CN111204811B - Preparation method of vanadium-based spinel material and preparation method of battery anode - Google Patents
Preparation method of vanadium-based spinel material and preparation method of battery anode Download PDFInfo
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- CN111204811B CN111204811B CN202010031177.3A CN202010031177A CN111204811B CN 111204811 B CN111204811 B CN 111204811B CN 202010031177 A CN202010031177 A CN 202010031177A CN 111204811 B CN111204811 B CN 111204811B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a vanadium-based spinel material, which comprises the following steps: A) mixing manganese acetate and vanadyl acetylacetonate in alcohol, and heating and evaporating the obtained mixed solution to dryness to obtain a gel precursor; B) drying the gel-like precursor to obtain a dried substance; C) annealing the dried material obtained in the step B) in a protective atmosphere to obtain MnV2O4Spinel; the annealing temperature is 600-1000 ℃, and the annealing time is 6-18 hours. The invention firstly uses a sol-gel method to obtain a precursor which is uniformly mixed, and then uses a calcination method to obtain MnV with good crystallinity2O4Spinel. The vanadium-based spinel material prepared by the method disclosed by the invention is good in crystallinity and high in purity, can be widely applied to the fields of batteries, capacitors, electrocatalysis, electromagnetic refrigeration and the like, and particularly has excellent electrochemical properties. The invention also provides a preparation method of the battery anode.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to a preparation method of a vanadium-based spinel material and a preparation method of a battery anode.
Background
MnV2O4Is a common ternary material, and the crystal lattice structure of the ternary material is a face-centered cubic lattice. The chemical formula is AB2O4Wherein the A site is a divalent manganese ion occupying a tetrahedral site of oxygen; the B site is trivalent vanadium ion and occupies an octahedral site of oxygen. The material has excellent physical and chemical properties, and has great practical prospect in the fields of energy storage, electrocatalysis, magnetic refrigeration, sensor magnetic switches, composite materials and the like.
Such excellent materials have been widely studied in various fields, but the synthesis methods thereof are limited to chemical vapor transport, multi-step solid phase methods, microwave-assisted synthesis methods, and the like. The existing synthesis method not only has complex synthesis steps and harsh required conditions, but also has small once synthesis amount and difficult large-scale production.
Disclosure of Invention
The invention aims to provide a preparation method of a vanadium-based spinel material and a preparation method of a battery anode, wherein the preparation method is simple and controllableObtaining MnV2O4The spinel phase is pure, and has excellent electrochemical performance.
The invention provides a preparation method of a vanadium-based spinel material, which comprises the following steps:
A) mixing manganese acetate and vanadyl acetylacetonate in alcohol, and heating and evaporating the obtained mixed solution to dryness to obtain a gel precursor;
B) drying the gel-like precursor to obtain a dried substance;
C) annealing the dried material obtained in the step B) in a protective atmosphere to obtain MnV2O4Spinel;
the annealing temperature is 600-1000 ℃, and the annealing time is 6-18 hours.
Preferably, the molar concentration of manganese acetate in the mixed solution is 0.5-3 x 10-4mol/L；
The molar concentration of vanadyl acetylacetonate in the mixed solution is 1.6-2.4 multiplied by 10-4mol/L。
Preferably, the heating temperature in the step A) is 50-80 ℃.
Preferably, the drying temperature in the step B) is 30-60 ℃;
the drying time in the step B) is 12-24 hours.
Preferably, the alcohol in the step A) is one or more of absolute ethyl alcohol, absolute propyl alcohol, methanol and ethylene glycol;
preferably, manganese acetate and vanadyl acetylacetonate are mixed in alcohol, and then ultrasonic treatment is carried out until the solution is clear and has no precipitate, so as to obtain a mixed solution;
the time of the ultrasonic treatment is 2-4 hours.
Preferably, the obtained mixed solution is heated and evaporated to dryness under the condition of magnetic stirring;
the rotating speed of the magnetic stirring is 400-500 rpm.
The invention provides a preparation method of a battery anode, which is characterized in that a vanadium-based spinel active material is prepared according to the preparation method, and then the vanadium-based spinel active material is prepared into the battery anode.
