CN110615479A - Self-assembled hollow tubular tungsten disulfide nano material and preparation method and application thereof - Google Patents
Self-assembled hollow tubular tungsten disulfide nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a self-assembled hollow tubular tungsten disulfide nano material as well as a preparation method and application thereof, and the self-assembled hollow tubular tungsten disulfide nano material comprises the following steps: adding tungsten hexachloride and thioacetamide into ethanol, and stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a suspension A; step two, adding glucose and PVP into the suspension A, and stirring until the glucose and the PVP are completely dissolved to obtain a solution B; carrying out solvothermal reaction on the solution B at the reaction temperature of 200-240 ℃, and cooling after the reaction is finished; washing and drying a product of the solvothermal reaction to obtain a dried sample; and fifthly, annealing the dried sample, wherein the calcining temperature is 400-600 ℃, and obtaining the hollow tubular tungsten disulfide nano material. The hollow tubular tungsten disulfide nano material is prepared by a one-step solvothermal method, and the unique self-assembled hollow tubular structure can greatly relieve the volume expansion of the hollow tubular tungsten disulfide nano material in the charging and discharging processes, so that the structural stability is effectively maintained.
Description
Technical Field
The present invention relates to WS2Preparation of nano material, in particular to a self-assembly hollow tubular tungsten disulfide nano material and a preparation method and application thereof.
Background
WS2The nano-sheet is a typical two-dimensional layered transition metal dichalcogenide, covalent bonds (S-W-S) with strong acting force are arranged in the layer, van der Waals force with weak acting force is arranged between the layers, the interlayer spacing is about 0.62nm, metal ions with small size can be favorably diffused in a matrix, and the special structure can promote further reaction of lithium ions and sodium ions with the matrix material. WS2The structure of the nanoplatelets is similar to graphite, where 2D monolayers are stacked by weak van der waals interactions, and the 2D structure can provide large surface area and 2D percolation channels to facilitate rapid transport of electrons within a monolayer, so sodium and lithium ions can be readily transported from WS2Insertion and extraction into the nanosheet, therefore WS2Also considered as a potential anode material.
Although WS2Has larger specific surface area, but has lower electron mobility and can provide smaller capacitance. And large volume expansion during charge and discharge thereof causes collapse of the structure, resulting in poor cycle stability thereof.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a self-assembled hollow tubular tungsten disulfide nano material, a preparation method and application thereof, and the self-assembled hollow tubular structure is obtained, and the stability is improved when the self-assembled hollow tubular structure is used as a cathode material.
The invention is realized by the following technical scheme:
a preparation method of a self-assembled hollow tubular tungsten disulfide nano material comprises the following steps:
adding tungsten hexachloride and thioacetamide into ethanol, and stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a suspension A;
step two, adding glucose and PVP into the suspension A, and stirring until the glucose and the PVP are completely dissolved to obtain a solution B;
carrying out solvothermal reaction on the solution B at the reaction temperature of 200-240 ℃, and cooling after the reaction is finished;
washing and drying a product of the solvothermal reaction to obtain a dried sample;
and fifthly, annealing the dried sample, wherein the calcining temperature is 400-600 ℃, and obtaining the hollow tubular tungsten disulfide nano material.
Preferably, in step one, the molar ratio of tungsten hexachloride to thioacetamide is 1: 10.
Preferably, in the first step, the stirring speed is 500-800 r/min, and the stirring time is 30-120 min.
Preferably, in the second step, the mass ratio of the glucose to the PVP is 5:1, and the molar ratio of the thioacetamide to the glucose is (5-10): 1-3;
preferably, in the second step, the stirring speed is 500-800 r/min, and the stirring time is 10-30 min.
Preferably, in the third step, the reaction time is 4-48 h.
Preferably, in the fourth step, the drying is freeze-drying for 8-12 h at-40 to-70 ℃ and under a vacuum degree of 10-40 Pa.
Preferably, in the fifth step, the calcination time is 1-4 h, and the temperature rise rate is 5-20 ℃/min.
The self-assembly hollow tubular tungsten disulfide nano material obtained by the preparation method has a hollow structure of tungsten disulfide.
