CN111180706A - Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery - Google Patents
Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery Download PDFInfo
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- CN111180706A CN111180706A CN202010018265.XA CN202010018265A CN111180706A CN 111180706 A CN111180706 A CN 111180706A CN 202010018265 A CN202010018265 A CN 202010018265A CN 111180706 A CN111180706 A CN 111180706A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 24
- 239000011734 sodium Substances 0.000 title claims abstract description 24
- 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 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 title description 3
- GHSTWBLYJDCUQQ-UHFFFAOYSA-N [Ti].[Mn].[Na] Chemical compound [Ti].[Mn].[Na] GHSTWBLYJDCUQQ-UHFFFAOYSA-N 0.000 title description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- WQSRKBDBMQHEKH-UHFFFAOYSA-N [O-2].[Mn+2].[Ti+4].[Na+] Chemical compound [O-2].[Mn+2].[Ti+4].[Na+] WQSRKBDBMQHEKH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 238000007605 air drying Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical group [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000012876 topography Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
-
- 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
- H01M4/485—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of sodium titanium manganese oxide as a positive electrode material of a sodium ion battery, which comprises the following steps: respectively adding a specific sodium source, a manganese source and a titanium source compound into an oxalic acid solution, uniformly mixing, stirring for 1h at 60 ℃, then placing in an air drying oven for evaporation for 12h at 70-90 ℃ to dry, then grinding for 20-30min in a mortar, then placing in a muffle furnace for sintering for 2-12 h at 800-1000 ℃ under a certain atmosphere, and cooling to room temperature to obtain Na with a stable structure and good circulation performance0.44TixMn1‑xO2And (3) a positive electrode material.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage and secondary battery electrode material preparation, in particular to a preparation method of a sodium ion battery anode material sodium titanium manganese oxide.
Background
In recent years, research and development of sodium ion batteries become a research hotspot in the field of energy storage at home and abroad, sodium is widely distributed in nature and is low in price, the sodium battery and lithium ion batteries are located in the same main group and have similar physical and chemical properties, the working principle of the sodium ion batteries is similar to that of the lithium ion batteries, but cheap transition metal elements can be utilized in the aspect of electrode materials, so that the sodium ion batteries have a larger development space in the aspects of reducing cost and dependence on natural resource supply, and the sodium ion batteries are expected to become future large-scale energy storage battery devices.
Currently, positive electrode materials of sodium ion batteries that are receiving attention include transition metal oxides, polyanionic materials, prussian blue materials, organic positive electrode materials, and the like. The transition metal manganese element with rich resources, low price, green and innocuity in the transition metal oxide is widely used, and sodium manganate such as Na with a tunnel structure0.44MnO2Materials are representative thereof.
Na0.44MnO2The material provides a tunnel type structure which is beneficial to sodium ion extraction and insertion, but still has the defects of unstable structure and the like, and the basic structure and the surface composition of the material need to be further improved through means of doping, surface coating and the like, so that the electrochemical performance of the material is improved. In the currently published research work, various elements such as Fe, Co, Ti, K and the like are adopted for structural optimization, but it is noted that the performances of the obtained materials do not show significant improvement, and the main reason is that the preparation process is not fully optimized when the elements are doped. Therefore, a method for efficiently preparing sodium titanium manganese oxide serving as a positive electrode material of a sodium ion battery is urgently needed at present, so that the sodium titanium manganese oxide can show a stable effect when being used as the positive electrode material of the sodium ion battery.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide the sodium titanate manganese acid sodium for the positive electrode material of the sodium-ion battery, which has the advantages of simple and efficient preparation process, environmental protection and good cycle performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of sodium titanium manganese oxide serving as a positive electrode material of a sodium ion battery comprises the following steps:
(1) respectively adding a specific sodium source, a manganese source and a titanium source compound into a pre-prepared oxalic acid solution, and uniformly mixing to obtain a product I;
(2) stirring the first product at 60 ℃ for 1h, then placing the first product in an air drying oven at 70-90 ℃ for 12h to evaporate the first product to dryness, then grinding the second product in a mortar for 20-30min to obtain a second product, placing the second product in a muffle furnace, sintering the second product at 800-1000 ℃ for 2-12 h under a certain atmosphere condition, and cooling to room temperature to obtain Na0.44TixMn1-xO2，0.05≤x≤0.35。
Further, in the step (1), the concentration of the oxalic acid solution is 3-6 mol/L.
