CN110880597A - Tungsten sulfide/CNTs @ C composite electrode material and preparation method thereof - Google Patents
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Abstract
The invention provides a tungsten sulfide/CNTs @ C composite electrode material and a preparation method thereof, wherein the preparation method comprises the following steps: adding CNTs into an ethanol solution, performing ultrasonic dispersion, adding tungsten hexachloride and thioacetamide, stirring, transferring to a microwave hydrothermal kettle, performing microwave hydrothermal reaction, controlling the microwave hydrothermal temperature at 200-220 ℃, the pressure at 0.5-5 MPa, and the reaction time at 0.5-4 h; washing and drying the reaction product to obtain black WS2a/CNTs composite; dissolving sucrose in water, adding WS2mixing/CNTs composite material, and freeze drying to obtain WS2Calcining the precursor of/CNTs @ C for 1-3 h at 400-650 ℃ under the protection of argon atmosphere to obtain WS2a/CNTs @ C composite. The obtained composite electrode material has excellent cycle stability.
Description
Technical Field
The present invention relates to WS2The technical field of nano material preparation, in particular to WS2a/CNTs @ C composite electrode material and a preparation method thereof.
Background
The two-dimensional transition metal sulfide is of a layered structure and exists in a form of X-M-X, and chalcogen element atoms are separated by transition metal atoms to form a sandwich structure to isolate the two-dimensional transition metal sulfide in two hexagonal space layered structures. The overall structure of the two-dimensional transition metal chalcogenide is a quadrangle or a hexagon. WS2As a transition metal chalcogenide, the transition metal chalcogenide has a hexagonal phase graphene-like laminated structure and large interlayer spacing
The unique layered structure and the larger interlayer distance are beneficial to the intercalation and deintercalation of sodium ions, and are potential sodium ion battery negative electrode materials. But the material has a larger volume expansion problem in the charging and discharging process, so that the cycling stability of the material is poor. And the material itself has poor conductivity, which is not conducive to electron transport. At present, the common solution to the problem of volume expansion is to synthesize a composite material using carbon as a matrix, relieve the stress generated in the volume expansion process, and enhance the conductivity of the material.
According to literature reports, the electrochemical performance of the composite material can be effectively improved by synthesizing the composite material with the carbon material as the matrix. The carbon material is beneficial to electron transmission, and can relieve stress generated by volume expansion of the electrode material in the charge-discharge process and prevent particle agglomeration. For example, Guowei Huang et al complexes tungsten disulfide with graphene oxide in three dimensions (Huang G, Liu H, Wang S, et al. structural architecture of WS2nanosheets on graphene frameworks with enhanced electrochemical propertiesfor lithium storage and hydrogen evolution[J]Journal of Materials chemistry A2015, 3(47): 24128-24138) as a negative electrode for lithium ion batteriesThe electrochemical performance of the material and the tungsten disulfide after compounding is greatly improved, but the cycling stability of the material and the tungsten disulfide is still to be further improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a tungsten sulfide/CNTs @ C composite electrode material and a preparation method thereof, and the obtained composite electrode material has excellent cycle stability.
The invention is realized by the following technical scheme:
a preparation method of a tungsten sulfide/CNTs @ C composite electrode material comprises the following steps:
the method comprises the following steps: adding CNTs into an ethanol solution, and performing ultrasonic dispersion to obtain a suspension A;
step two: adding tungsten hexachloride and thioacetamide into the suspension A, and stirring to obtain a solution B;
step three: transferring the solution B into a microwave hydrothermal kettle, sealing the microwave hydrothermal kettle, putting the microwave hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument for microwave hydrothermal reaction, controlling the microwave hydrothermal temperature at 200-220 ℃, the pressure at 0.5-5 MPa, and the reaction time at 0.5-4 h;
step four: washing and drying the reaction product to obtain black WS2a/CNTs composite;
step five: dissolving sucrose in water, adding WS2mixing/CNTs composite material, and freeze-drying to obtain black WS2CNTs @ C precursor;
step six: the above WS2Calcining the/CNTs @ C precursor for 1-3 h at 400-650 ℃ under the protection of argon atmosphere, wherein the obtained product is WS2a/CNTs @ C composite.
Preferably, in the step one, the concentration of CNTs in the suspension A is 0.5-2 mg/mL.
Preferably, in the second step, the mass ratio of the CNTs to the tungsten hexachloride is (30-60) mg: (0.275-0.55) g.