The self-assembled hollow tubular tungsten disulfide nano material is applied to a battery as a negative electrode material.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention utilizes a one-step solvothermal method to prepare the hollow tubular tungsten disulfide nano material. The experimental scheme is simple, the raw material cost is low, the reaction temperature is easy to control, and the used time is short. The growth of tungsten disulfide is assisted by a template method, the nucleation growth of tungsten disulfide is assisted by PVP, the shape and size of tungsten disulfide are effectively controlled, and a low-temperature calcination annealing process is combined to successfully synthesize the self-assembled hollow tubular structure. The unique self-assembly hollow tubular structure can greatly relieve the volume expansion of the material in the charging and discharging process, thereby effectively maintaining the structural stability. Meanwhile, the nanoscale size ensures that the electrolyte has a larger specific surface area, the contact area of the electrolyte is increased, and the nanoscale size can shorten the transmission of ions and electrons in the electrochemical reaction process, so that the electrolyte has excellent electrochemical performance and has wide research value and application value in the electrochemical field.
The tungsten disulfide nano material with the hollow tubular structure, which is prepared by the invention, is used as a cathode material of a sodium ion battery, so that the volume expansion of an electrode material in the charging and discharging processes can be effectively relieved, and the stability of the structure is ensured. The larger specific surface area of the catalyst enables the catalyst to have more reactive sites, and the catalyst has good cycling stability and excellent rate performance.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the hollow tubular tungsten disulfide nanomaterial prepared in example 3
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the hollow tubular tungsten disulfide nano material prepared in example 3
Fig. 3 is a Transmission Electron Microscope (TEM) photograph of the hollow tubular tungsten disulfide nanomaterial prepared in example 3.
FIG. 4 shows the cycle performance and rate capability of the prepared hollow tubular tungsten disulfide nano material as the negative electrode material of the sodium ion battery.
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.
A method for preparing a self-assembly hollow tubular tungsten disulfide electrode material. The method comprises the following steps:
step one, 0.2975-2.36 g of tungsten hexachloride and 0.567-4.5 g of thioacetamide are added into 30-60 mL of ethanol and are magnetically stirred until the thioacetamide is completely dissolved to form a blue-black suspension A, the stirring speed is 500-800 r/min, and the stirring time is 30-120 min. The molar ratio of the tungsten source to the sulfur source is controlled to be 1: 10.
Adding 0.27-1.08 g of glucose and 0.054-0.216 g of PVP into the suspension A, stirring until the mixture is completely dissolved to obtain a solution B, controlling the mass ratio of the glucose to the PVP to be 5:1, and controlling the molar ratio of the sulfur source to the glucose to be (5-10) to (1-3); the stirring speed is 500-800 r/min, and the stirring time is 10-30 min.
And step three, transferring the solution B to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200-240 ℃, the reaction time is 4-48 h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4-6 times, and drying the product in a freeze dryer at the temperature of-40 to-70 ℃ and the vacuum degree of 10-40 Pa for 8-12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 400-600 ℃, the heat preservation time is 1-4 h, and the heating rate is 5-20 ℃/min. Obtaining the hollow tubular tungsten disulfide nano material.
Example 1
The method comprises the following steps: 0.2975g of tungsten hexachloride and 0.567g of thioacetamide are added into 30mL of ethanol solution and stirred magnetically until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension A, the stirring speed is 500r/min, and the stirring time is 30min. Controlling the molar ratio of tungsten hexachloride to thioacetamide to be 1: 10;
step two: adding 0.27g of glucose and 0.054g of PVP into the suspension A, stirring until the mixture is completely dissolved, and controlling the mass ratio of the glucose to the PVP to be 5:1 and the molar ratio of thioacetamide to the glucose to be 5: 1; the stirring speed is 700r/min, and the stirring time is 10 min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 4 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-40 ℃ and the vacuum degree of 10Pa for 8 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 500 ℃, the heat preservation time is 4h, and the heating rate is 5 ℃/min. Obtaining the self-assembled hollow tubular tungsten disulfide nano material.
Example 2
The method comprises the following steps: 2.36g of tungsten hexachloride and 4.5g of thioacetamide are added into 60mL of ethanol solution and stirred magnetically until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension A, the stirring speed is 800r/min, and the stirring time is 120 min. The molar ratio of tungsten hexachloride to thioacetamide was controlled to 1: 10.