Further, in the step (1), the sodium source is sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate or sodium acetate.
Further, in the step (1), the manganese source is manganese acetate, manganese carbonate, manganese sesquioxide or manganese dioxide.
Further, in the step (1), the titanium source is n-butyl titanate or nano titanic acid.
Further, in the step (2), the certain atmosphere condition is an air or oxygen atmosphere.
Further, in the step (2), the gas supply amount under the certain atmosphere condition is 1L-10L/min per gram of the target material.
Further, in step (2), x is equal to 0.05, 0.11, 0.22 or 0.33.
The invention has the beneficial effects that: the preparation method provided by the invention has the advantages of easily available and cheap raw materials, mild reaction conditions, low requirements on equipment, convenience for industrial popularization and application, simple and efficient synthesis process, low synthesis cost, greenness and no pollution, and the sodium titanium manganese oxide used for preparing the sodium ion battery anode material has a stable structure and good cycle performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows a positive electrode material Na for a sodium-ion battery prepared in example 1 of the present invention0.44Ti0.22Mn0.78O2SEM surface topography of (a);
FIG. 2 shows the positive electrode material Na of the Na-ion battery prepared in example 2 of the invention0.44Ti0.11Mn0.89O2SEM surface topography of (a);
FIG. 3 shows the positive electrode material Na of the Na-ion battery prepared in example 1 of the present invention0.44Ti0.22Mn0.78O2XRD spectrum of (1);
FIG. 4 shows the positive electrode material Na of the Na-ion battery prepared in example 2 of the invention0.44Ti0.11Mn0.89O2The charge-discharge curve of the prepared experimental sodium-ion battery is shown.
Detailed Description
The following describes embodiments of the present invention in further detail through a description of examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a preparation method of sodium titanium manganese oxide serving as a positive electrode material of a sodium ion battery, which comprises the following technological processes:
respectively adding a specific sodium source, a specific manganese source and a specific titanium source compound into a pre-prepared oxalic acid solution, and uniformly mixing to obtain a product I;
step (2), stirring the product I at 60 ℃ for 1h, then placing the product I in an air drying oven at 70-90 ℃ for 12h to evaporate the product to dryness, then grinding the product I in a mortar for 20-30min to obtain a product II, placing the product II in a muffle furnace, sintering the product II at 800-1000 ℃ for 2-12 h under a certain atmosphere condition, and cooling to room temperature to obtain Na0.44TixMn1-xO2，0.05≤x≤0.35。
Further, in the step (1), the concentration of the oxalic acid solution is 3-6 mol/L.
Further, in the step (1), the sodium source is sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate or sodium acetate.
Further, in the step (1), the manganese source is manganese acetate, manganese carbonate, manganese sesquioxide or manganese dioxide.
Further, in the step (1), the titanium source is n-butyl titanate or nano titanic acid.
Further, in the step (2), the certain atmosphere condition is an air or oxygen atmosphere.
Further, in the step (2), the gas supply amount under the certain atmosphere condition is 1L-10L/min per gram of the target material.
Further, in step (2), x is equal to 0.05, 0.11, 0.22 or 0.33.
Example 1
A preparation method of sodium titanium manganese oxide serving as a positive electrode material of a sodium ion battery comprises the following steps:
in a pre-prepared oxalic acid solution, the ratio of 0.44: 0.22: adding sodium carbonate, manganese acetate and n-butyl titanate in a molar ratio of 0.78 in sequence, and uniformly mixing to obtain a product I; stirring the product I at 60 ℃ for 1h, then placing the product I in an air drying oven to evaporate at 80 ℃ for 12h to dryness, then grinding the product I in a mortar for 30min to obtain a product II, placing the product II in a muffle furnace to sinter the product II at 900 ℃ for 3h under the air atmosphere condition, and then cooling the product II to room temperature to obtain Na0.44Ti0.22Mn0.78O2FIG. 1 shows the SEM surface topography of the material, as shown in FIG. 3Shown as the material XRD spectrum. .
