CN113321192A - Preparation method and application of cubic molybdenum nitride - Google Patents
Preparation method and application of cubic molybdenum nitride Download PDFInfo
- Publication number
- CN113321192A CN113321192A CN202110560014.9A CN202110560014A CN113321192A CN 113321192 A CN113321192 A CN 113321192A CN 202110560014 A CN202110560014 A CN 202110560014A CN 113321192 A CN113321192 A CN 113321192A
- Authority
- CN
- China
- Prior art keywords
- molybdenum nitride
- melamine
- urea
- preparation
- ammonium molybdate
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 discloses a preparation method and application of cubic molybdenum nitride, belonging to the field of lithium ion battery electrode materials, wherein the preparation method comprises the following steps: s1, mixing the ethanol solution of urea, the ethanol solution of melamine and the ethanol solution of ammonium molybdate tetrahydrate, and stirring to obtain a mixed solution; the mass ratio of ammonium molybdate tetrahydrate, urea and melamine in the mixed solution is 5-11: 100: 3-6; s2, aging the mixed solution at room temperature to form sol/gel, and freeze-drying to form solid; s3, pre-burning the obtained solid, and then carrying out heat treatment to obtain precursor powder; s4, roasting the obtained precursor powder in a nitrogen atmosphere, and cooling to room temperature to obtain a molybdenum nitride electrode material; the invention obtains the nanometer molybdenum nitride powder product through simple process, the product has cubic structure, small crystal grain size and uniform granularity, and the product has excellent cycle performance and higher specific capacity when used as the cathode material of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery electrode materials, in particular to a preparation method of cubic molybdenum nitride and application of the cubic molybdenum nitride in lithium ion battery cathode materials.
Background
Among the key materials for manufacturing lithium ion batteries, the negative electrode material is an important factor in determining the operating performance and price thereof. At present, a commercialized cathode material is mainly a graphite carbon material, but the theoretical capacity of the graphite carbon material is only 372mAh/g, and meanwhile, a lithium precipitation phenomenon easily occurs during large-current charging and discharging, so that the safety is poor, and the development of a lithium ion battery is limited. So nowadays more and more people are studying some transition metal compounds to replace graphite electrode materials. Wherein molybdenum nitride (Mo)2N) has the advantages of stable chemical property, high hardness, high conductivity and the like, and is a good lithium storage electrode material. The high theoretical specific capacity, stable cycling stability and considerable electrochemical energy storage characteristics of the material can be formally used as a better electrode cathode material for people. Currently, Mo is prepared2N commonly used methods include a programmed temperature control method, a hydrothermal method, a template method and the like. These processes are in the preparation of Mo2There are many disadvantages in the N anode material: if the preparation period is long, the process is complicated, and NH is also used3And the oxygen content of the product is high. (preparation and characterization of electrode active material molybdenum nitride), good Li academic, Zhang-in, build-up, Ludao Rong, Wan Hualin, proceedings of Hefei university of Industrial science, Vol.23, No. 5, published as 2000 and 10 months) discloses preparation of molybdenum nitride by high-temperature reaction of molybdenum trioxide and ammonia gas and by a programmed heating method. However, the preparation process requires strict control of the temperature rising rate and the reaction temperature. The rapid rate of temperature rise will be detrimental to the reaction and lead to the presence of various reaction intermediates; the increase or decrease of the temperature also causes the reduction of the specific surface area, and not only the synthesis conditions are harsh, but also the cost is high and the oxygen content of the obtained product is high.
Chinese patent CN102161478A discloses nitrogenThe improved preparation process of the molybdenum oxide comprises the following preparation steps: mixing ammonium molybdate and hexamethylenetetramine in ammonia water according to the mass ratio of 3.5:6 by taking ammonia water as a solvent, drying at 60 ℃ for 24-26 h, roasting at 800 ℃ for 15h to obtain Mo2And N is added. The preparation process is simple, the oxygen content in the product is effectively reduced, and the purity of the obtained molybdenum nitride is high; however, ammonia water is used as a solvent in the preparation method, so that the safety is poor, the environment is polluted, and meanwhile, the molybdenum nitride prepared by the preparation method has no cubic structure.
