CN110690419B - Transition metal chalcogenide composite material and preparation method and application thereof - Google Patents

Transition metal chalcogenide composite material and preparation method and application thereof Download PDF

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CN110690419B
CN110690419B CN201910853622.1A CN201910853622A CN110690419B CN 110690419 B CN110690419 B CN 110690419B CN 201910853622 A CN201910853622 A CN 201910853622A CN 110690419 B CN110690419 B CN 110690419B
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transition metal
precursor
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carbon source
mixing
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CN110690419A (en
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唐永炳
张阁
欧学武
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01M10/052—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
    • H01M10/05—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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 belongs to the technical field of batteries, and particularly relates to a transition metal chalcogenide composite material as well as a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: mixing a transition metal precursor and a carbon source in a solvent, and then freeze-drying to obtain a compound precursor; mixing the compound precursor with the chalcogen precursor to obtain a mixture; and calcining the mixture in a reducing atmosphere to prepare the transition metal chalcogenide composite carbon microsphere. The preparation method is simple and controllable, high in yield, low in production cost, short in preparation period and good in process repeatability, and can be applied to large-scale production and preparation of the transition metal chalcogenide composite material.

Description

Transition metal chalcogenide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a transition metal chalcogenide composite material as well as a preparation method and application thereof.
Background
The traditional lithium ion battery mainly adopts graphite as a negative electrode, but because the capacity of the graphite negative electrode is insufficient, the compaction density is low, and the capacity of the graphite in the aspects of sodium storage and potassium storage is limited, the development of a novel negative electrode material is very important. As a potential negative electrode material, the transition metal chalcogenide has the characteristics of large interlayer spacing, high specific capacity and the like, receives great attention of people, and is widely researched and applied to metal ion batteries (lithium, sodium, potassium, magnesium and the like).
At present, methods for preparing transition metal chalcogenides mainly include chemical vapor deposition and hydrothermal synthesis. The chemical vapor deposition method can realize the controllable preparation of the layered material, but the yield is low, and the large-scale production and application are difficult to realize; the transition metal layered material synthesized by the hydrothermal synthesis method has non-uniform morphology and size and limited crystallinity, and the performance of the material is difficult to ensure. In addition, the synthesis method is often carried out at high temperature, and has complex operation and large energy consumption. Therefore, the development of a simple and efficient process for the preparation of transition metal chalcogenides is key to its scale-up.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a transition metal chalcogenide composite material, aiming at simplifying the preparation process of the transition metal chalcogenide.
Another object of the present invention is to provide a transition metal chalcogenide composite material prepared by the above preparation method.
The invention also aims to provide application of the transition metal chalcogenide composite material in preparing a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery or a dual-ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a transition metal chalcogenide composite material, comprising the steps of:
providing a transition metal precursor, a carbon source and a solvent, wherein the carbon source can undergo oxidative self-polymerization in the solvent, and the transition metal precursor can be dissolved in the solvent and has oxidizing property; mixing the transition metal precursor and the carbon source in the solvent, and then freeze-drying to obtain a compound precursor;
mixing the compound precursor with the chalcogen precursor to obtain a mixture;
and calcining the mixture in a reducing atmosphere to prepare the transition metal chalcogenide composite carbon microsphere.
According to the preparation method of the transition metal chalcogenide composite material, transition metal cations are compounded with a carbon source through a simple liquid phase reaction, then freeze-drying is carried out, and the compound is mixed with a chalcogen precursor and calcined, so that the controllable preparation of the transition metal chalcogenide composite carbon microsphere is realized. Compared with the traditional silicon dioxide template method, hydrothermal method and chemical vapor deposition method, the preparation method provided by the invention is simple and controllable, high in yield, low in production cost, short in preparation period and good in process repeatability, and can be applied to large-scale production and preparation of the transition metal chalcogenide composite material.
Correspondingly, the transition metal chalcogenide composite material comprises a transition metal chalcogenide and a carbon microsphere; the transition metal chalcogenide has a lamellar structure and is embedded in the surface of the carbon microsphere.