Example 2
A preparation method of sodium titanium manganese oxide serving as a positive electrode material of a sodium ion battery comprises the following steps:
in a pre-prepared oxalic acid solution, the ratio of 0.44: 0.10: adding sodium carbonate, manganese acetate and n-butyl titanate in a molar ratio of 0.90 in sequence, and uniformly mixing to obtain a product I; stirring the product I at 60 ℃ for 1h, then placing the product I in an air drying oven to evaporate at 80 ℃ for 12h to dryness, then grinding the product I in a mortar for 30min to obtain a product II, placing the product II in a muffle furnace to sinter the product II at 900 ℃ for 3h under the air atmosphere condition, and then cooling the product II to room temperature to obtain Na0.44Ti0.11Mn0.89O2FIG. 2 shows the SEM surface topography of the material.
Test example
Taking the product prepared in the example 2, a conductive agent Super P and a binder PVDF according to the mass ratio of 8: 1: 1, adding a certain amount of 1-methyl-2-pyrrolidone (NMP), stirring for 3 hours on a magnetic stirrer to prepare paste, coating the paste on an aluminum foil, drying for 12 hours in a vacuum drying oven at the temperature of 100 ℃, taking the uniformly coated place, cutting the aluminum foil into round pieces with the diameter of 14mm, drying for 12 hours in the vacuum drying oven at the temperature of 100 ℃, and transferring the round pieces into an argon glove box to be assembled. The sodium sheet is used as a negative electrode, the diaphragm is glass fiber, and the electrolyte is 1MNaClO4and/EC/PC, standing the assembled battery for 6h to be tested. The electrochemical test is carried out on a Land test system, the voltage range is 2-4V, and the current density is 20 mA/g. The charge-discharge curve of the experimental sodium-ion battery thus produced is shown in fig. 4. As can be seen, the second week material can release a reversible specific capacity of 107mAh/g, can also maintain a reversible specific capacity of 98 mAh/g after 200 weeks, and has excellent specific capacity and cycle performance.
Finally, it should be noted that the above preferred embodiments are only intended to illustrate the technical solution of the present invention and not to limit it, and it should be understood that various changes in form and details can be made by those skilled in the art without inventive efforts. In general, various changes in form and detail may be made by those skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. A preparation method of sodium titanium manganese oxide serving as a positive electrode material of a sodium ion battery is characterized by comprising the following steps:
(1) respectively adding a specific sodium source, a manganese source and a titanium source compound into a pre-prepared oxalic acid solution, and uniformly mixing to obtain a product I;
(2) stirring the first product at 60 ℃ for 1h, then placing the first product in an air drying oven at 70-90 ℃ for 12h to evaporate the first product to dryness, then grinding the second product in a mortar for 20-30min to obtain a second product, placing the second product in a muffle furnace, sintering the second product at 800-1000 ℃ for 2-12 h under a certain atmosphere condition, and cooling to room temperature to obtain Na0.44TixMn1-xO2，0.05≤x≤0.35。
2. The method for preparing the sodium titanium manganese oxide as the positive electrode material of the sodium-ion battery as claimed in claim 1, wherein in the step (1), the concentration of the oxalic acid solution is 3-6 mol/L.
3. The method for preparing the sodium titanium manganese oxide as the positive electrode material of the sodium-ion battery as claimed in claim 1, wherein in the step (1), the sodium source is sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate or sodium acetate.
4. The method for preparing the sodium titanium manganese oxide as the positive electrode material of the sodium-ion battery according to claim 1, wherein in the step (1), the manganese source is manganese acetate, manganese carbonate, manganese sesquioxide or manganese dioxide.
5. The method for preparing the sodium titanium manganese oxide as the positive electrode material of the sodium-ion battery according to claim 1, wherein in the step (1), the titanium source is n-butyl titanate or nano titanic acid.
6. The method for preparing the sodium titanium manganese oxide as the positive electrode material of the sodium-ion battery according to claim 1, wherein in the step (2), the certain atmosphere condition is an air or oxygen atmosphere.
