CN113809289A - Vanadium carbide modified hard carbon material and preparation method and application thereof - Google Patents
Vanadium carbide modified hard carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113809289A CN113809289A CN202110868367.5A CN202110868367A CN113809289A CN 113809289 A CN113809289 A CN 113809289A CN 202110868367 A CN202110868367 A CN 202110868367A CN 113809289 A CN113809289 A CN 113809289A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- vanadium carbide
- vanadium
- modified hard
- energy storage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of batteries, and discloses a vanadium carbide modified hard carbon composite energy storage material, a preparation method and application thereof. The preparation method comprises the following steps: (1) adding a carbon source and a vanadium source into the aqueous solution, stirring for a certain time, adding the mixed solution into a reaction kettle for hydrothermal reaction, and centrifuging, washing and drying the product after the reaction is finished; (3) and carbonizing the obtained product in a protective atmosphere to obtain the vanadium carbide modified hard carbon composite energy storage material. The preparation method is simple, and the prepared vanadium carbide modified hard carbon composite energy storage material has high tap density and excellent electrochemical stability, and has good market application prospect in the aspect of energy storage.
Description
Technical Field
The invention belongs to the field of energy storage materials and preparation thereof, and particularly relates to a vanadium carbide modified hard carbon material and a preparation method and application thereof.
Background
With the continuous development of society, at present, people face two new problems: first, fossil fuels such as coal, oil, natural gas, etc. are increasingly exhausted; second, the natural environment is constantly deteriorating. The increased research on renewable energy and clean energy is the key to solving such problems, and it is important to develop a high-performance energy storage system with high energy density, high power density and long cycle life. The efficient energy storage and conversion device is the key for utilizing new energy, the electrode material is used as the key for determining the performance of the energy storage device, and the research on the electrode material with excellent performance has important research significance on the development of the energy storage device. Hard carbon materials are considered as the most promising negative electrode materials due to low cost, good conductivity, low voltage platform, easy synthesis and reproducibility, and are widely applied to various energy storage devices such as lithium ion batteries, sodium ion batteries, potassium ion batteries and the like.
The sodium ion battery and the potassium ion battery have similar action mechanisms as the lithium ion battery, but the diameters of the sodium ions and the potassium ions are much larger than those of the lithium ions, so that the speed of an ion intercalation/deintercalation electrode is reduced, and the current commercial graphite interlayer spacing is small, so that the intercalation/deintercalation of the sodium ions and the potassium ions is not facilitated. However, the hard carbon material refers to a carbon material with a very low graphitization degree, and is generally prepared by a method of pyrolysis of a polymer. The hard carbon material is represented as a disordered structure in a macroscopic view, and represented as graphite microcrystals with different orientations in a microscopic view, and lithium ions, sodium ions and potassium ions can be embedded into gaps among the graphite microcrystals with different orientations and also can be partially embedded into sheets of the graphite microcrystals, so that the hard carbon material represents a good low-voltage platform and excellent energy storage performance, and is considered as a negative electrode material with the greatest application prospect. However, the coulombic efficiency of the hard carbon head ring is low, mainly because the electrolyte reacts with the electrode material on a solid-liquid interface, the electrolyte is reduced and decomposed to form a solid electrolyte interface film (SEI film) and sodium ions are irreversibly embedded between amorphous carbon or graphite microcrystal layers. The specific surface area of the material is increased, the active sites on the surface of the material are increased, the coulombic efficiency can be effectively improved, but the specific surface area of the material is increased by preparing the porous material, so that the material has lower tap density and lower volume energy density, and the practical application of the sodium-ion battery is limited. The vanadium carbide modified hard carbon composite energy storage material is prepared by modifying and modifying the hard carbon material aiming at the defects of the hard carbon material, has high tap density, improves the coulombic efficiency of the material, increases the capacity of a low-potential platform, reduces the side reaction on the surface of an electrode, and improves the electrochemical performance.
Disclosure of Invention
In view of the above-mentioned deficiencies and drawbacks of the prior art, it is a primary object of the present invention to provide a vanadium carbide modified hard carbon material.
A vanadium carbide modified hard carbon material is prepared by loading vanadium carbide particles on the surface of a spherical carbon material.
Further, the diameter of the spherical carbon material is 200-2000 nm; the content of vanadium carbide is 0.5-30%, and the particle size of vanadium carbide is 10-200 nm.
