CN114229901B - Transition metal vanadate material and preparation method and application thereof - Google Patents

Transition metal vanadate material and preparation method and application thereof Download PDF

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CN114229901B
CN114229901B CN202111555365.7A CN202111555365A CN114229901B CN 114229901 B CN114229901 B CN 114229901B CN 202111555365 A CN202111555365 A CN 202111555365A CN 114229901 B CN114229901 B CN 114229901B
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manganese salt
metal vanadate
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CN114229901A (en
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赵彦明
文妮
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South China Institute of Collaborative Innovation
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    • C01G45/00—Compounds of manganese
    • H—ELECTRICITY
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    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
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    • C01—INORGANIC CHEMISTRY
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a transition metal vanadate material, and a preparation method and application thereof, and belongs to the field of vanadate materials. The preparation method comprises the following steps: (1) Adding ammonium metavanadate and manganese salt into water, stirring until the ammonium metavanadate and manganese salt are fully dissolved, adding citric acid monohydrate as a chelating agent and a carbon source, continuously stirring in a water bath until the water is evaporated completely, and then drying; (2) Pre-calcining the dried product in argon or reducing atmosphere, naturally cooling, and grinding to obtain a powdery material; (3) Calcining the powdery material under argon or reducing atmosphere, and naturally cooling to obtain the transition metal vanadate material. The pure-phase MnV 2O4 is synthesized by adopting a sol-gel method, and the method has the advantages of simple preparation process, environmental protection, rich raw material sources and controllable yield, and is suitable for large-scale production. In addition, the MnV 2O4 synthesized by the method can be used as a negative electrode material of a lithium ion battery and a positive electrode material of a zinc ion battery at the same time, and has excellent performance.

Description

Transition metal vanadate material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of vanadate materials, and particularly relates to a transition metal vanadate material, and a preparation method and application thereof.
Background
Lithium ion batteries are one of the most promising energy storage systems at present, and are widely applied to electric automobiles and portable electronic products. The negative electrode material plays an important role in the performance of a lithium ion battery as one of the key components thereof. Currently, graphite and lithium titanate are the most commonly used commercially used materials in various lithium ion battery anode materials. However, the limited theoretical specific capacity of graphite (372 mA h g -1) and potential safety hazards limit its application, and the high discharge/charge potential plateau of lithium titanate (-1.6V vs Li/Li +) reduces the energy and power density of the whole battery. Therefore, there is an urgent need to find a negative electrode material having good electrochemical properties. In recent years, mixed transition metal oxides have been widely studied in lithium ion anode materials because of their ultra-high theoretical specific capacities and synergistic effects between bimetallic elements. Considering the multiple valence states of vanadium and manganese and the high electrochemical activity of the vanadium and manganese, the transition metal vanadate MnV 2O4 is expected to be a high-performance anode material.
In addition, among various electrochemical energy storage systems, rechargeable aqueous zinc ion batteries are the most promising lithium ion battery substitutes in future large-scale energy storage technologies due to their low cost, abundant raw materials and environmental friendliness. At present, manganese-based and vanadium-based oxides are main positive electrode materials of zinc ion batteries, wherein the voltage window of the manganese-based oxides is 0.8-1.8V, and the voltage window of the vanadium-based oxides is 0.1-1.4V. Inspired by the synergistic effect of the bimetallic elements in the mixed transition metal oxide in the lithium ion battery, the manganese-based oxide and the vanadium-based oxide are combined, and the synergistic effect is utilized to realize the zinc ion battery positive material with wider voltage window and excellent performance.
At present, although the preparation of MnV 2O4 is reported, the synthetic method is complex in steps, needs further modification, has small synthesis amount each time, and is not suitable for large-scale preparation; the raw materials used have certain toxicity and do not meet the requirement of environmental protection.
Disclosure of Invention
In order to overcome the defects, the primary aim of the invention is to provide a preparation method of a transition metal vanadate material.
Another object of the present invention is to provide a transition metal vanadate material prepared by the above method.
It is still another object of the present invention to provide the use of the above-described transition metal vanadate material in the field of lithium ion batteries and zinc ion batteries.
The aim of the invention is achieved by the following technical scheme.
A preparation method of a transition metal vanadate material comprises the following steps:
(1) Preparing a precursor: adopting a sol-gel method to synthesize MnV 2O4, adding ammonium metavanadate (NH 4VO3) and manganese salt into water, stirring until the ammonium metavanadate and the manganese salt are fully dissolved, adding citric acid monohydrate as a chelating agent and a carbon source, and continuously stirring under a water bath until the water is evaporated completely and then drying;
(2) Pretreatment: pre-calcining the dried product in the step (1) under argon or reducing atmosphere, naturally cooling, and grinding to obtain a powdery material;
(3) High-temperature calcination: calcining the powdery material obtained in the step (2) under argon or reducing atmosphere, and naturally cooling to obtain the transition metal vanadate material.