Preferably, in the third step, the filling ratio of the microwave hydrothermal kettle is 30-60%.
Preferably, in the fourth step, the drying is carried out for 8-12 h in a freeze dryer with the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa.
Preferably, in step five, sucrose and WS2The mass ratio of/CNTs is (1-3) to (2-5).
Preferably, in the sixth step, the temperature rise rate is 5-20 ℃/min.
The tungsten sulfide/CNTs @ C composite electrode material is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention successfully prepares WS by utilizing a microwave hydrothermal method and combining a low-temperature calcination carbonization process2a/CNTs @ C composite. The existence of the carbon nano tube effectively improves the conductivity of the material, enhances the transmission of electrons in the electrochemical reaction process, the carbon nano tube is used as a matrix to grow the tungsten disulfide, the tungsten disulfide has excellent mechanical and electronic properties, is considered to be one of the hardest and strongest fibers, has excellent conductivity, and has light weight, so that the tungsten disulfide has huge application potential in reinforced composite materials, nano electronics, sensors and nano mechanical equipment. Meanwhile, a multi-level composite structure is synthesized by carbon coating, and the volume expansion in the charging and discharging process is effectively inhibited by utilizing the synergistic effect among the multi-level structures, so that the carbon-coated composite material has excellent cycle stability. The preparation method is simple and easy to operate, the process parameters are easy to control, the application range is wide, the reaction time is greatly shortened, the reaction efficiency is improved, the repeatability is high, and the yield is high.
WS prepared according to the invention2the/CNTs @ C composite material has the advantages of uniform appearance, high electrochemical performance and stability and great application prospect in the application of the cathode of the sodium-ion battery.
Drawings
FIG. 1 shows WS prepared in example 32X-ray diffraction (XRD) pattern of/CNTs @ C composite.
FIG. 2 shows WS prepared in example 32Scanning Electron Microscope (SEM) pictures of the/CNTs @ C composite material, (a)20K, (b) 100K.
FIG. 3 shows WS prepared in example 32Permeability of/CNTs @ C composite materialElectron emission microscope (TEM) images.
FIG. 4 shows WS prepared in example 32CNTs and WS2the/CNTs @ C composite material (a) has cycle performance, and (b) has a rate performance graph.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The microwave hydrothermal method of the invention is used for preparing WS2A method of forming a/CNTs @ C composite, comprising the steps of:
the method comprises the following steps: under the condition of room temperature, 30-60 mg of CNTs are added into 30-60 mL of ethanol solution for ultrasonic treatment for 2-6 h, the concentration of the CNTs is controlled to be 0.5-2 mg/mL, and the ultrasonic power is 300-1000W, so that suspension A with good dispersibility is formed.
Step two: adding 0.275-0.55 g of tungsten hexachloride and 0.5625-1.125 g of thioacetamide into the suspension A, stirring at the speed of 500-800 r/min for 0.5-3 h to obtain a solution B.
Step three: and transferring the solution B into a microwave hydrothermal kettle, controlling the filling ratio to be 30-60%, then sealing the microwave hydrothermal kettle, putting the microwave hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature to be 200-220 ℃, the pressure to be 0.5-5 MPa and the reaction time to be 0.5-4 h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out a product, sequentially washing the product by absolute ethyl alcohol and deionized water, performing centrifugal separation, repeatedly washing for 4-6 times, placing the product in a freeze dryer with the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for drying for 8-12 hours to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 10-30 mL of aqueous solution, and adding WS2/CNTs composite, control m (sucrose): m (WS)2CNTs (1-3) and (2-5), stirring for 2-4 h, fully mixing, drying in a freeze dryer at-40 to-70 ℃ and a vacuum degree of 10-40 Pa for 8-12 h to obtain black WS2CNTs @ C precursor.
Step six: the above WS2/CNPlacing the Ts @ C precursor in a low-temperature tube furnace, calcining at 400-650 ℃ under the protection of argon atmosphere, keeping the temperature for 1-3 h at the heating rate of 5-20 ℃/min, and obtaining a product WS2a/CNTs @ C composite.
Example 1
The method comprises the following steps: under the condition of room temperature, 40mg of CNTs is added into 40mL of ethanol solution and is subjected to ultrasonic treatment for 2h, the concentration of the solution is controlled to be 1mg/mL, and the ultrasonic power is 1000W, so that suspension A with good dispersibility is formed.
Step two: 0.275g of tungsten hexachloride and 0.5625g of thioacetamide were added to the suspension A, and the mixture was stirred at a rate of 800r/min for 3 hours to obtain a solution B.