The invention provides a preparation method of a vanadium-based spinel material, which comprises the following steps: A) mixing manganese acetate and vanadyl acetylacetonate in alcohol, and heating and evaporating the obtained mixed solution to dryness to obtain a gel precursor; B) drying the gel-like precursor to obtain a dried substance; C) annealing the dried material obtained in the step B) in a protective atmosphere to obtain MnV2O4Spinel; the annealing temperature is 600-1000 ℃, and the annealing time is 6-18 hours. The invention firstly uses a sol-gel method to obtain a precursor which is uniformly mixed, and then uses a calcination method to obtain MnV with good crystallinity2O4Spinel. The vanadium-based spinel material prepared by the method disclosed by the invention is good in crystallinity and high in purity, can be widely applied to the fields of batteries, capacitors, electrocatalysis, electromagnetic refrigeration and the like, and particularly has excellent electrochemical properties.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows MnV in example 1 of the present invention2O4A picture of a spinel object;
FIG. 2 shows MnV in example 1 of the present invention2O4Scanning electron microscope pictures of spinel;
FIG. 3 shows MnV in example 1 of the present invention2O4Transmission electron microscope pictures of spinel;
FIG. 4 shows MnV obtained in example 1 of the present invention2O4An X-ray diffraction pattern of spinel;
FIG. 5 shows MnV obtained in example 2 of the present invention2O4An X-ray diffraction pattern of spinel;
FIG. 6 shows MnV obtained in example 3 of the present invention2O4An X-ray diffraction pattern of spinel;
FIG. 7 shows MnV obtained in example 4 of the present invention2O4An X-ray diffraction pattern of spinel;
FIG. 8 shows MnV obtained in example 4 of the present invention2O4Scanning electron micrographs of spinel;
FIG. 9 shows MnV obtained in example 5 of the present invention2O4An X-ray diffraction pattern of spinel;
FIG. 10 shows MnV obtained in example 5 of the present invention2O4Scanning electron micrographs of spinel;
FIG. 11 shows MnV obtained by the present invention2O4Spinel zinc ion battery performance data plot.
Detailed Description
The invention provides a preparation method of a vanadium-based spinel material, which comprises the following steps:
A) mixing manganese acetate and vanadyl acetylacetonate in alcohol, and heating and evaporating the obtained mixed solution to dryness to obtain a gel precursor;
B) drying the gel-like precursor to obtain a dried substance;
C) annealing the dried material obtained in the step B) in a protective atmosphere to obtain MnV2O4Spinel;
the annealing temperature is 600-1000 ℃, and the annealing time is 6-18 hours.
The invention takes manganese acetate and vanadyl acetylacetonate as raw materials and adopts a sol-gel method to prepare a gelatinous precursor. Preferably, the manganese acetate and vanadyl acetylacetonate are mixed in anhydrous alcohol, a clear and uniform solution is obtained by ultrasonic treatment, and then the obtained mixed solution is heated and evaporated to dryness under the condition of magnetic stirring to obtain the gel-like precursor.
In the invention, the anhydrous alcohol is preferably one or more of anhydrous ethanol, anhydrous propanol, methanol and glycol, and the alcohol such as the anhydrous ethanol is used as a solvent, so that manganese acetate and vanadyl acetylacetonate can be more fully mixed, and the purity of a final product is improved.
In the invention, the molar concentration of manganese acetate in the mixed solution is preferably 0.5-3 × 10-4mol/L, more preferably 1 to 2X 10-4mol/L; the preferable molar concentration of vanadyl acetylacetonate in the mixed solution is 1.6-2.4 x 10- 4mol/L, more preferably 2X 10-4mol/L. In the invention, the molar ratio of manganese acetate to vanadyl acetylacetonate is preferably 1 (1-3), more preferably 1: 2.
in the invention, the frequency of the ultrasonic wave is preferably 50-100 Hz, and more preferably 60-90 Hz; the time of the ultrasonic treatment is preferably 2-4 hours. If the sonication is not carried out or the sonication time is not sufficient, the powders cannot be mixed sufficiently, which may lead to the presence of manganese or vanadium oxide impurities in the final sample.
In the invention, the heating temperature is preferably 50-80 ℃, more preferably 60-70 ℃, and specifically, in the embodiment of the invention, the heating temperature can be 80 ℃; the heating time is not particularly limited in the present invention, and the heating is performed until the mixed solution contains no alcohol solvent.
In the invention, the rotation speed of the magnetic stirring is preferably 400-500 rpm.
After obtaining the gel-like precursor, drying the precursor to obtain a dried product, wherein the drying temperature is preferably 30-60 ℃, and more preferably 40-50 ℃; the drying time is preferably 12 to 24 hours, and more preferably 15 to 20 hours. According to the invention, the precursor is preferably placed in an oven for drying.
After obtaining the dried product, annealing the dried product in protective atmosphere to obtain MnV2O4Spinel.
In the invention, the protective atmosphere is preferably argon, nitrogen and the like, and in the invention, the protective gas is preferably introduced for 5-10 min before the annealing temperature rise, so that oxygen in the annealing device is removed.
In the invention, the annealing temperature is preferably 600-1000 ℃, more preferably 700-900 ℃, and most preferably 800 ℃; the temperature is too high, the sintered sample is seriously caked, the temperature is too low, and the crystallinity is not good; the annealing time is preferably 6 to 18 hours, more preferably 8 to 16 hours, and most preferably 10 to 12 hours.