The second purpose of the invention is to provide a preparation method of the vanadium carbide modified hard carbon material, which comprises the following steps:
1) adding a carbon source and a vanadium source into the aqueous solution according to a predetermined ratio, uniformly stirring, carrying out hydrothermal reaction in a reaction kettle, cooling, taking out, cleaning and drying;
2) carbonizing the product obtained in the step 1) in a protective atmosphere to obtain the vanadium carbide modified hard carbon material.
Further, in the preparation method, the water in the step 1) is one of deionized water, distilled water or ultrapure water.
Further, in the preparation method, the carbon source in the step 1) is glucose, and the molar concentration in the total reaction system is controlled to be 0.25-5mol/L, preferably 0.25-2 mol/L; the carbon source is sucrose, and the molar concentration in the total reaction system is controlled to be 0.125-3mol/L, preferably 0.125-1 mol/L.
Further, in the preparation method, the vanadium source in the step 1) is vanadium salt, preferably vanadium oxalate, and the molar concentration in the total reaction system is controlled to be 0.002mol/L-0.1 mol/L.
Further, in the preparation method, the hydrothermal reaction temperature in the step 1) is 120-.
Further, in the preparation method, the carbonization temperature in the step 2) is 1100-2000 ℃, and the temperature is kept for 2-20 h.
The third purpose of the invention is to provide the application of the vanadium carbide modified hard carbon material in the preparation of composite energy storage materials. In particular to the preparation of hard carbon cathode materials of batteries.
Further, the battery includes any one of a lithium ion battery, a sodium ion battery and a potassium ion battery.
Compared with the prior art, the invention has the advantages that:
the invention successfully grows the carbon spheres with regular appearance and the diameter of 200-2000nm by a hydrothermal method; then further carbonizing under the condition of protective atmosphere to successfully grow vanadium carbide on the carbon sphere carrier, wherein the vanadium carbide grows uniformly and well adheres to the carbon spheres; the vanadium carbide modified hard carbon composite energy storage material prepared by the method shows good electrochemical performance when being used as an electrode material; the invention has simple production process and low cost and can carry out large-scale industrial production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
FIG. 1 is an XRD (X-ray diffraction) pattern of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the invention.
Fig. 2 is an SEM image of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention.
FIG. 3 is a TEM image of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention.
FIG. 4 is a CV curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention at a scan rate of 0.1 mV/s.
FIG. 5 is a constant current charge-discharge curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention at a current density of 0.1A/g.
FIG. 6 is a cycle performance curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention at 0.1A/g.
FIG. 7 is a cycle performance curve of 0.05-1A/g for the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention.
FIG. 8 is an XRD pattern of the vanadium carbide modified hard carbon composite energy storage material prepared in example 2 of the present invention.
FIG. 9 is a CV curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 2 of the present invention at a scan rate of 0.1 mV/s.
FIG. 10 is a constant current charge-discharge curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 2 of the present invention at a current density of 0.1A/g.
FIG. 11 is a cycle performance curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 2 of the present invention at 0.1A/g.
FIG. 12 is a cycle performance curve of 0.05-1A/g for the vanadium carbide modified hard carbon composite energy storage material prepared in example 2 of the present invention.
FIG. 13 is a CV curve of the vanadium carbide modified hard carbon composite energy storage material prepared in comparative example 1 of the present invention at a scan rate of 0.1 mV/s.
FIG. 14 is a constant current charge and discharge curve of the hard carbon energy storage material prepared in comparative example 1 of the present invention at a current density of 0.1A/g.
FIG. 15 is a graph of the cycle performance at 0.1A/g for the hard carbon energy storage material prepared in comparative example 1 of the present invention.
FIG. 16 is a graph of the cycle performance of the hard carbon energy storage material of comparative example 1 of the present invention at 0.05-1A/g.
Fig. 17 is a histogram comparing the capacities of the slope region and the plateau region of the second turn at 0.05A/g for the vanadium carbide-modified hard carbon composite energy storage material prepared in example 1 of the present invention, the vanadium carbide-modified hard carbon composite energy storage material prepared in example 2, and the hard carbon energy storage material prepared in comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
In this example, unless otherwise specified, the chemical reagents used were analytical reagents, all of which were common commercial products or prepared by conventional means, and the equipment used was conventional in the art, and the following are some examples of the inventors in the experiment:
example 1
Mixing vanadium pentoxide and oxalic acid in a molar ratio of 1: 3, adding the mixture into the aqueous solution, heating and stirring the mixture for 4 hours at the temperature of 80 ℃, and preparing 0.3mol/L vanadium oxalate solution.