Preferably, in the step (1), the manganese salt is one of manganese acetate (Mn (CH 3COO)2), manganese chloride (MnCl 2), manganese carbonate (MnCO 3) and manganese sulfate (MnSO 4), and the molar ratio of vanadium in ammonium metavanadate to manganese in the manganese salt is 2:1.
Preferably, the molar ratio of the citric acid to the manganese salt in the step (1) is 1:1-1:3, and more preferably 1:3.
Preferably, the temperature of the water bath in step (1) is 70-100 ℃, more preferably 70 ℃.
Preferably, the temperature of the precalcination in step (2) is 300-400 ℃, the time is 2-6h, and more preferably, the precalcination is carried out at 350 ℃ for 5h.
Preferably, the reducing atmosphere in the step (2) and the step (3) is argon containing 5% of hydrogen.
Preferably, the calcination temperature in step (3) is 500-800 ℃, and the calcination time is 5-12 hours, and more preferably, the calcination is performed at 600 ℃ for 8 hours.
A transition metal vanadate material obtainable by the preparation method of any of the preceding claims.
The application of the transition metal vanadate material in preparing the lithium ion battery cathode material is provided.
The application of the transition metal vanadate material in preparing the zinc ion battery anode material is provided.
Compared with the prior art, the invention has the following advantages:
(1) The pure-phase MnV 2O4 is synthesized under the protective atmosphere by adopting the sol-gel method, and the preparation method has the advantages of simple process, environmental protection, rich raw material sources and controllable yield, and is suitable for large-scale production.
(2) The MnV 2O4 synthesized by the method can be used as a negative electrode material of a lithium ion battery and a positive electrode material of a zinc ion battery at the same time, and has excellent performance.
(3) The MnV 2O4 synthesized by the method has wide application, and can be used for electrode materials in the energy storage field, and can also be used in the fields of catalysis, refrigeration and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of MnV 2O4 in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of MnV 2O4 in example 1 of the present invention.
FIG. 3 is a graph showing the cycle performance of MnV 2O4 as a negative electrode of a lithium ion battery in example 1 of the present invention.
Fig. 4 is a scanning electron microscope image of MnV 2O4 of example 1 of the present invention before cycling as a negative electrode of a lithium ion battery.
Fig. 5 is a scanning electron microscope image of MnV 2O4 of example 1 of the present invention after 100 cycles as a negative electrode of a lithium ion battery.
Fig. 6 is a scanning electron microscope image of MnV 2O4 of example 1 of the present invention after 500 cycles as a negative electrode of a lithium ion battery.
FIG. 7 is an X-ray diffraction pattern of MnV 2O4 in example 2 of the present invention.
FIG. 8 is a graph showing the cycle performance of MnV 2O4 as the positive electrode of a zinc ion battery in example 2 of the present invention.
FIG. 9 is an X-ray diffraction pattern of MnV 2O4 in example 3 of the present invention.
Fig. 10 is a graph showing cycle performance of MnV 2O4 as a negative electrode of a lithium ion battery in example 3 of the present invention.
FIG. 11 is an X-ray diffraction pattern of MnV 2O4 in example 4 of the present invention.
Fig. 12 is a graph showing cycle performance of MnV 2O4 as a negative electrode of a lithium ion battery in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples and drawings, but embodiments of the present invention are not limited thereto. All materials and reagents used in the present invention are commercially available conventional materials and reagents unless otherwise specified.
Example 1
NH 4VO3 and Mn (CH 3COO)2) are added into deionized water according to the stoichiometric ratio of V: mn=2:1, stirred until the mixture is fully dissolved, then added with citric acid monohydrate (the molar ratio of citric acid to manganese salt is 1:3) as a chelating agent and a carbon source, and continuously stirred in a water bath at 70 ℃ until the water is evaporated completely and then dried, the obtained uniformly mixed precursor is pre-calcined for 5 hours at 350 ℃ in an argon atmosphere containing 5% of hydrogen, naturally cooled and ground to obtain a powdery material, and calcined for 8 hours at 600 ℃ in an argon atmosphere containing 5% of hydrogen and naturally cooled to obtain MnV 2O4.
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 1. As can be seen from fig. 1, pure-phase cubic-crystal MnV 2O4 material was synthesized by sol-gel method. The purity of the product is high as shown by the absence of impurity peaks in the spectrogram. The scanning electron microscope of the product is shown in fig. 2, and it can be seen that MnV 2O4 has an irregularly shaped block structure with a size of several hundred nanometers to tens of micrometers.