Step two: adding 3.08g of glucose and 0.616g of PVP into the suspension A, stirring until the mixture is completely dissolved, and controlling the mass ratio of the glucose to the PVP to be 5:1 and the molar ratio of thioacetamide to the glucose to be 7: 2; the stirring speed is 800r/min, and the stirring time is 20 min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 220 ℃, the reaction time is 48 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4 times, and drying the product in a freeze dryer at the temperature of-70 ℃ and the vacuum degree of 40Pa for 12 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 600 ℃, the heat preservation time is 1h, and the heating rate is 20 ℃/min. Obtaining the hollow tubular tungsten disulfide nano material.
Example 3
The method comprises the following steps: 1.18g of tungsten hexachloride and 2.25g of thioacetamide are added into 60mL of ethanol solution and stirred magnetically until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension A, the stirring speed is 800r/min, and the stirring time is 60 min. The molar ratio of tungsten hexachloride to thioacetamide was controlled to 1: 10.
Step two: adding 0.68g of glucose and 0.136g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the mass ratio of the glucose to the PVP to be 5:1 and the molar ratio of thioacetamide to the glucose to be 8: 1; the stirring speed is 800r/min, and the stirring time is 20 min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 200 ℃, the reaction time is 24 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out the product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 4-6 times, and drying the product in a freeze dryer with the temperature of-70 ℃ and the vacuum degree of 15Pa for 10 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 500 ℃, the heat preservation time is 2h, and the heating rate is 10 ℃/min. Obtaining the hollow tubular tungsten disulfide nano material.
Example 4
The method comprises the following steps: 1.18g of tungsten hexachloride and 2.25g of thioacetamide are added into 45mL of ethanol solution and stirred by magnetic force until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension A, the stirring speed is 600r/min, and the stirring time is 90 min. The molar ratio of tungsten hexachloride to thioacetamide was controlled to 1: 10.
Step two: adding 1.62g of glucose and 0.324g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the mass ratio of the glucose to the PVP to be 5:1 and the molar ratio of thioacetamide to the glucose to be 10: 3; the stirring speed is 800r/min, and the stirring time is 30min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction at the reaction temperature of 240 ℃ for 36h, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 5 times, and drying the product in a freeze dryer at the temperature of-50 ℃ and the vacuum degree of 25Pa for 9 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 400 ℃, the heat preservation time is 3h, and the heating rate is 10 ℃/min. Obtaining the hollow tubular tungsten disulfide nano material.
Example 5
The method comprises the following steps: 1.67g of tungsten hexachloride and 3.18g of thioacetamide are added into 40mL of ethanol solution and stirred magnetically until the tungsten hexachloride and the thioacetamide are completely dissolved to form a blue-black suspension A, the stirring speed is 800r/min, and the stirring time is 120 min. The molar ratio of tungsten hexachloride to thioacetamide was controlled to 1: 10.
Step two: adding 1.69g of glucose and 0.339g of PVP into the solution A, stirring until the glucose and the PVP are completely dissolved, and controlling the mass ratio of the glucose to the PVP to be 5:1 and the molar ratio of thioacetamide to the glucose to be 9: 2; the stirring speed is 500r/min, and the stirring time is 25 min.
Step three: and transferring the solution to a 100mL polytetrafluoroethylene reaction kettle for homogeneous reaction, wherein the reaction temperature is 210 ℃, the reaction time is 12 hours, and naturally cooling to room temperature after the reaction is finished.
Step four: and opening the reaction kettle, taking out a product, washing the product by using absolute ethyl alcohol and deionized water in sequence, performing centrifugal separation, repeatedly washing for 6 times, and drying the product in a freeze dryer at the temperature of-55 ℃ and the vacuum degree of 40Pa for 8 hours.
Step five: and (3) taking the dried sample, and carrying out annealing treatment in a low-temperature tube furnace, wherein the calcining temperature is 600 ℃, the heat preservation time is 3h, and the heating rate is 5 ℃/min. Obtaining the hollow tubular tungsten disulfide nano material.