7. The method for preparing sodium titanium manganese oxide as the positive electrode material of the sodium-ion battery according to claim 6, wherein in the step (2), the gas supply amount under the certain atmosphere condition is 1L-10L/min per gram of the target material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010018265.XA CN111180706A (en) | 2020-01-08 | 2020-01-08 | Preparation method of sodium titanium manganese acid sodium as positive electrode material of sodium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114655991A (en) * | 2022-03-24 | 2022-06-24 | 西北工业大学深圳研究院 | Modified sodium manganate material and preparation method and application thereof |
| CN114784262A (en) * | 2022-01-05 | 2022-07-22 | 山东理工大学 | Design and preparation of P2/T composite phase sodium ion battery anode material |
| CN114864891A (en) * | 2022-04-22 | 2022-08-05 | 四川大学 | Preparation method of heterojunction sodium ion battery sodium manganese oxygen positive electrode material and positive electrode material |
| CN115020694A (en) * | 2022-05-25 | 2022-09-06 | 江苏理工学院 | Anion-cation co-modified tunnel oxide material and preparation method and application thereof |
| WO2023098168A1 (en) * | 2021-11-30 | 2023-06-08 | 广东邦普循环科技有限公司 | Preparation method for p2-type manganese-based sodium-ion battery positive electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263583A (en) * | 2004-03-19 | 2005-09-29 | National Institute Of Advanced Industrial & Technology | Crystal material of alkali-transition metal oxide and its producing method |
| CN105692721A (en) * | 2016-01-29 | 2016-06-22 | 太原理工大学 | Sodium ion battery positive electrode material, and preparation method and application method thereof |
| CN105977486A (en) * | 2016-06-22 | 2016-09-28 | 浙江大学 | Preparation method and application of sodium-rich transition metal silicate as sodium ion battery cathode material |
| US20180090758A1 (en) * | 2016-09-29 | 2018-03-29 | Uchicago Argonne, Llc | High performance layered cathode materials for high voltage sodium-ion batteries |
-
2020
- 2020-01-08 CN CN202010018265.XA patent/CN111180706A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263583A (en) * | 2004-03-19 | 2005-09-29 | National Institute Of Advanced Industrial & Technology | Crystal material of alkali-transition metal oxide and its producing method |
| CN105692721A (en) * | 2016-01-29 | 2016-06-22 | 太原理工大学 | Sodium ion battery positive electrode material, and preparation method and application method thereof |
| CN105977486A (en) * | 2016-06-22 | 2016-09-28 | 浙江大学 | Preparation method and application of sodium-rich transition metal silicate as sodium ion battery cathode material |
| US20180090758A1 (en) * | 2016-09-29 | 2018-03-29 | Uchicago Argonne, Llc | High performance layered cathode materials for high voltage sodium-ion batteries |
Non-Patent Citations (2)
| Title |
|---|
| DING ZHANG等: "Fast and scalable synthesis of durable Na0.44MnO2 cathode material via an oxalate precursor method for Na-ion batteries", 《ELECTROCHIMICA ACTA》 * |
| YUESHENG WANG等: "Ti-substituted tunnel-type Na0.44MnO2 oxide as a negative electrode for aqueous sodium-ion batteries", 《NATURE COMMUNICATIONS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023098168A1 (en) * | 2021-11-30 | 2023-06-08 | 广东邦普循环科技有限公司 | Preparation method for p2-type manganese-based sodium-ion battery positive electrode material |
| GB2618967A (en) * | 2021-11-30 | 2023-11-22 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for p2-type manganese-based sodium-ion battery positive electrode material |
| CN114784262A (en) * | 2022-01-05 | 2022-07-22 | 山东理工大学 | Design and preparation of P2/T composite phase sodium ion battery anode material |
| CN114655991A (en) * | 2022-03-24 | 2022-06-24 | 西北工业大学深圳研究院 | Modified sodium manganate material and preparation method and application thereof |
| CN114655991B (en) * | 2022-03-24 | 2024-01-09 | 西北工业大学深圳研究院 | Modified sodium manganate material and preparation method and application thereof |
| CN114864891A (en) * | 2022-04-22 | 2022-08-05 | 四川大学 | Preparation method of heterojunction sodium ion battery sodium manganese oxygen positive electrode material and positive electrode material |
| CN115020694A (en) * | 2022-05-25 | 2022-09-06 | 江苏理工学院 | Anion-cation co-modified tunnel oxide material and preparation method and application thereof |
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Application publication date: 20200519 |