyte, fluoroethylene carbonate (FEC) is used as an electrolyte additive (the molar ratio of FEC to EC + DMC is 1:20), and a battery is assembled in a glove box filled with argon gas to carry out a charge-discharge test (the voltage range is 2-4V). NaCu in positive electrode x Fe y Mn z O 2 Composite material of/C or NaCu x Fe y Mn z O 2 The mass percentage of the binder PVDF to the conductive agent SP is 94:3: 3.
The test results are shown in the following table.
| Item | 0.2C gram capacity (mAh/g) | 1C gram Capacity (mAh/g) |
| Example 1 | 118.6 | 106.9 |
| Example 2 | 125.3 | 116.7 |
| Example 3 | 122.7 | 118.1 |
| Comparative example 1 | 109.8 | 89.6 |
As can be seen from the above table, the 1C gram capacity of the materials of examples 1-3 is much higher than that of comparative example 1, which shows that the method is very effective for improving the high-current discharge performance of the materials.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a sodium ion positive electrode material is characterized by comprising the steps of adding triethanolamine in the preparation process; the raw material of the sodium ion cathode material comprises Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 。
2. The method for preparing the sodium ion positive electrode material according to claim 1, wherein triethanolamine is added together with a solvent, or the triethanolamine is added after being made into a solution;
optionally, the solvent is selected from one or more of ethanol, methanol, ethanol, propanol, butanol and isopropanol;
optionally, the solvent used is 60-80 wt% of the total weight of the raw materials for preparing the sodium ion cathode material.
3. The method for producing a sodium ion positive electrode material according to claim 1 or 2, wherein triethanolamine is added in an amount of MnO 2 0.5-3 times of the material quality, and optionally 1.5-3 times of the material quality; and/or the presence of a gas in the gas,
Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 the molar ratio of (1) to (4-4.5) to (3) (0.95-4).
4. A method for preparing a sodium ion positive electrode material according to any one of claims 1 to 3, characterized in that the preparation method comprises ball milling all raw materials;
the ball milling rotating speed is preferably 100-200 rpm; the ball milling time is preferably 8 to 16 hours.
5. The method for preparing a sodium ion positive electrode material according to any one of claims 1 to 4, wherein the preparation method comprises drying the ball-milled material; optionally, the drying temperature is 80-120 ℃; alternatively, the drying time is 1-2 hours.
6. The method for preparing a sodium ion positive electrode material according to any one of claims 1 to 5, wherein the preparation method comprises sintering a dried precursor after ball milling; optionally, the obtained precursor is sintered for 0.5-1 hour at the temperature rising rate of 5-10 ℃/min to 350-500 ℃ under the protection of inert atmosphere, and then is transferred to air atmosphere for sintering for 5-10 hours at the temperature of 700-900 ℃.
7. The method for producing a sodium ion positive electrode material according to any one of claims 1 to 6, comprising:
1) mixing Na 2 CO 3 、Fe 2 O 3 、CuO、MnO 2 Adding the mixture into a ball milling tank according to the required stoichiometric ratio, and then adding triethanolamine and ethanol, wherein the addition amount of the triethanolamine is MnO 2 0.5-3 times of the mass, and the total mass of the ethanol is 60-80% of the total mass of the materials;
2) adding grinding balls into the ball milling tank; the ball milling speed is 100 and 200rpm, and the ball milling time is 8-16 hours;
3) drying the material obtained in the step 2) in a vacuum oven at the temperature of 80-120 ℃ for 1-2 hours; and obtaining the precursor of the finished product.
4) And (3) under the protection of nitrogen, heating the precursor obtained in the step 3) at a heating rate of 10 ℃/min to 350-500 ℃ for sintering for 0.5-1 h, transferring to an air atmosphere, and sintering at 900 ℃ for 5-10h at 700-2 ℃.
8. A sodium ion positive electrode material, characterized by being produced by the method according to any one of claims 1 to 7;
optionally, the sodium ion cathode material is NaCu x Fe y Mn z O 2 the/C composite anode material is characterized in that x is more than 0 and less than or equal to 0.3; y is more than 0 and less than or equal to 0.5; z is more than 0 and less than or equal to 0.3; alternatively, x is 0.225 or 0.3; y is 0.3; z is 0.475 or 0.5.
9. The use of the sodium ion positive electrode material of claim 7 in the manufacture of a sodium ion battery;
optionally, the sodium ion battery is NaCu x Fe y Mn z O 2 A sodium ion battery; wherein x is more than 0 and less than or equal to 0.3; y is more than 0 and less than or equal to 0.5; z is more than 0 and less than or equal to 0.3; alternatively, x is 0.225 or 0.3; y is 0.3; z is 0.475 or 0.5.
10. A sodium ion battery comprising the sodium ion positive electrode material according to claim 7;
optionally, the sodium ion battery is NaCu x Fe y Mn z O 2 A sodium ion battery; wherein x is more than 0 and less than or equal to 0.3; y is more than 0 and less than or equal to 0.5; z is more than 0 and less than or equal to 0.3; alternatively, x is 0.225 or 0.3; y is 0.3; z is 0.475 or 0.5.
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