The transition metal chalcogenide composite material is prepared by the preparation method, and the transition metal chalcogenide is inserted and embedded on the surface of the carbon microsphere, on one hand, the carbon microsphere is used as a supporting framework of the transition metal chalcogenide, and when the transition metal chalcogenide composite material is applied to the preparation of a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery or a dual-ion battery, the material structure damage caused by volume change in the process of inserting/extracting alkali metal ions by the transition metal chalcogenide can be avoided; on the other hand, the carbon microsphere has good conductivity, and the conductivity of the transition metal chalcogenide can be further improved, so that the battery prepared from the transition metal chalcogenide composite material has good electrochemical performance.
Correspondingly, the transition metal chalcogenide composite material prepared by the preparation method or the application of the transition metal chalcogenide composite material in preparing a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery or a dual-ion battery.
Relevant experimental tests prove that the transition metal chalcogenide composite material serving as the negative electrode material is applied to lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, calcium ion batteries or dual-ion batteries, shows higher specific capacity and excellent cycle performance, and has good electrochemical performance.
Drawings
FIG. 1 is an electron microscope scanning image of the tungsten diselenide composite carbon microsphere prepared in example 1 under different multiples;
fig. 2 is a graph showing the results of X-ray diffraction analysis of the tungsten diselenide composite carbon microspheres prepared in example 1;
fig. 3 is a result of electrochemical performance test of the assembled half-cell in the test example, which compares the electrochemical performance of the tungsten diselenide composite carbon microspheres prepared in example 1 with that of a commercial layered tungsten diselenide product.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method for preparing a transition metal chalcogenide composite material, comprising the steps of:
s01, providing a transition metal precursor, a carbon source and a solvent, wherein the carbon source can undergo oxidative self-polymerization in the solvent, and the transition metal precursor can be dissolved in the solvent and has oxidizability; mixing the transition metal precursor and the carbon source in the solvent, and then freeze-drying to obtain a compound precursor;
s02, mixing the compound precursor with the chalcogen precursor to obtain a mixture;
and S03, calcining the mixture in a reducing atmosphere to prepare the transition metal chalcogenide composite carbon microsphere.
According to the preparation method of the transition metal chalcogenide composite material provided by the embodiment of the invention, transition metal cations and a carbon source are compounded through a simple liquid phase reaction, then freeze-drying is carried out, and the compound is mixed with a chalcogen precursor and calcined, so that the controllable preparation of the transition metal chalcogenide composite carbon microsphere is realized, and the transition metal chalcogenide composite carbon microsphere prepared by the preparation method has the advantages of controllable morphology, small size distribution and high purity. Compared with the traditional silicon dioxide template method, hydrothermal method and chemical vapor deposition method, the preparation method provided by the embodiment of the invention is simple and controllable, high in yield, low in production cost, short in preparation period and good in process repeatability, and can be applied to large-scale production and preparation of the transition metal chalcogenide composite material.
