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

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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
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doped graphene
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陈远富
马飞
张小娟
张子恒
王滨
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University of Electronic Science and Technology of China
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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.
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