Step three: and transferring the solution B into a 100mL microwave hydrothermal kettle, controlling the filling ratio at 40%, then sealing the hydrothermal kettle, putting the hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature at 200 ℃, the pressure at 2MPa and the reaction time at 0.5h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, repeatedly washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 10 hr to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 10mL of water solution, adding WS2/CNTs composite, control m (sucrose): m (WS)2Stirring for 4h at 1: 2/CNTs, mixing, drying at-70 deg.C under vacuum degree of 10Pa for 10h to obtain black WS2CNTs @ C precursor.
Step six: placing the precursor in a low-temperature tube furnace, calcining at 400 ℃ under the protection of argon atmosphere, keeping the temperature for 1h at the heating rate of 5 ℃/min, and obtaining the product WS2a/CNTs @ C composite.
Example 2
The method comprises the following steps: under the condition of room temperature, 60mg of CNTs is added into 30mL of ethanol solution for ultrasonic treatment for 2h, the concentration of the solution is controlled to be 2mg/mL, and the ultrasonic power is 1000W, so that suspension A with good dispersibility is formed.
Step two: 0.55g of tungsten hexachloride and 1.125g of thioacetamide are added into the suspension A, the stirring speed is 800r/min, the stirring is carried out for 2h, and the obtained solution is a solution B.
Step three: and transferring the solution B into a 100mL microwave hydrothermal kettle, controlling the filling ratio at 30%, then sealing the hydrothermal kettle, putting the hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature at 220 ℃, the pressure at 3.5MPa and the reaction time at 2h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, repeatedly washing for 6 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 10 hr to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 10mL of water solution, adding WS2/CNTs composite, control m (sucrose): m (WS)2Stirring for 4h under 2:5 for thoroughly mixing, placing at-70 deg.C and vacuum degree of 40Pa, and drying in freeze dryer for 12h to obtain black WS2CNTs @ C precursor.
Step six: placing the precursor in a low-temperature tube furnace, calcining at 600 ℃ under the protection of argon atmosphere, keeping the temperature for 2h at the heating rate of 15 ℃/min, and obtaining the product WS2a/CNTs @ C composite.
Example 3
The method comprises the following steps: under the condition of room temperature, 60mg of CNTs is added into 60mL of ethanol solution for ultrasonic treatment for 4h, the concentration of the solution is controlled to be 1mg/mL, and the ultrasonic power is 800W, so that suspension A with good dispersibility is formed.
Step two: 0.38g of tungsten hexachloride and 1.18g of thioacetamide are added into the suspension A, the stirring speed is 800r/min, the stirring is carried out for 1.5h, and the obtained solution is a solution B.
Step three: and transferring the solution B into a microwave hydrothermal kettle, controlling the filling ratio to be 60%, then sealing the hydrothermal kettle, putting the hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature to be 210 ℃, the pressure to be 1MPa, and the reaction time to be 4h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 4 times, drying in a freeze dryer at-50 deg.C and vacuum degree of 35Pa for 12 hr to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 30mL of water solution, adding WS2/CNTs composite, control m (sucrose): m (WS)2Stirring for 4h at a ratio of 3:5, mixing thoroughly, drying in a freeze dryer at-70 deg.C and vacuum degree of 40Pa for 8h to obtain black WS2CNTs @ C precursor.
Step six: placing the precursor in a low-temperature tube furnace, calcining at 500 ℃ under the protection of argon atmosphere, heating at a rate of 10 ℃/min, and preserving heat for 2h to obtain a product WS2a/CNTs @ C composite.
Example 4
The method comprises the following steps: under the condition of room temperature, adding 60mg of CNTs into 30mL of ethanol solution, and carrying out ultrasonic treatment for 2-6 h, wherein the concentration of the CNTs is controlled to be 2mg/mL, and the ultrasonic power is 500W, so that a suspension A with good dispersibility is formed.
Step two: 0.45g of tungsten hexachloride and 0.78g of thioacetamide are added into the suspension A, the stirring speed is 750r/min, the stirring is carried out for 2 hours, and the obtained solution is a solution B.