Specifically, in step S01, the transition metal precursor is used to provide transition metal atoms, and in the embodiment of the present invention, the transition metal precursor is capable of being dissolved in the solvent and has an oxidizing property. As an embodiment, the solvent is water; the transition metal precursor is soluble salt of transition metal, and comprises at least one of tungsten salt, cobalt salt, vanadium salt, molybdenum salt, iron salt and zinc salt. On one hand, the metal ions of the metal salts have multiple valence states, and the price is relatively cheap, so that different use requirements can be easily met; on the other hand, chalcogenides formed from the metal atoms of these metal salts have a layered structure and are stable in structure, and when used as a negative electrode material for batteries, they are advantageous for intercalation/deintercalation of cations. In some embodiments, the tungsten salt is preferably at least one of sodium tungstate, calcium tungstate, potassium tungstate, lithium tungstate, magnesium tungstate, zinc tungstate, aluminum tungstate, ammonium tungsten oxide hydrate, phosphotungstic acid, sodium phosphotungstate, ammonium phosphotungstate trihydrate, ammonium tetrathiotungstate, tungsten trioxide, and phosphotungstic acid hydrate; in other embodiments, the cobalt salt is preferably at least one of cobalt carbonate, cobalt nitrate, cobalt chloride, cobalt oxide, and cobalt sulfate; in still other embodiments, the vanadium salt is preferably at least one of sodium vanadate, ammonium vanadate, vanadium sulfate, vanadium oxalate, and vanadyl oxalate; in still other embodiments, the molybdenum salt is preferably at least one of sodium dimolybdate, sodium molybdate, sodium octamolybdate, sodium paramolybdate, potassium molybdate, sodium pentamolybdate, sodium phosphomolybdate, lithium molybdate, cadmium molybdate, iron molybdate, manganese molybdate, magnesium molybdate, calcium molybdate, ammonium tetramolybdate, ammonium molybdate tetrahydrate, zinc molybdate, ammonium heptamolybdate, ammonium octamolybdate, ammonium tetrathiomolybdate, molybdenum trioxide, ammonium dimolybdate, ammonium phosphomolybdate; in still other embodiments, the iron salt is preferably at least one of iron sulfate, iron nitrate, and iron chloride; in other embodiments, the zinc salt is preferably at least one of zinc nitrate, zinc chloride, and zinc sulfate.
In the embodiment of the present invention, the carbon source can undergo oxidative self-polymerization in the solvent, and it can be subjected to subsequent lyophilization and calcination processes to form carbon microspheres, which serve as the conductive support framework of the transition metal chalcogenide composite material of the embodiment of the present invention. As an embodiment, the carbon source includes at least one of dopamine hydrochloride, 3, 4-dibenzyloxy-trans- β -nitrostyrene, 2- (3, 4-dimethoxyphenyl) ethylamine, (3, 4-dimethoxyphenyl) acetonitrile, N-oleoyl dopamine, 2- (3, 4-dihydroxyphenyl) ethylamine, 3-acryloyldopamine, hydroxytyrosol, 3, 4-dihydroxyphenylacetic acid, ractopamine hydrochloride, polyaniline, polypyrrole, and glucose.
Specifically, the transition metal precursor and the carbon source are mixed in the solvent, so that the transition metal precursor and the carbon source are fully and uniformly mixed. During the mixing process, the carbon source is oxidized and self-polymerized, and the transition metal cation is reduced and adhered to the surface of the carbon source polymer. As an example, the carbon source is dopamine hydrochloride, the transition metal precursor is sodium tungstate, the sodium tungstate and the dopamine hydrochloride are dissolved in a solvent, the dopamine hydrochloride undergoes oxidative autopolymerization in the solvent, hydroxyl groups in a catechol group are deprotonated to generate dopamine quinone and release electrons, then the dopamine quinone undergoes nucleophilic reaction, intramolecular rearrangement and structural rearrangement in a short time to generate Polydopamine (PDA), and at the same time, electrons obtained from the sodium tungstate are reduced to form tungsten oxide and adhere to the surface of the PDA to form a tungsten-based oxide/PDA composite.