Manufacturing an electrode plate: the MnV 2O4, the conductive agent Super P and the binder sodium alginate prepared in the embodiment are fully mixed and ground in deionized water according to the ratio of 7:2:1 to obtain uniform slurry, the slurry is smeared on a current collector copper foil, the surface water solvent is naturally volatilized to dryness, and finally the electrode slice is obtained after the electrode slice is dried in a vacuum oven at 90 ℃ for one night.
And (3) battery assembly: and (3) assembling the obtained MnV 2O4 pole piece serving as a working electrode, a lithium piece serving as a counter electrode and EC: DEC: EMC (1:1:1 vol%) serving as electrolyte and Celgard2320 serving as a diaphragm into the CR2032 type button battery in a high-purity argon glove box.
And (3) battery testing: the button cell prepared above was tested in a marchantia blue electrical system, and the room temperature was constant at 25 ℃.
The MnV 2O4 of the embodiment is used as a lithium battery cathode material, and is circulated 500 times when the current density is 200mA/g in the voltage range of 0.01-3V, and the circulation performance is shown in figure 3. As can be seen from fig. 3, the initial charge specific capacity is about 340mAh/g, and the specific capacity is increasing as the cycle proceeds. After 500 cycles, the specific capacity of the battery reaches 1325mAh/g. The MnV 2O4 prepared by the embodiment has high specific capacity as a lithium ion battery anode material, and is a lithium ion battery anode material with great potential.
The scanning electron microscope diagrams of the MnV 2O4 used as the anode material of the lithium ion battery in the embodiment after 100 times of circulation and 500 times of circulation are respectively shown in fig. 4, fig. 5 and fig. 6. As can be seen from the fresh electrode before cycling of fig. 4, irregularly shaped MnV 2O4 pieces are uniformly dispersed over the entire electrode surface and the pieces size of the fresh MnV 2O4 electrode surface are more uniform than MnV 2O4 powder. This is because MnV 2O4 powder, conductive carbon black and binder are mixed and ground together during the preparation of fresh MnV 2O4 electrode, thereby breaking up some relatively large particles. Although the MnV 2O4 pieces were surrounded by binder and conductive carbon black, the exposed bulk surface was smooth. As can be seen from the electrode after 100 cycles of fig. 5, large aggregates appear on the electrode surface, varying in size from a few micrometers to tens of micrometers, which appear to consist of the recombination reaction product stacked on the unreacted block. Because of the inadequate reaction, the material is only broken up at the surface, so that these large aggregates are not in good contact with each other and there are very large gaps. In contrast, the surface where the reaction takes place is very rough and contains many small particles. It can be appreciated that after 100 cycles, the surface of the MnV 2O4 block was powdered, increasing the specific surface area and the number of surface active sites of the MnV 2O4 electrode, resulting in an increase in specific capacity. It should be noted that the pulverization of the block occurs only at the surface and the internal reaction does not completely occur at this time, so that the diffusion control process is weaker than the surface capacitance control process. As can be seen from the electrode after 500 cycles of fig. 6, cracks were not observed on the surface, and a large number of nanoparticles were uniformly distributed on the surface, indicating that MnV 2O4 blocks were further pulverized, contributing to shortening the diffusion path of lithium ions, thereby promoting electrochemical kinetics of the electrode material, which is reflected in an increase in specific capacity. Therefore, the specific capacity of the MnV 2O4 provided by the invention can be improved by using the MnV 2O4 as a negative electrode of a lithium ion battery. Clearly, micron-sized blocks do not facilitate intercalation/deintercalation of lithium ions, and only allow rapid electrochemical reactions at the surface, providing relatively low specific capacities. From the morphological analysis of the MnV 2O4 electrode in different states, the MnV 2O4 block is gradually crushed along with the increase of the cycle times, which increases the specific surface area and the number of active sites of the MnV 2O4 electrode and shortens the lithium ion diffusion path. Thus, the contribution of the surface capacitance control and diffusion control processes to the total specific capacity will increase. However, in the early stage of the reaction, pulverization mainly occurs on the surface, and the reaction is insufficient, and the diffusion control effect is weaker than the capacitance control effect. The reaction is relatively more sufficient due to the pulverization in the later-stage materials, and the diffusion control effect is enhanced.