1) Adding 70mL of 0.5mol/L glucose solution and 0.5mL of vanadium oxalate solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, heating for 12h at 180 ℃, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 1300 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the vanadium carbide modified hard carbon composite energy storage material.
3) And preparing the obtained vanadium carbide modified hard carbon composite energy storage material into a sodium ion battery cathode for electrochemical test.
FIG. 1 is an X-ray diffraction (XRD) spectrum of the vanadium carbide modified hard carbon composite material prepared in example 1, and from the spectrum, it can be seen that besides two obvious broad carbon peaks, there are several sharp diffraction peaks, compared with PDF card, the diffraction peak corresponding to VC has better crystallinity; FIG. 2 is a Scanning Electron Microscope (SEM) spectrum of the vanadium carbide modified hard carbon composite material prepared in example 1, and it can be seen from the graph that the obtained product has a nano-sphere structure, a diameter of about 600-800nm, uniform size and no agglomeration phenomenon; fig. 3 is a Transmission Electron Microscope (TEM) image of the hard carbon composite material modified with vanadium carbide prepared in example 1, and it can be seen from the image that vanadium carbide nanoparticles are uniformly attached to the outer layer of the carbon sphere, and these vanadium carbide nanoparticles can accelerate electron mobility, improve first turn coulombic efficiency, and improve electrochemical properties of the material. Fig. 4 is a CV curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention at a scanning rate of 0.1mV/s, and it can be seen from the graph that a pair of distinct redox peaks are found in a low potential region (0-0.1V), which is very consistent with the hard carbon material for sodium storage, indicating that the electrochemical mechanical mechanism is mainly controlled by reversible sodium insertion/extraction, and that after the first cycle, the curves of all samples overlap well, indicating that good reversibility is provided. Fig. 5 is a constant current charge-discharge curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention at a current density of 0.1A/g, and it can be seen from the graph that all other discharge-charge curves are highly overlapped except for the initial discharge curve, indicating that a relatively stable SEI layer is formed, indicating that the prepared vanadium carbide modified hard carbon composite energy storage material has excellent cycle stability and reversibility. Fig. 6 is a cycle performance curve of the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention at 0.1A/g, and it can be seen from the curve that after 100 cycles, the capacity retention rate is very high, and compared with the comparative example, the vanadium carbide modified hard carbon composite energy storage material has a higher coulombic efficiency (75%), which indicates that the prepared vanadium carbide modified hard carbon composite energy storage material has excellent cycle stability and capacity reversibility. FIG. 7 is a cycle performance curve of 0.05-1A/g for the vanadium carbide modified hard carbon composite energy storage material prepared in example 1 of the present invention, and it can be seen from the curve that the specific charge/discharge capacity is as high as 420mA h/g at a current density of 0.05mA/g, which indicates that the vanadium carbide modified hard carbon composite energy storage material prepared under a low current exhibits a good energy storage performance. Fig. 17 is a histogram comparing the capacities of the slope region and the plateau region of the second turn of the vanadium carbide-modified hard carbon composite energy storage material prepared in examples 1 and 2 of the present invention and the hard carbon energy storage material prepared in comparative example 1 at 0.05A/g, and it can be seen from the histogram that the capacities of the slope region and the plateau region of example 1 are both increased, especially the plateau region is increased by 150mA h/g, indicating that vanadium carbide can significantly improve the capacity of the plateau region and optimize the electrochemical performance of the hard carbon material.
Example 2
Mixing vanadium pentoxide and oxalic acid in a molar ratio of 1: 3, adding the mixture into the aqueous solution, heating and stirring the mixture for 4 hours at the temperature of 80 ℃, and preparing 0.3mol/L vanadium oxalate solution.
1) Adding 70mL of 2mol/L glucose solution and 2mL of vanadium oxalate solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, carrying out hydrothermal treatment at 160 ℃ for 12h, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 1500 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the vanadium carbide modified hard carbon composite energy storage material.