In the step of mixing the transition metal precursor and the carbon source in the solvent, the concentration of the carbon source, the mixing ratio of the carbon source and the transition metal precursor, the mixing temperature and the mixing time affect the shape and the size of the transition metal chalcogenide composite carbon microsphere synthesized by reaction. As an embodiment, in the step of mixing the transition metal precursor and the carbon source in the solvent, the transition metal precursor and the carbon source are mixed in the solvent at a ratio of (0.1-1): 1-10) of the transition metal atom of the transition metal precursor to the carbon source. Thus, the transition metal chalcogenide is effectively compounded on the surface of the carbon microsphere, and the size of the transition metal chalcogenide compound carbon microsphere formed by the method is proper. In some embodiments, the transition metal atoms of the transition metal precursor and the carbon source are present in a molar ratio of 1:1, such that the size of the transition metal chalcogenide composite carbon microsphere formed is optimal. In another embodiment, in the step of mixing the transition metal precursor and the carbon source in the solvent, the concentration of the carbon source in the solvent is 0.001 to 1 mol/L. The size of the transition metal chalcogenide composite carbon microsphere formed in this concentration range is suitable, and in some embodiments, the concentration of the carbon source in the solvent is 0.02mol/L, so that the size of the transition metal chalcogenide composite carbon microsphere formed is optimal. As still another embodiment, in the step of performing the mixing treatment of the transition metal precursor and the carbon source in the solvent, the temperature of the mixing treatment is 25 to 100 ℃ and the time is 0.5 to 12 hours. Because the temperature and the reaction time are in a linear relation with the reaction intensity, when the temperature is higher than 100 ℃ and/or the reaction time is higher than 12 hours, the carbon microspheres can be stacked together by self, so that the size of the carbon microspheres is increased; meanwhile, the distribution of transition metal cations on the surface of the polymer is also influenced, and the total surface area of the carbon microsphere is reduced, so that the transition metal cations can cover a plurality of layers on the surface of the polymer, and the treated transition metal chalcogenide can agglomerate on the surface of the carbon microsphere. In some embodiments, the mixing process employs mechanical stirring, such as continuous stirring in a mechanical stirrer at a speed of 100-.
After the mixing treatment, freeze-drying is performed to remove moisture, and a composite structure formed by compounding the reduction product of the transition metal precursor and the polymer formed by self-polymerization of the carbon source is hardened to form a composite precursor having a carbon polymer skeleton. In some embodiments, the lyophilization is performed in a lyophilizer.
Specifically, in step S02, the composite precursor and the chalcogen precursor are mixed to obtain a mixture in which the composite precursor and the chalcogen precursor are mixed uniformly. The step of mixing the composite precursor with the chalcogen precursor may be performed by a conventional method in the art, and the embodiment of the present invention is not particularly limited. In some embodiments, the step of mixing the composite precursor with the chalcogen precursor comprises: crushing the compound precursor to particles with the size of 1-10 mu m, and then adding the chalcogen precursor for mixing and grinding until the compound precursor and the chalcogen precursor are fully and uniformly mixed; in other embodiments, the step of mixing the composite precursor with the chalcogen precursor comprises: mixing the compound precursor and the chalcogen precursor, and crushing to the particle size of 1-10 μm to further improve the uniform mixing degree of the compound precursor and the chalcogen precursor; in still other embodiments, the pulverization is by a method of grinding with a mortar.
In the embodiment of the present invention, the chalcogen precursor may provide chalcogen, such as sulfur, selenium, tellurium, etc., through a subsequent reaction. As an embodiment, the chalcogen precursor includes at least one of a sulfur source, a selenium source, and a tellurium source. The sulfur source is a sulfur simple substance and/or a sulfur-containing compound, the selenium source is a selenium simple substance and/or a selenium-containing compound, and the tellurium source is a tellurium simple substance and/or a tellurium-containing compound. In some embodiments, the chalcogen precursor is preferably at least one of sulfur powder, sodium persulfate, thiourea, sodium selenite, selenourea, sodium persulfate, and sodium sulfite.
In one embodiment, in the step of mixing the composite precursor with the chalcogen precursor, the chalcogen precursor is added to the composite precursor in a ratio of (1-10) to (1-30) in terms of the molar ratio of the transition metal atom of the transition metal precursor to the chalcogen of the chalcogen precursor.
Specifically, in step S03, the mixture is subjected to a calcination process in a reducing atmosphere, such that transition metal cations adhering to the surface of the carbon-derived polymer are reduced to form transition metal atoms, which react with the chalcogen precursor in situ during the calcination process to form a transition metal chalcogenide having a lamellar structure, and at the same time, the carbon polymer skeleton is calcined to form carbon microspheres, thereby obtaining transition metal chalcogenide composite carbon microspheres. In the transition metal chalcogenide composite carbon microsphere, the transition metal chalcogenide has a lamellar structure and is inserted and embedded on the surface of the carbon microsphere to form a core-shell structure taking the carbon microsphere as a core and the transition metal chalcogenide as a shell.