Chinese patent CN109399582A discloses a high-temperature and high-pressure preparation method of bulk material molybdenum nitride, which comprises the steps of taking molybdenum powder and melamine as raw materials, tabletting the molybdenum powder and the melamine respectively by using a hydraulic press to form a sandwich structure, and making the sandwich structure into a cylinder according to the size of a synthetic cavity; putting the cylindrical raw material into a heating container, putting the heating container into a synthesis cavity, and keeping the temperature and the pressure for 10 minutes at the pressure of 4-5 GPa and the temperature of 1500-1900 ℃; finally cooling and releasing pressure to prepare the molybdenum nitride bulk material. However, the massive molybdenum nitride is difficult to synthesize by a conventional method, the pressure of the preparation method reaches 4-5 GPa, the conditions are severe, and the prepared molybdenum nitride is not suitable for being applied to a lithium ion battery cathode material.
Therefore, a safe, environment-friendly and simple preparation method for preparing Mo with excellent appearance and performance is urgently needed2And N negative electrode material.
Disclosure of Invention
One of the objects of the present invention is to provide a method for synthesizing molybdenum nitride (Mo) by sol-gel method2N) preparation method of nano material, the method has simple reaction condition, easy chemical reaction and easy control of reaction process, the diffusion of system components is in nano range, and the Mo prepared by the method2The N material has a cubic structure, small grain size and uniform granularity.
The purpose of the invention is realized by the following technical scheme.
Cubic Mo2The preparation method of N specifically comprises the following steps:
s1, mixing the ethanol solution of urea, the ethanol solution of melamine and the ethanol solution of ammonium molybdate tetrahydrate, and stirring to obtain a mixed solution; the mass ratio of ammonium molybdate tetrahydrate, urea and melamine in the mixed solution is 5-11: 100: 3-6;
s2, aging the mixed solution obtained in the step S1 at room temperature for 24-72 hours to form sol/gel; freeze drying to obtain solid;
s3, pre-burning the solid obtained in the step S2, then performing heat treatment, and cooling to room temperature to obtain precursor powder;
s4, roasting the precursor powder obtained in the step S3 in an inert atmosphere, and cooling to room temperature to obtain Mo2And (3) N electrode material.
According to the preparation method, the urea, the melamine and the ammonium molybdate tetrahydrate are added into the ethanol solution respectively to form the ammonium molybdate tetrahydrate aqueous solution, the urea aqueous solution and the melamine aqueous solution respectively, and then the three bottles of solutions are mixed, so that the urea, the melamine and the ammonium molybdate tetrahydrate are dispersed in the ethanol solution more uniformly.
The preparation method takes ammonium molybdate tetrahydrate as a molybdenum source, urea as a nitrogen source and melamine as a dispersing agent. Preparation of nanoscale, cubic Mo by sol-gel method2The N electrode material is subjected to a solution reaction step in the reaction process, so that the raw materials are uniformly mixed in the solution at the molecular level, and a sol-gel system is formed after aging; the components in the system are diffused in a nanometer range in the sol-gel process, and a p-pi conjugated system is formed by a large pi bond in a melamine structure and p electrons in ammonium molybdate, so that the formation of sol/gel and the size control of nanoparticles are facilitated. Then freeze drying is assisted to slowly crystallize the product, and the growth of product crystal grains can be controlled to obtain Mo with a clear cube structure edge angle2And (3) N material. During the heat treatment process, the carbonaceous components in the raw materials are removed by pre-burning, and the Mo is promoted by high-temperature roasting under the protection of nitrogen2And (4) forming N.
In the above preparation method, the aqueous solution of ethanol has good solubility to urea, and the solution is alkaline after dissolution, which makes ammonium molybdate stably exist in the mixed solution without adding any solventA precipitate will be generated; the melamine is difficult to dissolve in an ethanol aqueous solution system, and can only be suspended in the solution and adsorbed on the surface of urea and ammonium molybdate reaction product particles; the melamine adsorbed on the surface prevents agglomeration among particles, hinders the mass transfer process of the particles, reduces the crystal growth rate and enables the product particles to be uniform in size. The melamine adsorbed on different crystal faces is helpful for reducing surface tension, promoting directional growth of microcrystals and finally generating cubic Mo2And (3) N electrode material.
Preferably, the mass ratio of ammonium molybdate tetrahydrate, urea and melamine in the mixed solution is 7:100: 4.5.
Preferably, in the step S1, the mass ratio of the absolute ethyl alcohol to the water to the urea in the ethanol solution of urea is 2.4:1: 1; the mass ratio of the absolute ethyl alcohol to the water to the melamine in the melamine ethanol solution is 240:100: 3-6; the mass ratio of the absolute ethanol to the water to the ammonium molybdate tetrahydrate in the ethanol solution of the ammonium molybdate tetrahydrate is 240:100: 5-11;
preferably, the stirring time in the step S1 is 12 h.
Preferably, the pre-sintering temperature in the step S3 is 300-350 ℃, and the time is 2-3 h; the heat treatment temperature is 400-500 ℃, and the time is 0.5-1 h.
More preferably, the pre-sintering temperature in the step S3 is 300 ℃, and the time is 2 h; the heat treatment temperature is 400 ℃ and the time is 0.5 h.
Preferably, the roasting temperature in the step S4 is 700-900 ℃, and the time is 2 h.
The cubic structure obviously increases Mo2The specific surface area of the N material can provide more contact opportunities for lithium ions when being used as a raw material for preparing the lithium ion battery cathode material, shorten the diffusion distance of the lithium ions and facilitate the transfer of the lithium ions; the pore channel formed by stacking the cubic structure can effectively bear the volume expansion of the electrode material in the charging and discharging processes, so that Mo2The N material has excellent cycle performance.
Another object of the present invention is to provide cubic Mo2Application of N in preparation of lithium ion battery cathode material。
Compared with the prior art, the invention has the beneficial effects that:
1. the sol-gel method and the melamine are mutually matched and act together, the growth rate of the crystal is reduced, the product is slowly crystallized, the crystal appearance of the product is good, and the specific surface area is large. Meanwhile, the preparation method has the advantages of simple operation, low equipment requirement, low synthesis temperature, easy chemical reaction and easy control of the reaction process.
2. Mo prepared by the invention2The N material has a cubic structure, uniform particle size and increased specific surface area, can provide more contact opportunities for lithium ions, shortens the diffusion distance of the lithium ions and is beneficial to the transfer of the lithium ions; mo2The N nano material has higher specific charge-discharge capacity, and the first discharge capacity can reach 420 mAh/g.
3. The pore channel formed by stacking the cubic structure can effectively bear the volume expansion of the electrode material in the charging and discharging processes, so that Mo2The N material has good cycle performance, and the specific discharge capacity of the material after 100 cycles is 600.5 mAh/g.
Drawings
FIG. 1 is an X-ray diffraction pattern of materials prepared in examples of the present invention and comparative examples;
FIG. 2 shows Mo prepared in example 2 of the present invention2Transmission electron microscopy of the N material;
FIG. 3 is a transmission electron micrograph of a material prepared according to comparative example 1 of the present invention;
FIG. 4 is a charge and discharge curve of the materials prepared in example 2 of the present invention and comparative example 1 under the condition of 0.1A/g.
Detailed Description
The applicant will now make further details of the process of the present invention with reference to specific examples in order to enable the skilled person to understand the invention clearly. The following examples should not be construed to limit the scope of the claims to the invention in any way.
The medicines used in the following examples and comparative examples were purchased from national pharmaceutical products group chemical Co. The freeze-drying method adopted is as follows: the sol obtained after aging is precooled for 2h at-5 ℃, and then is dried for 24h by sublimation at-45 ℃ and under vacuum of 18 Pa. In the sol-gel method of the following examples, a sol is formed when the aging time is short (e.g., aging for 24 hours), and a gel is formed when the aging time is long (e.g., aging for 72 hours).
Example 1
Cubic Mo2The preparation method of N comprises the following steps:
respectively adding 0.5g of ammonium molybdate tetrahydrate, 10g of urea and 0.6g of melamine into an ethanol solution prepared from 24g of absolute ethanol and 10g of distilled water, uniformly stirring to respectively obtain an ethanol solution of ammonium molybdate tetrahydrate, an ethanol solution of urea and an ethanol solution of melamine, then mixing the three bottles of solutions, and stirring for 12 hours to obtain a mixed solution; aging the obtained mixed solution at room temperature for 24h to form sol; and freeze-drying the obtained product to form a solid, then pre-burning the obtained solid in air at 300 ℃ for 2h, then carrying out heat treatment at 400 ℃ for 0.5h, and cooling to room temperature to obtain precursor powder. Roasting the obtained powder for 2h at 700 ℃ in nitrogen atmosphere, and cooling to room temperature to obtain Mo2And (3) N electrode material.
Example 2
Cubic Mo2The preparation method of N comprises the following steps:
respectively adding 0.7g of ammonium molybdate tetrahydrate, 10g of urea and 0.45g of melamine into an ethanol solution prepared from 24g of absolute ethanol and 10g of distilled water, uniformly stirring to respectively obtain an ethanol solution of ammonium molybdate tetrahydrate, an ethanol solution of urea and an ethanol solution of melamine, then mixing the three bottles of solutions, and stirring for 12 hours to obtain a mixed solution; aging the obtained mixed solution at room temperature for 24h to form sol; and freeze-drying the obtained product to form a solid, then pre-burning the obtained solid in air at 300 ℃ for 2h, then carrying out heat treatment at 400 ℃ for 0.5h, and cooling to room temperature to obtain precursor powder. Roasting the obtained powder for 2h at 800 ℃ in nitrogen atmosphere, and cooling to room temperature to obtain Mo2And (3) N electrode material.
Example 3
Cubic Mo2The preparation method of N comprises the following steps:
respectively adding 0.9g of ammonium molybdate tetrahydrate, 10g of urea and 0.45g of melamine into an ethanol solution prepared from 24g of absolute ethanol and 10g of distilled water, uniformly stirring to respectively obtain an ethanol solution of ammonium molybdate tetrahydrate, an ethanol solution of urea and an ethanol solution of melamine, then mixing the three bottles of solutions, and stirring for 12 hours to obtain a mixed solution; aging the obtained mixed solution at room temperature for 36h to form sol; and freeze-drying the obtained product to form a solid, then pre-burning the obtained solid in air at 300 ℃ for 2h, then carrying out heat treatment at 400 ℃ for 0.5h, and cooling to room temperature to obtain precursor powder. Roasting the obtained powder for 2h at 900 ℃ in nitrogen atmosphere, and cooling to room temperature to obtain Mo2And (3) N electrode material.
Example 4
Cubic Mo2The preparation method of N comprises the following steps:
respectively adding 1.1g of ammonium molybdate tetrahydrate, 10g of urea and 0.3g of melamine into an ethanol solution prepared from 24g of absolute ethanol and 10g of distilled water, uniformly stirring to respectively obtain an ethanol solution of ammonium molybdate tetrahydrate, an ethanol solution of urea and an ethanol solution of melamine, then mixing the three bottles of solutions, and stirring for 12 hours to obtain a mixed solution; aging the obtained mixed solution at room temperature for 72h to form gel; and freeze-drying the obtained product to form a solid, then pre-burning the obtained solid in air at 300 ℃ for 2h, then carrying out heat treatment at 400 ℃ for 0.5h, and cooling to room temperature to obtain precursor powder. Roasting the obtained powder for 2h at 800 ℃ in nitrogen atmosphere, and cooling to room temperature to obtain Mo2And (3) N electrode material.
Comparative example 1
In comparison with example 2, in this comparative example, melamine was not added, and the preparation method was different from example 2 in that 0.7g of ammonium molybdate tetrahydrate and 10g of urea were added to ethanol solutions prepared from 24g of anhydrous ethanol and 10g of distilled water, respectively, and stirred uniformly to obtain ethanol solutions of ammonium molybdate tetrahydrate and urea, respectively, and then the two bottles of solutions were mixed and stirred for 12 hours to obtain a mixed solution.
Application example
The samples prepared in examples 1-4 and comparative example 1 were prepared into half cells for electrochemical performance measurement, and the half cell assembly methods were as follows: the prepared anode material to be detected, Super P Li conductive carbon black and PVDF are mixed according to the mass ratio of 8: 1:1, mixing, uniformly mixing with N-methyl pyrrolidone, stirring to form a viscous state, then coating the viscous state on a copper foil, drying for 6 hours at the temperature of 60 ℃ in vacuum (-0.1MPa), cooling and cutting into circular films with the diameter of about 1 cm. The half cell is assembled by CR2016 type button cell in glove box, the diaphragm is Celgard 2400 polypropylene diaphragm, the electrolyte is 1M LiPF6The electrolyte mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) was prepared (the volume ratio of EC to DEC in the electrolyte mixture was 1:1), the negative electrode was a commercial round lithium plate (diameter: 1.5cm), and the electrochemical performance test was performed on a blue CT2001A type battery test system (manufactured by blue electronic Co., Ltd., Wuhan City).
FIG. 1 is an X-ray diffraction pattern of the materials prepared in examples 1 to 4 and comparative example 1, and it can be seen from the XRD pattern that the characteristic peaks of examples 1 to 4 correspond to Mo at 2 theta of 37.38, 43.45 and 63.11 respectively2Crystal faces (111), (200) and (220) of N, characteristic peaks of crystal structure of material and Mo2The standard map of N (JCPDS Card No.25-1366) is basically identical, indicating that Mo in the product2N has already been synthesized. However, in the XRD pattern of comparative example 1, the crystal diffraction peaks appearing at 2 θ of 34.47, 39.54 and 52.29 ° are respectively assigned to Mo2Crystal planes (021), (200) and (121) of C are represented by typical beta-Mo2XRD profile of C indicated that the product was Mo2C。
FIG. 2 shows Mo prepared in example 22Transmission electron microscopy of N material. As can be seen from fig. 2, the prepared material has a cubic shape and the sample particles are uniform in size.
FIG. 3 is a transmission electron micrograph of the material prepared in comparative example 1. As can be seen from fig. 3, the prepared material has no cubic structure and is irregular in shape.
FIG. 4 shows the results of example 2 and comparative example 1 at 0.1ACharge and discharge curves in g. As can be seen from FIG. 4, Mo prepared in example 22The specific capacity of the N material in first discharge can reach 420.2mAh/g, which is very close to that of Mo2Theoretical specific discharge capacity of N (430.2 mAh/g). Under the condition of 0.1A/g, the specific capacity of the material is not attenuated basically in the circulation process, the specific discharge capacity of the material after 100 cycles is 600.5mAh/g, and the specific discharge capacity retention rate is 88%. The specific discharge capacity of the material after 100 cycles is higher than the first specific discharge capacity, and the analysis reason is probably that the material is activated in the charging and discharging processes, the discharging capacity is enhanced, and the specific discharge capacity is increased. The specific first discharge capacity of the material prepared in comparative example 1 is only 261.5mAh/g, which is far lower than that of example 2.
Comparing examples with comparative example 1, it can be seen that comparative example 1 lacks melamine and Mo having no cubic structure is produced2C, the first discharge specific capacity is only 261.5 mAh/g; the sol-gel method and the melamine are mutually matched and act together, the growth rate of the crystal is reduced, the product is slowly crystallized, the crystal appearance of the product is good, and the specific surface area is large.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The preparation method of the cubic molybdenum nitride is characterized by comprising the following steps of:
s1, mixing the ethanol solution of urea, the ethanol solution of melamine and the ethanol solution of ammonium molybdate tetrahydrate, and stirring to obtain a mixed solution; the mass ratio of ammonium molybdate tetrahydrate, urea and melamine in the mixed solution is 5-11: 100: 3-6;
s2, aging the mixed solution obtained in the step S1 at room temperature for 24-72 hours to form sol/gel, and freeze-drying to form a solid;
s3, pre-burning the solid obtained in the step S2, then performing heat treatment, and cooling to room temperature to obtain precursor powder;
and S4, roasting the precursor powder obtained in the step S3 in a nitrogen atmosphere, and cooling to room temperature to obtain the molybdenum nitride electrode material.
2. The method for preparing cubic molybdenum nitride according to claim 1, wherein the mass ratio of ammonium molybdate tetrahydrate, urea and melamine in step S1 is 7:100: 4.5.
3. The method for preparing cubic molybdenum nitride according to claim 1, wherein in step S1, the mass ratio of absolute ethanol to water to urea in the ethanol solution of urea is 2.4:1: 1; the mass ratio of the absolute ethyl alcohol to the water to the melamine in the melamine ethanol solution is 240:100: 3-6; the mass ratio of the absolute ethyl alcohol to the water to the ammonium molybdate tetrahydrate in the ethyl alcohol solution of the ammonium molybdate tetrahydrate is 240:100: 5-11.
4. The method as claimed in claim 1, wherein the stirring time in step S1 is 12 h.
5. The method for preparing cubic molybdenum nitride according to claim 1, wherein the pre-sintering temperature in step S3 is 300-350 ℃ for 2-3 h; the heat treatment temperature is 400-500 ℃, and the time is 0.5-1 h.
6. The method for preparing cubic molybdenum nitride according to claim 5, wherein the pre-sintering temperature in step S3 is 300 ℃ for 2 h; the heat treatment temperature is 400 ℃ and the time is 0.5 h.
7. The method for preparing cubic molybdenum nitride according to claim 1, wherein the calcination temperature in step S4 is 700-900 ℃ for 2 hours.
8. Application of the cubic molybdenum nitride prepared by the preparation method of any one of claims 1 to 7 in preparation of a lithium ion battery cathode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110560014.9A CN113321192B (en) | 2021-05-21 | 2021-05-21 | Preparation method and application of cubic molybdenum nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110560014.9A CN113321192B (en) | 2021-05-21 | 2021-05-21 | Preparation method and application of cubic molybdenum nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113321192A true CN113321192A (en) | 2021-08-31 |
| CN113321192B CN113321192B (en) | 2022-02-08 |
Family
ID=77416223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110560014.9A Active CN113321192B (en) | 2021-05-21 | 2021-05-21 | Preparation method and application of cubic molybdenum nitride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113321192B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114156455A (en) * | 2021-11-30 | 2022-03-08 | 电子科技大学 | Heterostructure material for lithium metal battery lithium negative electrode protection, preparation and application |
| CN114551813A (en) * | 2022-02-28 | 2022-05-27 | 华中科技大学 | Metal lithium composite electrode, preparation method, application and battery |
| CN114669316A (en) * | 2022-04-01 | 2022-06-28 | 上饶师范学院 | Molybdenum-based nitrogen carrier and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786888A (en) * | 2018-06-20 | 2018-11-13 | 上海电力学院 | A kind of carbonitride Supported Nitrides nano particle photochemical catalyst and its preparation method and application |
| CN110171807A (en) * | 2019-06-10 | 2019-08-27 | 陕西师范大学 | A method of preparing three nickel by powder of nano silicon nitride |
| JP2020142980A (en) * | 2019-02-28 | 2020-09-10 | 国立大学法人北海道大学 | Method for producing molybdenum nitride and composite molybdenum nitride |
-
2021
- 2021-05-21 CN CN202110560014.9A patent/CN113321192B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786888A (en) * | 2018-06-20 | 2018-11-13 | 上海电力学院 | A kind of carbonitride Supported Nitrides nano particle photochemical catalyst and its preparation method and application |
| JP2020142980A (en) * | 2019-02-28 | 2020-09-10 | 国立大学法人北海道大学 | Method for producing molybdenum nitride and composite molybdenum nitride |
| CN110171807A (en) * | 2019-06-10 | 2019-08-27 | 陕西师范大学 | A method of preparing three nickel by powder of nano silicon nitride |
Non-Patent Citations (2)
| Title |
|---|
| CRISTINA GIORDANO ET AL.: "Synthesis of crystalline metal nitride and metal carbide nanostructures by sol-gel chemistry", 《NANO TODAY》 * |
| IFFAT ASHRAF ET AL.: "A Comprehensive Review on the Synthesis and Energy Applications of Nano-structured Metal Nitrides", 《FRONTIERS IN MATERIALS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114156455A (en) * | 2021-11-30 | 2022-03-08 | 电子科技大学 | Heterostructure material for lithium metal battery lithium negative electrode protection, preparation and application |
| CN114156455B (en) * | 2021-11-30 | 2023-04-07 | 电子科技大学 | Heterostructure material for lithium metal battery lithium negative electrode protection, preparation and application |
| CN114551813A (en) * | 2022-02-28 | 2022-05-27 | 华中科技大学 | Metal lithium composite electrode, preparation method, application and battery |
| CN114551813B (en) * | 2022-02-28 | 2024-02-02 | 华中科技大学 | Metal lithium composite electrode, preparation method, application and battery |
| CN114669316A (en) * | 2022-04-01 | 2022-06-28 | 上饶师范学院 | Molybdenum-based nitrogen carrier and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113321192B (en) | 2022-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113321192B (en) | Preparation method and application of cubic molybdenum nitride | |
| Marincaş et al. | Review on synthesis methods to obtain LiMn 2 O 4-based cathode materials for Li-ion batteries | |
| Alsamet et al. | Synthesis and characterization of nano-sized LiFePO4 by using consecutive combination of sol-gel and hydrothermal methods | |
| Sha et al. | Hierarchical carbon-coated acanthosphere-like Li4Ti5O12 microspheres for high-power lithium-ion batteries | |
| KR101135621B1 (en) | Method of producing crystalline titanium oxide power, method of producing negative active material, negative active material and rechargeable lithium battery | |
| CN106876705B (en) | Preparation method of in-situ synthesized carbon/carbon nanotube coated lithium iron phosphate composite material | |
| EP2125615A1 (en) | Method for preparing lithium iron phosphate as a positive electrode active material for a lithium ion secondary battery | |
| CN111106335B (en) | Preparation method of lithium ion battery composite negative electrode material | |
| CN112151804A (en) | Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof | |
| CN104241626A (en) | Sol-gel preparation method of lithium vanadate negative electrode material of lithium ion battery | |
| CN111564612B (en) | High-thermal-conductivity and high-electrical-conductivity lithium battery positive electrode material and preparation method thereof | |
| JP4798507B2 (en) | Method for producing single-crystal LiMn2O4 nanowire and high-rate Li-ion battery using single-crystal LiMn2O4 nanowire | |
| WO2014012258A1 (en) | Auto-thermal evaporative liquid-phase synthesis method for cathode material for battery | |
| CN115043387B (en) | Preparation method of ammonium ferromanganese phosphate, lithium ferromanganese phosphate and application thereof | |
| KR101617836B1 (en) | Carbon coated electrode active material for secondary battery, and fabrication methode for preparing the same | |
| CN114702022B (en) | Preparation method and application of hard carbon anode material | |
| Xiong et al. | A universal, facile and ultrafast monomer-tuned strategy to construct multi-dimensional hierarchical polymer structures and applications for lithium-ion batteries | |
| CN105591107B (en) | A kind of ultra-thin stratiform V5S8And preparation method thereof with the application in lithium ion/sodium-ion battery | |
| CN108598411B (en) | Nitrogen-doped carbon-coated tin oxide/iron oxide composite material, preparation method thereof and lithium battery material | |
| CN106887580B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN115064676B (en) | Sodium ion battery anode material and preparation method and application thereof | |
| Chen et al. | Core@ shell Sb@ Sb 2 O 3 nanoparticles anchored on 3D nitrogen-doped carbon nanosheets as advanced anode materials for Li-ion batteries | |
| CN115986090A (en) | Nitrogen-doped bismuth/carbon composite microsphere material and preparation method and application thereof | |
| CN114639808A (en) | Preparation method and application of nitrogen-doped carbon-coated sodium-rich cobalt ferricyanide material | |
| CN112331842B (en) | Molybdenum dioxide nanoparticle/carbon assembled zigzag nano hollow sphere material and preparation and application thereof |
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 |