The invention also provides a preparation method of the battery anode, the battery anode comprises an active material, the active material is the vanadium-based spinel material prepared by the preparation method, the vanadium-based spinel material is prepared by the preparation method, and then the vanadium-based spinel material is prepared into the battery anode.
The specific method for preparing the battery anode from the vanadium-based spinel is not particularly limited, and the battery anode material and the preparation method which are commonly used in the field can be adopted.
The invention provides a preparation method of a vanadium-based spinel material, which comprises the following steps: A) mixing manganese acetate and vanadyl acetylacetonate in alcohol, and heating and evaporating the obtained mixed solution to dryness to obtain a gel precursor; B) drying the gel-like precursor to obtain a dried substance; C) annealing the dried material obtained in the step B) in a protective atmosphere to obtain MnV2O4Spinel; the annealing temperature is 600-1000 ℃, and the annealing time is 6-18 hours. The invention firstly uses a sol-gel method to obtain a precursor which is uniformly mixed, and then uses a calcination method to obtain MnV with good crystallinity2O4Spinel. The vanadium-based spinel material prepared by the method disclosed by the invention is good in crystallinity and high in purity, can be widely applied to the fields of batteries, capacitors, electrocatalysis, electromagnetic refrigeration and the like, and particularly has excellent electrochemical properties.
Compared with the prior art, the invention has the advantages that:
1) the invention has simple production process flow and controllable yield, and can realize large-scale production only by correspondingly increasing the amount of manganese acetate, vanadyl acetylacetonate and absolute ethyl alcohol.
2) The raw materials used in the invention have wide sources and low price, so the production cost is low.
3) The production process is safe, and the annealing is carried out under the protection of inert gas, so that the method is safe and harmless.
4) The invention is harmless to the environment in the experimental process, and does not produce waste liquid and waste material.
5) MnV produced by the invention2O4The spinel has wide application, not only can be used as an electrode material in the field of energy storage, but also can be used in the fields of catalysis, electromagnetic refrigeration and the like.
In order to further illustrate the present invention, the following will describe in detail the preparation method of a vanadium-based spinel material and the preparation method of a battery positive electrode provided by the present invention with reference to the examples, which should not be construed as limiting the scope of the present invention.
Example 1
a. 0.245g (1mmol) of manganese acetate and 0.5303g (2mmol) of vanadyl acetylacetonate are treated by ultrasonic treatment in 100mL of absolute ethanol for 2 hours to obtain a clear and uniform solution;
b. b, evaporating the solution obtained in the step a to dryness by means of magnetic stirring and heating at the rotating speed of 400rpm at the temperature of 80 ℃ to obtain a gel-like precursor, and drying the precursor in a drying oven at the temperature of 50 ℃ for 12 hours;
c. annealing the dried substance obtained in the step b for 12 hours at 800 ℃ under the protection of argon atmosphere to obtain MnV2O4Spinel. MnV2O4The yield of spinel was 87.85%.
Obtained MnV2O4The spinel material picture is shown in FIG. 1, and the Scanning Electron Microscope (SEM) picture and the Transmission Electron Microscope (TEM) picture are shown in FIGS. 2-3. As can be seen from FIGS. 2 to 3, MnV sintered at 800 ℃ is2O4The spinel has good crystallinity and uniform particles.
FIG. 4 shows MnV in this embodiment2O4X-ray diffraction pattern of spinel, as can be seen from FIG. 4, MnV obtained in this example2O4The spinel has no impurity phase, and the impurity exceeds the detection limit.
Manufacturing an electrode plate: mixing MnV2O4Spinel, conductive agent SP, binder PVDF, 7: 2: 1 in NMP (1-methyl-2 pyrrolidone) to obtain uniform slurry, coating the uniform slurry on a current collector steel mesh, pre-drying in an oven at 70 ℃ for 30 minutes, and finally drying at 100 DEG CCompletely drying in a vacuum oven overnight to obtain an electrode slice;
assembling the battery: subjecting the obtained MnV to2O4The 2032 type button cell is assembled in the air by taking the electrode slice as the anode, the zinc slice as the cathode, the 3M zinc trifluoromethanesulfonate as the electrolyte and the filter paper as the diaphragm.
And (3) testing the battery: the button cell prepared above was tested in the wuhan blue-electricity system with the room temperature constant at 25 ℃, and the performance test data is shown in fig. 11.
Example 2
MnV was prepared according to the method of example 12O4Spinel, except that the mass of manganese acetate and vanadyl acetylacetonate in step a in this example were 2.45g and 5.303g, respectively, and the absolute ethanol was 1L.
FIG. 5 shows MnV obtained in example 2 of the present invention2O4The X-ray diffraction pattern of spinel is shown in FIG. 5, and the product obtained by enlarging the dosage is also MnV2O4The production of MnV2O4The method of (3) is suitable for large-scale production.