3) And preparing the obtained vanadium carbide modified hard carbon composite energy storage material into a sodium ion battery cathode for electrochemical test. The results are shown in FIGS. 8, 9, 10, 11, 12, 17.
Example 3
Mixing vanadium pentoxide and oxalic acid in a molar ratio of 1: 3, adding the mixture into the aqueous solution, heating and stirring the mixture for 4 hours at the temperature of 80 ℃, and preparing 0.3mol/L vanadium oxalate solution.
1) Adding 70mL of 0.125mol/L sucrose solution and 0.5mL of vanadium oxalate solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, heating for 12h at 200 ℃, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 1800 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the vanadium carbide modified hard carbon composite energy storage material.
3) And preparing the obtained vanadium carbide modified hard carbon composite energy storage material into a sodium ion battery cathode.
Example 4
Mixing vanadium pentoxide and oxalic acid in a molar ratio of 1: 3, adding the mixture into the aqueous solution, heating and stirring the mixture for 4 hours at the temperature of 80 ℃, and preparing 0.3mol/L vanadium oxalate solution.
1) Adding 70mL of 1mol/L sucrose solution and 2mL of vanadium oxalate solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, carrying out hydrothermal treatment at 200 ℃ for 12h, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 2000 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the vanadium carbide modified hard carbon composite energy storage material.
3) And preparing the obtained vanadium carbide modified hard carbon composite energy storage material into a sodium ion battery cathode.
Example 5
Mixing vanadium pentoxide and oxalic acid in a molar ratio of 1: 3, adding the mixture into the aqueous solution, heating and stirring the mixture for 4 hours at the temperature of 80 ℃, and preparing 0.3mol/L vanadium oxalate solution.
1) Adding 70mL of 1mol/L glucose solution and 1mL of vanadium oxalate solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, carrying out hydrothermal treatment at 180 ℃ for 12h, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 1300 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the vanadium carbide modified hard carbon composite energy storage material.
3) And preparing the obtained vanadium carbide modified hard carbon composite energy storage material into a lithium ion battery cathode.
Example 6
Mixing vanadium pentoxide and oxalic acid in a molar ratio of 1: 3, adding the mixture into the aqueous solution, heating and stirring the mixture for 4 hours at the temperature of 80 ℃, and preparing 0.3mol/L vanadium oxalate solution.
1) Adding 70mL of 0.25mol/L glucose solution and 0.5mL of vanadium oxalate solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, heating for 12h at 200 ℃, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 1500 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the vanadium carbide modified hard carbon composite energy storage material.
3) And preparing the obtained vanadium carbide modified hard carbon composite energy storage material into a lithium ion battery cathode.
Comparative example 1
1) Adding 70mL of 0.5mol/L glucose solution into a 100mL reaction kettle, uniformly stirring, then putting the reaction kettle into a furnace, heating for 12h at 180 ℃, cooling, taking out, washing the obtained product with deionized water and ethanol, and putting the product into an oven for drying.
2) And carbonizing the product in a protective atmosphere, heating to 1000 ℃ at a heating rate of 10 ℃/min, heating to 1300 ℃ at a heating rate of 5 ℃/min, and preserving heat for 2h to obtain the hard carbon energy storage material.
3) The obtained hard carbon energy storage material is prepared into a sodium ion battery cathode and subjected to electrochemical test, and the results are shown in figures 13, 14, 15, 16 and 17.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A vanadium carbide modified hard carbon material is characterized in that vanadium carbide particles are loaded on the surface of a spherical carbon material.
2. The vanadium carbide modified hard carbon material as claimed in claim 1, wherein the spherical carbon material has a diameter of 200-2000 nm; the content of vanadium carbide is 0.5-30%, and the particle size of vanadium carbide is 10-200 nm.
3. A preparation method of a vanadium carbide modified hard carbon material is characterized by comprising the following steps:
1) adding a carbon source and a vanadium source into the aqueous solution according to a predetermined ratio, uniformly stirring, carrying out hydrothermal reaction in a reaction kettle, cooling, taking out, cleaning and drying;
2) carbonizing the product obtained in the step 1) in a protective atmosphere to obtain the vanadium carbide modified hard carbon material.