In one embodiment, the calcination temperature in the step of subjecting the mixture to calcination treatment under a reducing atmosphere is 400-800 ℃. At this temperature, the carbon source may be carbonized, and the chalcogen of the chalcogen precursor may be reacted with the reducing gas to promote the reaction of the chalcogen with the transition metal atoms into which the transition metal cations are reduced, thereby producing microspheres in which the transition metal chalcogenides are combined with carbon. Further, the calcination treatment comprises: heating to 400-800 ℃ at the heating rate of 2-20 ℃/min, and then carrying out heat preservation reaction for more than 2 hours.
The reducing atmosphere refers to an atmosphere containing a reducing gas. In one embodiment, the reducing atmosphere is a mixture of a reducing gas and an inert gas, and the volume percentage of the reducing gas is 1% to 10%. Under the reducing atmosphere, the chalcogen of the chalcogen precursor reacts with the chalcogen precursor, and simultaneously the transition metal cations are reduced into transition metal atoms, so that the chalcogen and the transition metal atoms reduced by the transition metal cations are promoted to react, and the microspheres compounded by the transition metal chalcogenides and carbon are generated. When the volume percentage of the reducing gas is more than 10%, it may cause etching of the transition metal chalcogenide by the reducing gas. In some embodiments, the reducing gas is hydrogen; in other embodiments, the inert gas is at least one of argon, helium, and nitrogen.
In summary, under the comprehensive effect of the optimized process conditions provided by the embodiments of the present invention, the transition metal chalcogenide composite material obtained by the preparation method provided by the embodiments of the present invention has the advantages of optimal comprehensive performance, controllable morphology, small size distribution and high purity. Compared with the prior art, the carbon source is introduced at the initial stage of the preparation of the transition metal chalcogenide, the carbon microsphere template is formed through the oxidative self-polymerization of the carbon source, and the transition metal chalcogenide precursor is uniformly deposited, so that the core-shell structure based on the carbon microsphere and the transition metal chalcogenide is finally obtained. The method greatly simplifies the preparation process, reduces the preparation cost, and the introduced carbon microspheres improve the structural stability and the conductivity of the transition metal chalcogenide to a certain extent.
Correspondingly, the transition metal chalcogenide composite material prepared by the preparation method comprises a transition metal chalcogenide and carbon microspheres; the transition metal chalcogenide has a lamellar structure and is embedded in the surface of the carbon microsphere.
The transition metal chalcogenide composite material provided by the embodiment of the invention is prepared by the preparation method, and the transition metal chalcogenide is inserted and embedded on the surface of the carbon microsphere, on one hand, the carbon microsphere is used as a supporting framework of the transition metal chalcogenide, and when the transition metal chalcogenide composite material is applied to the preparation of a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery or a dual-ion battery, the material structure damage caused by volume change of the transition metal chalcogenide in the process of inserting/extracting alkali metal ions can be avoided; on the other hand, the carbon microsphere has good conductivity, and the conductivity of the transition metal chalcogenide can be further improved, so that the battery prepared from the transition metal chalcogenide composite material has good electrochemical performance; in another aspect, the carbon microsphere also serves as a self-supporting material during the synthesis of the transition metal chalcogenide, which effectively prevents the agglomeration of the transition metal chalcogenide, thereby allowing the transition metal chalcogenide to be uniformly embedded on the surface of the carbon microsphere.
Specifically, in the transition metal chalcogenide composite material, the basic chemical formula of the transition metal chalcogenide is MX2Wherein M is selected from Mo, W, Co, V, Zn or Fe, and X is selected from S, Se or Te. Further, the transition metal chalcogenide has a structure of one or more layers, and is preferably a two-dimensional transition metal chalcogenide (TMDC). Further, the transition metal chalcogenide is inserted into the surface of the carbon microsphere in a form perpendicular to the surface of the carbon microsphere.
In one embodiment, the transition metal chalcogenide composite material has a particle size of 3 to 8 μm
Correspondingly, the transition metal chalcogenide composite material prepared by the preparation method or the application of the transition metal chalcogenide composite material in preparing a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a calcium ion battery or a dual-ion battery.