Example 2
NH 4VO3 and MnCO 3 are added into deionized water according to the stoichiometric ratio of V:Mn=2:1, and citric acid monohydrate (the molar ratio of citric acid to manganese salt is 1:3) is added after the mixture is stirred until the mixture is fully dissolved, and the mixture is continuously stirred in a water bath at 70 ℃ until the water is evaporated completely and then dried. Pre-calcining the obtained precursor mixed uniformly for 5 hours at 350 ℃ in pure argon atmosphere, naturally cooling, and grinding to obtain a powdery material; calcining for 10 hours at 680 ℃ under pure argon atmosphere, and naturally cooling to obtain MnV 2O4.
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 7. As can be seen from fig. 7, pure-phase cubic MnV 2O4 material was synthesized by sol-gel method. The purity of the product is high as shown by the absence of impurity peaks in the spectrogram.
Manufacturing an electrode plate: fully mixing MnV 2O4, a conductive agent Super P and a binder PVDF in a ratio of 7:2:1 in NMP (1-methyl-2 pyrrolidone) and grinding to obtain uniform slurry, smearing the slurry on a current collector titanium foil, and completely drying in a vacuum oven at 90 ℃ for one night to obtain an electrode slice;
And (3) battery assembly: and (3) assembling the obtained MnV 2O4 electrode plate serving as a working electrode, a zinc plate serving as a counter electrode, 3M zinc trifluoromethane sulfonate serving as an electrolyte and glass fiber serving as a diaphragm into the CR2032 button battery in air.
And (3) battery testing: the button cell prepared above was tested in a marchantia blue electrical system, and the room temperature was constant at 25 ℃.
The cycle performance of MnV 2O4 prepared in this example as a zinc electrode positive electrode material in the voltage range of 0.2-1.6V is shown in FIG. 8. Fig. 8 shows the activation behavior of VO (CH 3COO)2 as a positive electrode material of a zinc ion battery, the specific capacity of the first charge is about 85mAh/g, and after activation for 100 cycles, the specific capacity of the battery is as high as 166mAh/g, and there is no tendency of attenuation, which indicates that VO (CH 3COO)2 as a positive electrode material of a zinc ion battery has excellent cycle stability and is a very potential negative electrode material of a zinc ion battery) prepared by the embodiment.
Example 3
NH 4VO3 and MnCl 2 are added into deionized water according to the stoichiometric ratio of V:Mn=2:1, and after stirring until the mixture is fully dissolved, citric acid monohydrate (the molar ratio of citric acid to manganese salt is 1:3) is added as a chelating agent and a carbon source, and stirring is continued under a water bath at 70 ℃ until the water is evaporated completely and then dried. Pre-calcining the obtained precursor mixed uniformly for 5 hours at 350 ℃ in an argon atmosphere containing 5% of hydrogen, naturally cooling, and grinding to obtain a powdery material; calcining for 12 hours at 500 ℃ under the argon atmosphere containing 5% of hydrogen, and naturally cooling to obtain MnV 2O4.
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 9. As can be seen from fig. 9, pure-phase cubic MnV 2O4 material was synthesized by sol-gel method. The purity of the product is high as shown by the absence of impurity peaks in the spectrogram.
Manufacturing an electrode plate: the MnV 2O4, the conductive agent Super P and the binder sodium alginate prepared in the embodiment are fully mixed and ground in deionized water according to the ratio of 7:2:1 to obtain uniform slurry, the slurry is smeared on a current collector copper foil, the surface water solvent is naturally volatilized to dryness, and finally the electrode slice is obtained after the electrode slice is dried in a vacuum oven at 90 ℃ for one night.
And (3) battery assembly: and (3) assembling the obtained MnV 2O4 pole piece serving as a working electrode, a lithium piece serving as a counter electrode and EC: DEC: EMC (1:1:1 vol%) serving as electrolyte and Celgard2320 serving as a diaphragm into the CR2032 type button battery in a high-purity argon glove box.
And (3) battery testing: the button cell prepared above was tested in a marchantia blue electrical system, and the room temperature was constant at 25 ℃.
The MnV 2O4 of the embodiment is used as a lithium battery cathode material, and is circulated 500 times when the current density is 200mA/g in the voltage range of 0.01-3V, and the circulation performance is shown in figure 10. As can be seen from fig. 10, the initial charge specific capacity was about 257mAh/g, and the specific capacity was continuously increased as the cycle progressed. After 500 cycles, the specific capacity of the battery reaches 990mAh/g.