4. The method of claim 3, wherein in step 1), the water is one of deionized water, distilled water, or ultrapure water.
5. The preparation method according to claim 3, wherein in the step 1), the carbon source is glucose, and the molar concentration in the total reaction system is controlled to be 0.25-5 mol/L; the carbon source is sucrose, and the molar concentration in the total reaction system is controlled to be 0.125-3 mol/L.
6. The preparation method according to claim 3, wherein in the step 1), the vanadium source is a vanadium salt, preferably vanadium oxalate, and the molar concentration in the total reaction system is controlled to be 0.002mol/L-0.1 mol/L.
7. The production method according to claim 3, characterized in that: the hydrothermal reaction temperature in the step 1) is 120-250 ℃, and the reaction time is 1-60 h.
8. The production method according to claim 3, characterized in that: the carbonization temperature in the step 2) is 1100-.
9. Use of the vanadium carbide modified hard carbon material according to claim 1 or 2 or the vanadium carbide modified hard carbon material prepared by the method according to any one of claims 3 to 8 for preparing a composite energy storage material.
10. Use according to claim 9, in particular for the preparation of battery hard carbon negative electrode materials; in particular, the battery includes any one of a lithium ion battery, a sodium ion battery and a potassium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110868367.5A CN113809289B (en) | 2021-07-30 | 2021-07-30 | Vanadium carbide modified hard carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110868367.5A CN113809289B (en) | 2021-07-30 | 2021-07-30 | Vanadium carbide modified hard carbon material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113809289A true CN113809289A (en) | 2021-12-17 |
| CN113809289B CN113809289B (en) | 2022-11-08 |
Family
ID=78942510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110868367.5A Active CN113809289B (en) | 2021-07-30 | 2021-07-30 | Vanadium carbide modified hard carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113809289B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728524A (en) * | 2008-10-31 | 2010-06-09 | 中国电子科技集团公司第十八研究所 | Lithium ion battery/capacitor electrode material and preparation method thereof |
| WO2017070988A1 (en) * | 2015-10-27 | 2017-05-04 | 中国科学院物理研究所 | Negative electrode material for sodium ion secondary battery, and preparation method and use therefor |
| CN106684356A (en) * | 2017-01-11 | 2017-05-17 | 安徽工业大学 | VC@onion-shaped carbon/amorphous carbon nanometer composite and preparation method and application thereof |
| CN106935856A (en) * | 2017-03-28 | 2017-07-07 | 中南大学 | A kind of carbon-based composite negative pole material of sodium-ion battery and preparation method thereof |
| CN108511721A (en) * | 2018-04-04 | 2018-09-07 | 哈尔滨工业大学 | Sodium-ion battery cathode VC0.75@NPC composite materials, preparation and application |
| CN108598505A (en) * | 2018-05-09 | 2018-09-28 | 陕西科技大学 | A kind of preparation method and product of vanadium carbide/carbon cloth composite material |
| CN108654660A (en) * | 2018-05-09 | 2018-10-16 | 陕西科技大学 | A kind of vanadium carbide/carbon nano tube compound material, preparation method and its application in terms of hydrogen is produced in water-splitting |
| CN110707301A (en) * | 2019-09-05 | 2020-01-17 | 珠海恒力源机电有限公司 | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof |
| CN110914941A (en) * | 2017-09-01 | 2020-03-24 | 法拉德动力公司 | Method for making hard carbon material |
| CN111509198A (en) * | 2019-01-31 | 2020-08-07 | 贝特瑞新材料集团股份有限公司 | Core-shell structure composite material, preparation method thereof and application thereof in lithium ion battery |
| KR102214227B1 (en) * | 2019-08-29 | 2021-02-08 | 성균관대학교산학협력단 | Anode active material, preparing method of the same, lithium ion secondary battery including the same |
-
2021
- 2021-07-30 CN CN202110868367.5A patent/CN113809289B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728524A (en) * | 2008-10-31 | 2010-06-09 | 中国电子科技集团公司第十八研究所 | Lithium ion battery/capacitor electrode material and preparation method thereof |
| WO2017070988A1 (en) * | 2015-10-27 | 2017-05-04 | 中国科学院物理研究所 | Negative electrode material for sodium ion secondary battery, and preparation method and use therefor |
| CN106684356A (en) * | 2017-01-11 | 2017-05-17 | 安徽工业大学 | VC@onion-shaped carbon/amorphous carbon nanometer composite and preparation method and application thereof |