Relevant experimental tests prove that the transition metal chalcogenide composite material serving as the negative electrode material is applied to lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, calcium ion batteries or dual-ion batteries, shows higher specific capacity and excellent cycle performance, and has good electrochemical performance.
In order that the details of the above-described practice and operation of the present invention will be clearly understood by those skilled in the art, and the advanced nature of the transition metal chalcogenide composite material, its preparation and use of the embodiments of the present invention will be apparent, the practice of the present invention will now be illustrated by way of example.
Example 1
The embodiment provides a preparation method of a transition metal chalcogenide composite material, which specifically comprises the following steps:
1. dispersing 1mmol of sodium tungstate in a certain amount of water, adding 1mmol of dopamine hydrochloride after the sodium tungstate is fully dissolved, violently stirring for 30min, and freeze-drying to obtain a compound precursor;
2. grinding the compound precursor and 0.25g of selenium powder to obtain a mixture; putting the mixture into an alumina porcelain boat for later use;
3. placing the mixture of step 2 in a heating zone of a tube furnaceThe middle position of (a); before heating, Ar/H is firstly introduced into the tube furnace2Mixing the gas to remove air in the pipe; heating to 600 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2 hours, continuously introducing certain carrier gas flow in the heat preservation process, and naturally cooling to room temperature after the heat preservation is finished;
4. and (4) washing with water to remove salt particles in the product, and drying to obtain the tungsten diselenide composite carbon microsphere.
Taking the tungsten diselenide composite carbon microsphere prepared in the embodiment, performing electron microscope scanning to observe the structural form of the tungsten diselenide composite carbon microsphere, wherein fig. 1 is an electron microscope scanning image of the tungsten diselenide composite carbon microsphere under different multiples, the left figure shows that the tungsten diselenide composite carbon microsphere prepared in the embodiment is a spherical structure, the right figure shows that the tungsten diselenide composite carbon microsphere prepared in the embodiment is a core-shell structure, and the tungsten diselenide is in a sheet structure and is inserted into the surface of the carbon microsphere.
The tungsten diselenide composite carbon microspheres prepared in the present embodiment were taken and subjected to X-ray diffraction analysis, and it can be seen that the tungsten diselenide composite carbon microspheres prepared in the present embodiment have high sample purity, and fig. 2 is a detection result.
Examples 2-5 compared to example 1, the steps and materials used were the same except for the type of transition metal precursor used, and the specific variables are shown in table 1:
TABLE 1
Figure GDA0003009985500000101
Examples 6-11 compared to example 1, except that the mixing time of the mixing process was different, the steps and the materials used were the same, the specific variables are shown in table 2:
TABLE 2
Figure GDA0003009985500000102
Figure GDA0003009985500000111
Examples 12-16 compared to example 1, except for the amount of dopamine hydrochloride used, the procedure and the materials used were the same, see table 3 for specific variables:
TABLE 3
Figure GDA0003009985500000112
Examples 17-20 compared to example 1, the steps and materials used were the same except that the carbon source used was different, and the specific variables are shown in Table 4:
TABLE 4
Figure GDA0003009985500000113
Examples 21-25 compare example 1, except that the compounding temperature in the compounding treatment step was different, the remaining steps and the materials used were the same, and the specific variables are shown in table 5:
TABLE 5
Figure GDA0003009985500000114
Figure GDA0003009985500000121
Test example
1. Preparing a battery pole piece: adding 0.7g of tungsten diselenide composite carbon microspheres prepared in example 1, 0.2g of conductive carbon black and 0.1g of polyvinylidene fluoride into 2mL of N-methylpyrrolidone, and fully grinding to obtain uniform slurry; then the slurry is evenly coated on the surface of the copper foil and dried for 12 hours in vacuum at 80 ℃. The dried electrode sheet was cut into a wafer having a diameter of 10mm, compacted by an oil press (10MPa for 10 seconds), and placed in a glove box as a battery positive electrode for standby.