Step three: and transferring the solution B into a microwave hydrothermal kettle, controlling the filling ratio to be 60%, then sealing the hydrothermal kettle, putting the hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature to be 200 ℃, the pressure to be 1.5MPa and the reaction time to be 2h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 5 times, drying in a freeze dryer at-70 deg.C and vacuum degree of 30Pa for 10 hr to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 15mL of water solution, adding WS2/CNTs composite, control m (sucrose): m (WS)2CNTs) 3:2, stirring for 2.5h to obtainMixing completely, drying in a freeze drier at-70 deg.C and vacuum degree of 40Pa for 12 hr to obtain black WS2CNTs @ C precursor.
Step six: placing the precursor in a low-temperature tube furnace, calcining at 650 ℃ under the protection of argon atmosphere, keeping the temperature for 3h at the heating rate of 15 ℃/min, and obtaining the product WS2a/CNTs @ C composite.
Example 5
The method comprises the following steps: under the condition of room temperature, 50mg of CNTs is added into 50mL of ethanol solution and subjected to ultrasonic treatment for 2-6 h, the concentration of the solution is controlled to be 1mg/mL, and the ultrasonic power is 700W, so that suspension A with good dispersibility is formed.
Step two: 0.285g of tungsten hexachloride and 1.125g of thioacetamide are added into the suspension A, the stirring speed is 600r/min, the stirring is carried out for 2h, and the obtained solution is a solution B.
Step three: and transferring the solution B into a microwave hydrothermal kettle, controlling the filling ratio to be 50%, then sealing the hydrothermal kettle, putting the hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature to be 220 ℃, the pressure to be 0.5MPa, and the reaction time to be 3h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, washing for 6 times, drying in a freeze dryer at-40 deg.C and vacuum degree of 40Pa for 12 hr to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 30mL of water solution, adding WS2/CNTs composite, control m (sucrose): m (WS)2Stirring for 4h at 1: 5/CNTs, mixing, drying at-70 deg.C under vacuum degree of 40Pa for 12h to obtain black WS2CNTs @ C precursor.
Step six: placing the precursor in a low-temperature tube furnace, calcining at 550 ℃ under the protection of argon atmosphere, heating at a rate of 10 ℃/min, and preserving heat for 2h to obtain the product WS2a/CNTs @ C composite.
Example 6
The method comprises the following steps: under the condition of room temperature, 30mg of CNTs is added into 60mL of ethanol solution for ultrasonic treatment for 2h, the concentration of the solution is controlled to be 0.5mg/mL, and the ultrasonic power is 1000W, so that suspension A with good dispersibility is formed.
Step two: 0.450g of tungsten hexachloride and 0.78g of thioacetamide are added into the suspension A, the stirring speed is 800r/min, the stirring is carried out for 3h, and the obtained solution is a solution B.
Step three: and transferring the solution B into a 100mL microwave hydrothermal kettle, controlling the filling ratio at 60%, then sealing the hydrothermal kettle, putting the hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument, controlling the microwave hydrothermal temperature at 205 ℃, the pressure at 2MPa and the reaction time at 0.5h, and naturally cooling to room temperature after the reaction is finished.
Step four: opening the microwave reaction kettle, taking out the product, sequentially washing with anhydrous ethanol and deionized water, centrifuging, repeatedly washing for 6 times, drying in a freeze dryer at-50 deg.C and vacuum degree of 10Pa for 8 hr to obtain black WS2a/CNTs composite material.
Step five: dissolving sucrose in 10mL of water solution, adding WS2/CNTs composite, control m (sucrose): m (WS)2Stirring for 4h at 1: 3/CNTs, mixing, drying at-50 deg.C under vacuum degree of 10Pa for 8h to obtain black WS2CNTs @ C precursor.
Step six: placing the precursor in a low-temperature tube furnace, calcining at 400 ℃ under the protection of argon atmosphere, heating at the rate of 20 ℃/min, and preserving heat for 1h to obtain the product WS2a/CNTs @ C composite.
FIG. 1 shows WS prepared in example 32X-ray diffraction (XRD) pattern of/CNTs @ C composite. Sample and WS of hexagonal system having JCPDS number 08-02372The structures are consistent, which shows that the tungsten disulfide prepared by the method has higher purity and no impurity phase.
FIG. 2 shows WS prepared in example 32Scanning Electron Microscope (SEM) picture of/CNTs @ C composite. WS can be seen2The nano-sheet grows on the surface of the carbon nano-tube uniformly, and a thin carbon layer exists. WS prepared by the method of the invention2/CNTs @ C composite productThe dispersibility is better.
FIG. 3 shows WS prepared in example 32Transmission Electron Microscopy (TEM) pictures of the/CNTs @ C composite. WS can be seen2A thin carbon layer exists outside the nano sheet, and the thickness of the carbon layer is about 3-5 nm.