Example 4
NH 4VO3 and MnSO 4 are added into deionized water according to the stoichiometric ratio of V:Mn=2:1, and after stirring until the mixture is fully dissolved, citric acid monohydrate (the molar ratio of citric acid to manganese salt is 1:3) is added as a chelating agent and a carbon source, and stirring is continued under a water bath at 70 ℃ until the water is evaporated completely and then dried. Pre-calcining the obtained precursor mixed uniformly for 5 hours at 350 ℃ in pure argon atmosphere, naturally cooling, and grinding to obtain a powdery material; calcining for 5 hours at 800 ℃ under pure argon atmosphere, and naturally cooling to obtain MnV 2O4.
The X-ray diffraction pattern of the product obtained in this example is shown in FIG. 11. As can be seen from fig. 11, pure-phase cubic MnV 2O4 material was synthesized by sol-gel method. The purity of the product is high as shown by the absence of impurity peaks in the spectrogram.
As can be seen from the above examples, the transition metal vanadate material MnV 2O4 prepared by the method provided by the invention has excellent electrochemical performance as a negative electrode of a lithium ion battery and a positive electrode of a zinc ion battery, and has good cycle performance. Therefore, mnV 2O4 prepared by using a sol-gel method is expected to become a new battery electrode material of the next generation.
Manufacturing an electrode plate: the MnV 2O4, the conductive agent Super P and the binder sodium alginate prepared in the embodiment are fully mixed and ground in deionized water according to the ratio of 7:2:1 to obtain uniform slurry, the slurry is smeared on a current collector copper foil, the surface water solvent is naturally volatilized to dryness, and finally the electrode slice is obtained after the electrode slice is dried in a vacuum oven at 90 ℃ for one night.
And (3) battery assembly: and (3) assembling the obtained MnV 2O4 pole piece serving as a working electrode, a lithium piece serving as a counter electrode and EC: DEC: EMC (1:1:1 vol%) serving as electrolyte and Celgard2320 serving as a diaphragm into the CR2032 type button battery in a high-purity argon glove box.
And (3) battery testing: the button cell prepared above was tested in a marchantia blue electrical system, and the room temperature was constant at 25 ℃.
The MnV 2O4 of the embodiment is used as a lithium battery cathode material, and is circulated 500 times when the current density is 200mA/g in the voltage range of 0.01-3V, and the circulation performance is shown in figure 12. As can be seen from fig. 12, the initial charge specific capacity was about 308mAh/g, and the specific capacity was increasing as the cycle progressed. After 500 cycles, the specific capacity of the battery reaches 1027mAh/g.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (8)

1. The application of the transition metal vanadate material in preparing the lithium ion battery cathode material is characterized in that the preparation method of the transition metal vanadate material comprises the following steps:
(1) Adding ammonium metavanadate and manganese salt into water, stirring until the ammonium metavanadate and manganese salt are fully dissolved, adding citric acid monohydrate as a chelating agent and a carbon source, continuously stirring in a water bath until the water is evaporated completely, and then drying;
(2) Pre-calcining the dried product in the step (1) under argon or reducing atmosphere, naturally cooling, and grinding to obtain a powdery material;
(3) Calcining the powdery material obtained in the step (2) under argon or reducing atmosphere, and naturally cooling to obtain the transition metal vanadate material.
2. The application of the transition metal vanadate material in preparing the zinc ion battery anode material is characterized in that the preparation method of the transition metal vanadate material comprises the following steps:
(1) Adding ammonium metavanadate and manganese salt into water, stirring until the ammonium metavanadate and manganese salt are fully dissolved, adding citric acid monohydrate as a chelating agent and a carbon source, continuously stirring in a water bath until the water is evaporated completely, and then drying;
(2) Pre-calcining the dried product in the step (1) under argon or reducing atmosphere, naturally cooling, and grinding to obtain a powdery material;
(3) Calcining the powdery material obtained in the step (2) under argon or reducing atmosphere, and naturally cooling to obtain the transition metal vanadate material.
3. The use according to claim 1 or 2, wherein the manganese salt of step (1) is one of manganese acetate, manganese chloride, manganese carbonate and manganese sulphate; the molar ratio of vanadium in the ammonium metavanadate to manganese in the manganese salt is 2:1.
4. The use according to claim 1 or 2, wherein the molar ratio of citric acid to manganese salt in step (1) is 1:1-1:3.
5. Use according to claim 1 or 2, characterized in that the temperature of the water bath of step (1) is 70-100 ℃.
6. The use according to claim 1 or 2, wherein the pre-calcination in step (2) is carried out at a temperature of 300-400 ℃ for a time of 2-6 hours.
7. The use according to claim 1 or 2, wherein the reducing atmosphere in step (2) and step (3) is an argon atmosphere containing 5% hydrogen.
8. The use according to claim 1 or 2, wherein the calcination temperature in step (3) is 500 ℃ to 800 ℃ and the calcination time is 5 to 12 hours.
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