| CN106935856A (en) * | 2017-03-28 | 2017-07-07 | 中南大学 | A kind of carbon-based composite negative pole material of sodium-ion battery and preparation method thereof |
| CN110914941A (en) * | 2017-09-01 | 2020-03-24 | 法拉德动力公司 | Method for making hard carbon material |
| CN108511721A (en) * | 2018-04-04 | 2018-09-07 | 哈尔滨工业大学 | Sodium-ion battery cathode VC0.75@NPC composite materials, preparation and application |
| CN108598505A (en) * | 2018-05-09 | 2018-09-28 | 陕西科技大学 | A kind of preparation method and product of vanadium carbide/carbon cloth composite material |
| CN108654660A (en) * | 2018-05-09 | 2018-10-16 | 陕西科技大学 | A kind of vanadium carbide/carbon nano tube compound material, preparation method and its application in terms of hydrogen is produced in water-splitting |
| CN111509198A (en) * | 2019-01-31 | 2020-08-07 | 贝特瑞新材料集团股份有限公司 | Core-shell structure composite material, preparation method thereof and application thereof in lithium ion battery |
| KR102214227B1 (en) * | 2019-08-29 | 2021-02-08 | 성균관대학교산학협력단 | Anode active material, preparing method of the same, lithium ion secondary battery including the same |
| CN110707301A (en) * | 2019-09-05 | 2020-01-17 | 珠海恒力源机电有限公司 | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| MANI MAHAJAN ETAL.: ""Room temperature processed in-situ carbon-coated vanadium carbide (VC@C) as a high capacity robust Li/Na battery anode material"", 《CARBON》 * |
| 杜忆忱等: "硬碳作为钠离子电池负极材料的研究进展", 《化学教育(中英文)》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113809289B (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8900755B2 (en) | Lithium super-battery with a chemically functionalized disordered carbon cathode | |
| CN105932234A (en) | Doped porous carbon spheres used for negative electrode material of sodium ion battery and preparation method for doped porous carbon spheres | |
| CN108269982B (en) | Composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN108682820B (en) | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery | |
| CN108878826B (en) | Sodium manganate/graphene composite electrode material and preparation method and application thereof | |
| CN111063872A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN108878851A (en) | α-manganese sulfide of one-dimensional porous diamond shape blank pipe shape/molybdenum sulfide@carbon composite preparation method and applications | |
| CN108630911A (en) | A kind of SnO of oxygen-containing vacancy defect2Graphene nanocomposite material and application in room temperature sodium-ion battery cathode | |
| CN114335522A (en) | Coal-based carbon negative electrode material, preparation method and application thereof, and battery containing coal-based carbon negative electrode material | |
| CN108878774A (en) | A kind of complex carbon material and its preparation method and application | |
| CN114188533B (en) | Negative electrode material and preparation method and application thereof | |
| CN106848282B (en) | Negative electrode material for non-aqueous electrolyte secondary battery and preparation method and application thereof | |
| CN112018353A (en) | WTE2/MXene composite material and preparation method thereof | |
| CN107978755B (en) | Method for uniformly doping metal ions on surface of material, product and application thereof | |
| CN109494346B (en) | Preparation method of carbon quantum dot modified lithium-sulfur battery positive electrode material | |
| CN114400307A (en) | Tin-carbon composite material and preparation method and application thereof | |
| CN113782718A (en) | High-voltage lithium ion battery material, lithium ion battery and preparation method thereof | |
| CN112510187A (en) | Electrostatic self-assembly spherical molybdenum trioxide/MXene composite material and preparation method and application thereof | |
| CN113809289B (en) | Vanadium carbide modified hard carbon material and preparation method and application thereof | |
| CN113130879B (en) | Preparation method of high-adsorption catalytic performance cathode material of lithium-sulfur battery | |
| CN113307261B (en) | Preparation method of graphite intercalation compound cathode material suitable for quick-charging lithium ion battery, product and application thereof | |
| CN115188943A (en) | Tin dioxide quantum dot-titanium carbide based composite material, preparation thereof and application thereof in lithium-sulfur battery | |
| CN114289006A (en) | For Li-CO2Preparation method and application of battery carbon sphere catalyst | |
| CN110676441B (en) | Battery negative electrode material, sodium ion battery and preparation method thereof | |
| CN111668472A (en) | Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |