CN114014303B - Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof - Google Patents

Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof Download PDF

Info

Publication number
CN114014303B
CN114014303B CN202111296260.4A CN202111296260A CN114014303B CN 114014303 B CN114014303 B CN 114014303B CN 202111296260 A CN202111296260 A CN 202111296260A CN 114014303 B CN114014303 B CN 114014303B
Authority
CN
China
Prior art keywords
tungsten nitride
doped graphene
solution
ethanol
composite nitrogen
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.)
Active
Application number
CN202111296260.4A
Other languages
Chinese (zh)
Other versions
CN114014303A (en
Inventor
陈远富
马飞
张小娟
张子恒
王滨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Electronic Science and Technology of China
Original Assignee
University of Electronic Science and Technology of China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Electronic Science and Technology of China filed Critical University of Electronic Science and Technology of China
Priority to CN202111296260.4A priority Critical patent/CN114014303B/en
Publication of CN114014303A publication Critical patent/CN114014303A/en
Application granted granted Critical
Publication of CN114014303B publication Critical patent/CN114014303B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a tungsten nitride nano needle composite nitrogen doped graphene nano sheet and a preparation method and application thereof, and the preparation method comprises the following steps: (1) Preparing a uniformly dispersed solution by using tungsten chloride and graphene oxide in a mixed solution of water and ethanol; (2) placing the dispersion liquid into a hydrothermal kettle for reaction; (3) Cleaning the obtained product with water and ethanol and drying; (4) And (3) ammoniating the precursor to finally obtain the tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets. The tungsten nitride nano needle composite nitrogen doped graphene nano sheet diaphragm intermediate layer prepared by the method is used as an efficient polysulfide catalyst and adsorbent, and has excellent lithium-sulfur battery performance. The method provides a new idea for the design of the application of the multifunctional diaphragm of the lithium-sulfur battery.

Description

Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof
Technical Field
The invention belongs to the preparation of novel lithium sulfur battery diaphragm modification materials, and particularly relates to a preparation method and application of a tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheet.
Background
The rapid development of lithium sulfur batteries, by virtue of their ideal theoretical capacity (1675 mAh g -1 ) Energy Density (2600 Whk g) -1 ) Advantages such as cost effectiveness, non-toxicity, and earth abundance have become the first choice for the next generation of energy storage systems. However, the goal of achieving commercial applications of lithium ion batteries has been hampered by various bottlenecks. First, the insulation properties of sulfur and Li 2 S 2 /Li 2 The conductivity difference of S limits the utilization of sulfur, resulting in fast sulfur capacity decay with poor rate capability. Second, polysulfides dissolved in the electrolyte cause a shuttling effect, and at the same time, li 2 S deposits on lithium metal cathodes, resulting in lower coulombic efficiency and severe self-discharge behavior. From polysulfide to Li 2 S 2 Solid-liquid phase transition from Li 2 S 2 To Li 2 Solid-solid phase transition of S impedes the conversion of electrochemical kinetics, leading to premature termination of the discharge process and slow reaction kinetics. Thus, a great search for highly conductive electrocatalysts is a viable method to modulate the shuttle effect, accelerating polysulfide redox reaction kinetics.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a simple and efficient method for preparing the tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets and applying the method to modification of lithium-sulfur battery diaphragms.
In the invention, researchers find that a tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets are used for modifying lithium-sulfur battery diaphragms. The material integrated micro-nano structure is characterized in that: the nitrogen doped graphene nano-sheet obviously improves the conductivity of the material and enriches the conduction path of ion/electron transfer; the conductive tungsten nitride nanoneedle with a large number of active sites is not only beneficial to electron/ion transfer and improves the utilization of active substances, but also can promote Li as polysulfide anchoring medium 2 S, thereby enhancing the redox kinetics of polysulfide conversion. The invention has simple experimental process, good repeatability and low cost, and provides a feasible preparation method for the application of the transition metal nitride composite material in the lithium-sulfur battery.
In order to achieve the aim of the invention, the invention provides a tungsten nitride nano needle composite nitrogen-doped graphene nano sheet, and a preparation method and application thereof.
The preparation method of the tungsten nitride nano needle composite nitrogen doped graphene nano sheet comprises the following steps:
step 1: preparing a precursor: taking 50-100 mg of tungsten chloride and 1-5 mg of graphene oxide as raw materials, taking 25-40 ml of water and 25-40 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A, ultrasonically dispersing graphene in water to obtain a solution B, mixing the solution A and the solution B, and stirring at room temperature for 0.5 hour;
step 2: preparing a precursor: putting the mixed solution into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; carrying out hydrothermal reaction and collecting a product to obtain black precursor powder;
step 3: ammoniation process: and (3) carrying out high-temperature annealing treatment on the black precursor powder in an ammonia atmosphere through a tube furnace, and keeping the high-temperature annealing at 600 ℃ for 2 hours to obtain final product powder.
Preferably, step 1 further comprises: taking 50-100 mg of tungsten chloride and 1-5 mg of graphene oxide as raw materials, and taking 25-40 ml of water and 25-40 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A; graphene oxide was placed in deionized water, sonicated for 0.5 hours by a cell pulverizer to obtain a uniform dispersion B, and the solutions a and B were mixed and stirred at room temperature for 0.5 hours.
Preferably, in step 3, the temperature rise rate in the tube furnace is 5 ℃ per minute.
Preferably, step 1 further comprises: preparing a precursor: the preparation method comprises the steps of taking 60 mg of tungsten chloride and 3 mg of graphene oxide as raw materials, taking 30 ml of water and 30 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A, dispersing graphene in water by ultrasonic to obtain a solution B, mixing the solution A and the solution B, and stirring at room temperature for 0.5 hour.
In the step 2, the hydrothermal reaction product is centrifugally washed by water and ethanol, and finally, the product is dried for 12 hours in a vacuum drying oven at 60 ℃ to obtain black precursor powder.
The invention also provides the tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets prepared by the method.
Preferably, the nano needle-shaped tungsten nitride is uniformly dispersed on the whole surface of the graphene nanoplatelets.
The invention also provides application of the tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets in lithium-sulfur battery diaphragms, which is characterized in that: the tungsten nitride nanoneedle and the nitrogen doped graphene nanosheet can improve the cycle performance and the rate capability of the lithium-sulfur battery.
Compared with the prior art, the invention has the advantages that:
1. the material of the invention has the shape of a nano needle composite nano sheet structure, and has good conductivity, adsorption performance and catalysis performance.
2. The invention has simple experimental process, repeatability and low cost.
3. The tungsten nitride nano needle composite nitrogen doped graphene nano sheet provided by the invention shows excellent electrochemical performance of the lithium sulfur battery, and provides a new thought for the design of the application of the multifunctional diaphragm of the lithium sulfur battery. .
Drawings
FIG. 1 is an X-ray diffraction diagram of a tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelet prepared by the invention;
FIG. 2 is a scanning electron microscope image of a tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelet prepared by the invention;
FIG. 3 is a graph showing the cycle performance of the tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets prepared by the invention;
in fig. 1 and 3, WN 0.67 Represents pure tungsten nitride nanoneedle, WN 0.67 And @ NG represents a tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheet, and PP represents a diaphragm without material modification.
Fig. 1 is an X-ray diffraction diagram of a tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelet prepared by the invention, and it can be seen that the synthesized product accords with a standard PDF card of pure tungsten nitride.
Fig. 2 is a scanning electron microscope image of a tungsten nitride nano needle composite nitrogen doped graphene nano sheet prepared by the method, and the morphology of the nano needle is that the nano needle is uniformly loaded on a two-dimensional nano sheet.
Fig. 3 is a cycle performance chart of the tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets prepared by the method, and the material can be seen to have excellent cycle stability.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Comparative example
The preparation method of the tungsten nitride nanoneedle comprises the following steps:
step 1: preparing a precursor: dissolving tungsten chloride powder in ethanol to obtain solution A by using 60 mg of tungsten chloride and 60 ml of ethanol as solvents, and stirring the solution A for 0.5 hour at room temperature;
step 2: preparing a precursor: putting the solution A into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; carrying out hydrothermal reaction and collecting a product to obtain deep blue precursor powder;
step 3: ammoniation process: and (3) carrying out high-temperature annealing treatment on the deep blue precursor powder in an ammonia atmosphere by a tube furnace, and keeping the high-temperature annealing at 600 ℃ for 2 hours to obtain the tungsten nitride nano needle powder.
Examples
The preparation method of the tungsten nitride nano needle composite nitrogen doped graphene nano sheet comprises the following steps:
step 1: preparing a precursor: taking 50-100 mg of tungsten chloride and 1-5 mg of graphene oxide as raw materials, and taking 25-40 ml of water and 25-40 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A; placing graphene oxide into deionized water, performing ultrasonic treatment for 0.5 hour through a cell pulverizer to obtain uniform dispersion liquid B, mixing the solution A and the solution B, and stirring at room temperature for 0.5 hour;
step 2: preparing a precursor: putting the mixed solution into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; and carrying out hydrothermal reaction, collecting a product, centrifugally washing the hydrothermal reaction product with water and ethanol, and finally, drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain black precursor powder.
Step 3: ammoniation process: and (3) carrying out high-temperature annealing treatment on the black precursor powder in an ammonia atmosphere through a tube furnace, wherein the high-temperature annealing is carried out at 600 ℃ for 2 hours, and the heating rate in the tube furnace is 5 ℃ per minute. To obtain the final product powder.
The obtained tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets are shown in fig. 2, and the nano needle-shaped tungsten nitride is uniformly dispersed on the whole surface of the graphene nanoplatelets.
Example 1
The preparation method of the tungsten nitride nano needle composite nitrogen doped graphene nano sheet comprises the following steps:
step 1: preparing a precursor: using 60 mg of tungsten chloride and 3 mg of graphene oxide as raw materials and using 30 ml of water and 30 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A; graphene oxide was placed in deionized water, sonicated for 0.5 hours by a cell pulverizer to obtain a uniform dispersion B, and the solutions a and B were mixed and stirred at room temperature for 0.5 hours.
Step 2: preparing a precursor: putting the mixed solution into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; and carrying out hydrothermal reaction, collecting a product, centrifugally washing the hydrothermal reaction product with water and ethanol, and finally, drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain black precursor powder.
Step 3: ammoniation process: and (3) carrying out high-temperature annealing treatment on the black precursor powder in an ammonia atmosphere through a tube furnace, wherein the high-temperature annealing is carried out at 600 ℃ for 2 hours, and the heating rate in the tube furnace is 5 ℃ per minute. To obtain the final product powder.
Example 2
The preparation method of the tungsten nitride nano needle composite nitrogen doped graphene nano sheet comprises the following steps:
step 1: preparing a precursor: using 50 mg of tungsten chloride and 1 mg of graphene oxide as raw materials and using 25 ml of water and 25 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A; graphene oxide was placed in deionized water, sonicated for 0.5 hours by a cell pulverizer to obtain a uniform dispersion B, and the solutions a and B were mixed and stirred at room temperature for 0.5 hours.
Step 2: preparing a precursor: putting the mixed solution into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; and carrying out hydrothermal reaction, collecting a product, centrifugally washing the hydrothermal reaction product with water and ethanol, and finally, drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain black precursor powder.
Step 3: ammoniation process: and (3) carrying out high-temperature annealing treatment on the black precursor powder in an ammonia atmosphere through a tube furnace, wherein the high-temperature annealing is carried out at 600 ℃ for 2 hours, and the heating rate in the tube furnace is 5 ℃ per minute. To obtain the final product powder.
Example 3
The preparation method of the tungsten nitride nano needle composite nitrogen doped graphene nano sheet comprises the following steps:
step 1: preparing a precursor: taking 100 mg of tungsten chloride and 5 mg of graphene oxide as raw materials and 40 ml of water and 40 ml of ethanol as solvents, and dissolving tungsten chloride powder in ethanol to obtain a solution A; graphene oxide was placed in deionized water, sonicated for 0.5 hours by a cell pulverizer to obtain a uniform dispersion B, and the solutions a and B were mixed and stirred at room temperature for 0.5 hours.
Step 2: preparing a precursor: putting the mixed solution into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; and carrying out hydrothermal reaction, collecting a product, centrifugally washing the hydrothermal reaction product with water and ethanol, and finally, drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain black precursor powder.
Step 3: ammoniation process: and (3) carrying out high-temperature annealing treatment on the black precursor powder in an ammonia atmosphere through a tube furnace, wherein the high-temperature annealing is carried out at 600 ℃ for 2 hours, and the heating rate in the tube furnace is 5 ℃ per minute. To obtain the final product powder.
Performance analysis
The difference between example 1 and comparative example is that: graphene oxide was not added in the comparative example.
Example 1 differs from example 2 and example 3 in that: the amount of raw materials of the precursor and the volume of the solvent in step 1 are different.
The tungsten nitride nano needle composite nitrogen doped graphene nano sheet is filtered on a diaphragm through vacuum suction, and then is packaged on a CR2025 button cell, and the electrochemical performance of the cell is tested to obtain the following cycle performance table:
comparative example and comparative table of properties of example 3
Tungsten chloride Oxidized graphene Water and its preparation method Ethanol Cycle performance
Example 1 60 mg 3 mg 30 ml 30 ml 85.1％
Example 2 50 1 25 25 80.5％
Example 3 100 5 40 40 82.7％
Comparative example 60 mg 0 0 60 ml 78.9％
By comparison of comparative example and example 1, it can be concluded that: according to the invention, after the tungsten nitride nanoneedle is compounded with the nitrogen-doped graphene nanosheets, the cycle performance is remarkably improved by 6.2%.
Example 1 compares with examples 2 and 3, example 1 has the best cycle performance because under this condition, the tungsten nitride nanoneedle can be better loaded on the nitrogen doped graphene nanoplatelets, exposing more active sites, thereby promoting electrochemical reaction kinetics.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims of this invention, which are within the skill of those skilled in the art, can be made without departing from the spirit and scope of the invention disclosed herein.

Claims (7)

1. The preparation method of the tungsten nitride nano needle composite nitrogen doped graphene nano sheet is characterized by comprising the following steps of:
step 1: preparing a precursor: taking 50-100 mg of tungsten chloride and 1-5 mg of graphene oxide as raw materials, taking 25-40 ml of water and 25-40 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A, ultrasonically dispersing graphene in water to obtain a solution B, mixing the solution A and the solution B, and stirring at room temperature for 0.5 hour;
step 2: preparing a precursor: putting the mixed solution into a reaction kettle, and carrying out hydrothermal treatment for 3-12 hours at 180 ℃; carrying out hydrothermal reaction and collecting a product to obtain black precursor powder;
step 3: ammoniation process: carrying out high-temperature annealing treatment on black precursor powder through a tube furnace in an ammonia atmosphere, and keeping the high-temperature annealing at 600 ℃ for 2 hours to obtain final product powder;
the prepared tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets have the advantage that the nano needle-shaped tungsten nitride is uniformly dispersed on the whole surface of the graphene nanosheets.
2. The method for preparing the tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets according to claim 1, wherein the method comprises the following steps of: step 1 is further as follows:
taking 50-100 mg of tungsten chloride and 1-5 mg of graphene oxide as raw materials, and taking 25-40 ml of water and 25-40 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A; graphene oxide was placed in deionized water, sonicated for 0.5 hours by a cell pulverizer to obtain a uniform dispersion B, and the solutions a and B were mixed and stirred at room temperature for 0.5 hours.
3. The method for preparing the tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets according to claim 1, wherein the method comprises the following steps of: in step 3, the temperature rise rate in the tube furnace was 5 ℃ per minute.
4. The method for preparing the tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets according to claim 1, wherein the method comprises the following steps of: step 1 is further as follows: preparing a precursor: the preparation method comprises the steps of taking 60 mg of tungsten chloride and 3 mg of graphene oxide as raw materials, taking 30 ml of water and 30 ml of ethanol as solvents, dissolving tungsten chloride powder in ethanol to obtain a solution A, dispersing graphene in water by ultrasonic to obtain a solution B, mixing the solution A and the solution B, and stirring at room temperature for 0.5 hour.
5. The method for preparing the tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelets according to claim 1, wherein the method comprises the following steps of: in the step 2, the hydrothermal reaction product is centrifugally washed by water and ethanol, and finally, the product is dried for 12 hours in a 60 ℃ vacuum drying oven, so that black precursor powder is obtained.
6. A tungsten nitride nanoneedle composite nitrogen-doped graphene nanoplatelet prepared according to the method of any one of claims 1 to 5.
7. The application of the tungsten nitride nanoneedle composite nitrogen-doped graphene nanosheets in lithium-sulfur battery diaphragms, according to claim 6, is characterized in that: the tungsten nitride nanoneedle and the nitrogen doped graphene nanosheet can improve the cycle performance and the rate capability of the lithium-sulfur battery.
CN202111296260.4A 2021-11-03 2021-11-03 Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof Active CN114014303B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111296260.4A CN114014303B (en) 2021-11-03 2021-11-03 Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111296260.4A CN114014303B (en) 2021-11-03 2021-11-03 Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114014303A CN114014303A (en) 2022-02-08
CN114014303B true CN114014303B (en) 2023-06-20

Family

ID=80060658

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111296260.4A Active CN114014303B (en) 2021-11-03 2021-11-03 Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114014303B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114743804B (en) * 2022-03-31 2023-05-26 河北工业大学 Preparation method of tungsten nitride-graphene oxide composite material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934584B (en) * 2015-05-13 2017-04-05 陕西科技大学 A kind of porous hollow shell WO3/WS2Nano material and preparation method thereof
CN105336919B (en) * 2015-10-10 2017-12-15 岭南师范学院 One species graphene WS2The preparation method of/nitrogen, phosphor codoping graphene electrochemistry storage sodium combination electrode
CN111354932B (en) * 2020-03-10 2022-08-09 肇庆市华师大光电产业研究院 Preparation method of lithium-sulfur battery positive electrode material
CN111354933B (en) * 2020-03-11 2022-06-17 肇庆市华师大光电产业研究院 Preparation method of tungsten nitride/nitrogen-doped graphene/tungsten oxide composite material applied to lithium-sulfur battery cathode material
CN112216833A (en) * 2020-11-11 2021-01-12 榆林学院 WS (WS)2/TiO2Preparation method of/nitrogen-doped graphene nanocomposite

Also Published As

Publication number Publication date
CN114014303A (en) 2022-02-08

Similar Documents

Publication Publication Date Title
CN108598390B (en) Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery
CN109659544B (en) Preparation method of graphene-coated bimetallic sulfide lithium/sodium ion battery negative electrode material
CN106025217B (en) Graphene/polyaniline/phosphomolybdic acid composite material preparation method
CN112635706B (en) Preparation method of graphene-manganese dioxide nanorod-shaped negative electrode material
CN106299344B (en) A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof
CN112467139A (en) Lithium ion battery positive electrode pre-lithiation agent and preparation method and application thereof
CN114014303B (en) Tungsten nitride nano needle composite nitrogen doped graphene nano sheet and preparation method and application thereof
CN109786741B (en) Preparation method of sodium ion battery anode material of bimetallic sulfide
CN109755542B (en) Sodium-sulfur battery positive electrode material and preparation method thereof
CN109888236B (en) Preparation method of lithium-sulfur battery positive electrode material
CN111180717A (en) Novel silicon-carbon composite negative electrode material and preparation method thereof
CN113517427B (en) Preparation method and application of carbon-coated antimony/antimony trisulfide composite material
CN103066288A (en) Preparation method of molybdenum-carbon composite cathode material of lithium ion battery
CN110600719B (en) Porous silicon-carbon lithium ion battery cathode material with high rate performance and preparation method thereof
CN110783542A (en) Paper towel derived carbon fiber loaded MoS 2Preparation method of micro-flower composite material and application of micro-flower composite material in lithium-sulfur battery
CN113087014B (en) Preparation method of carbon/selenium-doped titanium dioxide lithium-sulfur battery positive electrode material
CN115207285A (en) Molybdenum disulfide @ tungsten disulfide @ carbon cloth electrode material, and preparation method and application thereof
CN113903915A (en) Preparation method of graphene-coated porous lead oxide-lead sulfide composite material
CN109835956B (en) Preparation method and application of lithium ion battery positive electrode material
CN105140509A (en) Porous CoV2O6 nanosheet electrode material and preparation method and application thereof
CN109616662A (en) Nickel carries tungstic acid negative electrode material and preparation method thereof and lithium ion battery
CN115566362A (en) Vanadium nitride for inhibiting shuttle effect and lithium dendrite of lithium-sulfur battery, and preparation and application thereof
CN115321588B (en) Lithium titanate bowl-shaped microsphere and preparation method and application thereof
CN114944479B (en) Composite material of graphene composite potassium-silicon co-doped sodium vanadium phosphate, preparation and application
CN111370671B (en) Preparation method of lithium-sulfur battery positive electrode material

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