2. Battery negative pole: commercially available lithium metal sheets.
3. Preparing an electrolyte: 1.36g of lithium hexafluorophosphate was weighed into a glove box and added to 9ml of ethylene carbonate: dimethyl carbonate: the mixture was stirred in ethyl methyl carbonate (v/v/v ═ 1:1:1) until lithium hexafluorophosphate was completely dissolved, and the mixture was used as an electrolyte solution.
4. Preparing a diaphragm: cutting the glass fiber paper into round pieces with the diameter of 16mm, vacuum drying 80 pieces for 12h, and placing the round pieces in a glove box to be used as diaphragms for standby.
5. Assembling a half cell: and (3) in a glove box in an argon atmosphere, tightly stacking the prepared positive electrode, the diaphragm and the negative electrode in sequence, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a shell to finish the assembly of the battery.
A commercial layered tungsten diselenide commodity was taken as a control sample and the half-cell used for the control was assembled according to steps 1-5.
The half-cells assembled in step 5 and step 6 were tested for electrochemical performance, and the results are shown in fig. 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A method for preparing a transition metal chalcogenide composite material, comprising the steps of:
providing a transition metal precursor, a carbon source and a solvent, wherein the carbon source can undergo oxidative self-polymerization in the solvent, and the transition metal precursor can be dissolved in the solvent and has oxidizing property; mixing the transition metal precursor and the carbon source in the solvent, and then freeze-drying to obtain a compound precursor; during the mixing material treatment, the carbon source is subjected to oxidative self-polymerization, and transition metal cations provided by the transition metal precursor are reduced and adhered to and distributed on the surface of the carbon-derived polymer;
mixing the compound precursor with the chalcogen precursor to obtain a mixture;
and calcining the mixture in a reducing atmosphere to prepare the transition metal chalcogenide composite carbon microsphere.
2. The production method according to claim 1, wherein in the step of subjecting the transition metal precursor and the carbon source to the mixing treatment in the solvent, the transition metal precursor and the carbon source are subjected to the mixing treatment in the solvent in a ratio of a transition metal atom of the transition metal precursor to a molar ratio of the carbon source of (0.1-1) to (1-10); and/or
And in the step of mixing the transition metal precursor and the carbon source in the solvent, the initial concentration of the carbon source in the solvent is 0.001-1 mol/L.
3. The method according to claim 1, wherein in the step of mixing the composite precursor with the chalcogen precursor, the chalcogen precursor is added to the composite precursor in a ratio such that a molar ratio of the transition metal atom of the transition metal precursor to the chalcogen of the chalcogen precursor is (1-10) to (1-30).
4. The production method according to claim 1, wherein in the step of subjecting the transition metal precursor and the carbon source to a mixing treatment in the solvent, the temperature of the mixing treatment is 25 to 100 ℃ for 0.5 to 12 hours; and/or
In the step of calcining the mixture in a reducing atmosphere, the calcining temperature is 400-800 ℃.
5. The production method according to any one of claims 1 to 4, characterized in that the solvent is water; and/or
The transition metal precursor is soluble salt of transition metal, and comprises at least one of tungsten salt, cobalt salt, vanadium salt, molybdenum salt, iron salt and zinc salt.
6. The method according to any one of claims 1 to 4, wherein the carbon source comprises at least one of dopamine hydrochloride, 3, 4-dibenzyloxy-trans- β -nitrostyrene, 2- (3, 4-dimethoxyphenyl) ethylamine, (3, 4-dimethoxyphenyl) acetonitrile, N-oleoyl dopamine, 2- (3, 4-dihydroxyphenyl) ethylamine, 3-acryloyldopamine, hydroxytyrosol, 3, 4-dihydroxyphenylacetic acid, ractopamine hydrochloride, polyaniline, polypyrrole and glucose; and/or
The chalcogen precursor comprises at least one of a sulfur source, a selenium source and a tellurium source.
7. The method according to any one of claims 1 to 4, wherein the reducing atmosphere is a mixed atmosphere of a reducing gas and an inert gas, and the volume percentage of the reducing gas is 1% to 10%.
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