Example 3
MnV was prepared according to the method of example 12O4Spinel, except that the volume of absolute ethanol in this example was 50 mL.
FIG. 6 shows MnV obtained in example 3 of the present invention2O4The X-ray diffraction pattern of spinel is shown in FIG. 6, and the product obtained by reducing the amount of absolute ethanol is still MnV2O4However, the somewhat heterogeneous phase indicates that reducing the amount of absolute ethanol will affect the purity.
Example 4
MnV was prepared according to the method of example 12O4Spinel, except that the annealing temperature in this example was 600 ℃.
FIG. 7 shows MnV obtained in example 4 of the present invention2O4As is clear from FIG. 7, the X-ray diffraction pattern of spinel shows that the phase produced at 600 ℃ is also MnV2O4Spinel, but it can be seen from FIG. 8 that the crystallinity is not at 800 ℃ CGood results are obtained.
FIG. 8 shows MnV obtained in example 4 of the present invention2O4Scanning electron micrographs of spinel.
Example 5
MnV was prepared according to the method of example 12O4Spinel, except that the annealing temperature in this example was 1000 ℃.
FIG. 9 shows MnV obtained in example 5 of the present invention2O4As is clear from FIG. 9, the X-ray diffraction pattern of spinel shows that the phase produced at 1000 ℃ is also MnV2O4Spinel, but it can be seen from fig. 10 that the crystallization temperature is too high and the agglomeration is severe.
FIG. 10 shows MnV obtained in example 5 of the present invention2O4Scanning electron micrographs of spinel.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a vanadium-based spinel material comprises the following steps:
A) mixing manganese acetate and vanadyl acetylacetonate in alcohol, and heating and evaporating the obtained mixed solution to dryness to obtain a gel precursor;
B) drying the gel-like precursor to obtain a dried substance;
C) annealing the dried material obtained in the step B) in a protective atmosphere to obtain MnV2O4Spinel;
the annealing temperature is 600-1000 ℃, and the annealing time is 6-18 hours.
2. The method according to claim 1, wherein the molar concentration of manganese acetate in the mixed solution is 0.5 to 3X 10-4mol/L；
Vanadyl acetylacetonate in the mixed solutionThe molar concentration of (A) is 1.6 to 2.4 x 10-4mol/L。
3. The method according to claim 1, wherein the heating temperature in the step A) is 50 to 80 ℃.
4. The preparation method according to claim 1, wherein the drying temperature in the step B) is 30-60 ℃;
the drying time in the step B) is 12-24 hours.
5. The preparation method according to claim 1, wherein the alcohol in step A) is one or more of absolute ethyl alcohol, absolute propyl alcohol, methanol and ethylene glycol.
6. The preparation method according to claim 1, wherein manganese acetate and vanadyl acetylacetonate are mixed in alcohol and then subjected to ultrasonic treatment until the solution is clear without precipitation to obtain a mixed solution;
the time of the ultrasonic treatment is 2-4 hours.
7. The production method according to claim 1 or 6, wherein the resulting mixed solution is heated to dryness under magnetic stirring;
the rotating speed of the magnetic stirring is 400-500 rpm.
8. The preparation method of the battery positive electrode is characterized in that the vanadium-based spinel material is prepared according to any one of claims 1 to 7, and then the vanadium-based spinel material is prepared into the battery positive electrode.
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| CN101423253A (en) * | 2008-11-26 | 2009-05-06 | 华中师范大学 | ZnV2O4 lithium storage materials and preparation method thereof |
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| CN104485450A (en) * | 2014-12-19 | 2015-04-01 | 中南大学 | Preparation method of lithium ion battery anode material FeV2O4 |
| CN105261744A (en) * | 2015-09-22 | 2016-01-20 | 中南大学 | Preparation method of porous vanadium manganese oxide anode material |
| CN107010950A (en) * | 2017-02-28 | 2017-08-04 | 南京航空航天大学 | A kind of preparation method of novel spinel multiferroic oxide ceramics |
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- 2020-01-13 CN CN202010031177.3A patent/CN111204811B/en active Active
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| CN101423253A (en) * | 2008-11-26 | 2009-05-06 | 华中师范大学 | ZnV2O4 lithium storage materials and preparation method thereof |
| CN102299314A (en) * | 2011-07-14 | 2011-12-28 | 上海微纳科技有限公司 | Preparation method of positive electrode material spinel LiMn2O4 for lithium ion battery |
| CN104485450A (en) * | 2014-12-19 | 2015-04-01 | 中南大学 | Preparation method of lithium ion battery anode material FeV2O4 |
| CN105261744A (en) * | 2015-09-22 | 2016-01-20 | 中南大学 | Preparation method of porous vanadium manganese oxide anode material |
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Non-Patent Citations (2)
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