FIG. 4 shows WS prepared in example 32CNTs and WS2the/CNTs @ C composite material (a) has cycle performance, and (b) has a rate performance graph. The cycle stability and the rate capability of the coated composite material are further improved.
In a word, the WS is successfully prepared by utilizing a microwave hydrothermal method and combining a low-temperature calcination carbonization process2a/CNTs @ C composite. The preparation method is simple and easy to operate, the process parameters are easy to control, and the repeatability is high. The existence of the carbon nano tube effectively improves the conductivity of the material, enhances the transmission of electrons in the electrochemical reaction process, and simultaneously, the carbon coating effectively inhibits the volume expansion in the charge and discharge process, so that the material has excellent electrochemical performance. WS prepared according to the invention2the/CNTs @ C composite material has the advantages of simple and feasible experimental scheme, high yield, uniform appearance and wide research value and application value in the field of application of sodium-ion battery cathodes.
Claims (8)
1. A preparation method of a tungsten sulfide/CNTs @ C composite electrode material is characterized by comprising the following steps:
the method comprises the following steps: adding CNTs into an ethanol solution, and performing ultrasonic dispersion to obtain a suspension A;
step two: adding tungsten hexachloride and thioacetamide into the suspension A, and stirring to obtain a solution B;
step three: transferring the solution B into a microwave hydrothermal kettle, sealing the microwave hydrothermal kettle, putting the microwave hydrothermal kettle into a high-flux ultrahigh-pressure microwave digestion instrument for microwave hydrothermal reaction, controlling the microwave hydrothermal temperature at 200-220 ℃, the pressure at 0.5-5 MPa, and the reaction time at 0.5-4 h;
step four: washing and drying the reaction product to obtain black WS2a/CNTs composite;
step five: dissolving sucrose in waterIn (b), the above-mentioned WS is added2mixing/CNTs composite material, and freeze-drying to obtain black WS2CNTs @ C precursor;
step six: the above WS2Calcining the/CNTs @ C precursor for 1-3 h at 400-650 ℃ under the protection of argon atmosphere, wherein the obtained product is WS2a/CNTs @ C composite.
2. The preparation method of the tungsten sulfide/CNTs @ C composite electrode material according to claim 1, characterized in that in the step one, the concentration of CNTs in the suspension A is 0.5-2 mg/mL.
3. The preparation method of the tungsten sulfide/CNTs @ C composite electrode material according to claim 1, wherein in the second step, the mass ratio of CNTs to tungsten hexachloride is (30-60) mg: (0.275-0.55) g.
4. The preparation method of the tungsten sulfide/CNTs @ C composite electrode material according to claim 1, characterized in that, in the third step, the filling ratio of the microwave hydrothermal kettle is 30% -60%.
5. The preparation method of the tungsten sulfide/CNTs @ C composite electrode material as claimed in claim 1, wherein in the fourth step, the drying is carried out for 8-12 h in a freeze dryer with the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa.
6. The method of claim 1, wherein in step five, sucrose and WS are added2The mass ratio of/CNTs is (1-3) to (2-5).
7. The preparation method of the tungsten sulfide/CNTs @ C composite electrode material according to claim 1, characterized in that in the sixth step, the temperature rise rate is 5-20 ℃/min.
8. The tungsten sulfide/CNTs @ C composite electrode material obtained by the preparation method of claim 1.
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| CN111704125A (en) * | 2020-06-16 | 2020-09-25 | 齐齐哈尔大学 | WS (WS)2Preparation method of (N-styrene-butadiene-styrene)/CNTs (carbon nanotubes) hybrid wave-absorbing material |
| CN112811469A (en) * | 2021-03-15 | 2021-05-18 | 陕西科技大学 | Preparation method of single-layer or few-layer tungsten disulfide nano material |
| CN112919544A (en) * | 2021-01-25 | 2021-06-08 | 齐齐哈尔大学 | Low-frequency-band electromagnetic wave absorption WS2/TiO2Method for preparing hybrid material |
| CN113611835A (en) * | 2021-07-31 | 2021-11-05 | 青岛科技大学 | g-C3N4@WS2Electroactive material, method for the production thereof and use thereof |
| CN114203984A (en) * | 2021-11-08 | 2022-03-18 | 南京航空航天大学 | WS (WS)2@MoS2@ C/rGO electrode material, and preparation method and application thereof |
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