A sample (hollow tubular tungsten disulfide nano material) is analyzed by a Japan science D/max2000 PCX-ray diffractometer, and an X-ray diffraction (XRD) pattern of the hollow tubular tungsten disulfide nano material prepared in example 3 is shown in figure 1, so that the sample and the WS of a hexagonal system with JCPDS serial numbers of 08-0237 are found2The structures are consistent, which indicates that the product prepared by the method is pure-phase tungsten disulfide and no other impurity phase exists.
The sample was observed with a Field Emission Scanning Electron Microscope (FESEM) and a transmission electron microscope. Fig. 2 is a Scanning Electron Microscope (SEM) photograph of the hollow tubular tungsten disulfide nanomaterial prepared in example 3. The morphology structure of the product is a uniform hollow cubic structure, and the prepared product has good dispersibility and uniform size distribution. Fig. 3 is a Transmission Electron Microscope (TEM) photograph of the hollow tubular tungsten disulfide nanomaterial prepared in example 3, the result is consistent with the scanning result, and the hollow structure can be clearly seen.
FIG. 4 shows the cycle performance and rate capability of the prepared hollow tubular tungsten disulfide nano material as the negative electrode material of the sodium ion battery. It can be seen that it is at 200mA g-1After 50 cycles at the current density of (1), the capacity retention rate is 84%. And it has excellent rate capability of 10A g-1At a current density of (2), the capacity of the capacitor was 141mAh g-1And when the current returns to a small current, the capacity of the capacitor rises to 366mAh g again-1. The electrochemical performance test shows that the structure has good cycling stability and excellent rate performance.
In a word, the tungsten disulfide nano material with a hollow tubular structure is successfully synthesized by utilizing one-step solvent heat and the template agent to assist in growing tungsten disulfide. The experimental operation process is simple, the raw material cost is low, the reaction temperature is easy to control, and the used time is short. The unique self-assembly hollow tubular structure can greatly relieve the volume expansion of the material in the charging and discharging process, thereby effectively maintaining the structural stability. Meanwhile, the nano-scale size can shorten the transmission of ions and electrons in the electrochemical reaction process, so that the electrochemical material has excellent electrochemical performance and has wide research value and application value in the electrochemical field.
Claims (10)
1. A preparation method of a self-assembled hollow tubular tungsten disulfide nano material is characterized by comprising the following steps:
adding tungsten hexachloride and thioacetamide into ethanol, and stirring until the tungsten hexachloride and the thioacetamide are completely dissolved to form a suspension A;
step two, adding glucose and PVP into the suspension A, and stirring until the glucose and the PVP are completely dissolved to obtain a solution B;
carrying out solvothermal reaction on the solution B at the reaction temperature of 200-240 ℃, and cooling after the reaction is finished;
washing and drying a product of the solvothermal reaction to obtain a dried sample;
and fifthly, annealing the dried sample, wherein the calcining temperature is 400-600 ℃, and obtaining the hollow tubular tungsten disulfide nano material.
2. The method for preparing the self-assembled hollow tubular tungsten disulfide nano material according to claim 1, wherein in the first step, the molar ratio of tungsten hexachloride to thioacetamide is 1: 10.
3. The method for preparing the self-assembly hollow tubular tungsten disulfide nano material as claimed in claim 1, wherein in the first step, the stirring speed is 500-800 r/min, and the stirring time is 30-120 min.
4. The method for preparing the self-assembled hollow tubular tungsten disulfide nano material according to claim 1, wherein in the second step, the mass ratio of glucose to PVP is 5:1, and the molar ratio of thioacetamide to glucose is (5-10): 1-3.
5. The method for preparing the self-assembly hollow tubular tungsten disulfide nano material according to claim 1, wherein in the second step, the stirring speed is 500-800 r/min, and the stirring time is 10-30 min.
6. The method for preparing the self-assembly hollow tubular tungsten disulfide nano material according to claim 1, wherein in the third step, the reaction time is 4-48 h.
7. The method for preparing the self-assembly hollow tubular tungsten disulfide nano material according to claim 1, wherein in the fourth step, the drying is carried out for 8-12 h under the conditions that the temperature is-40 to-70 ℃ and the vacuum degree is 10-40 Pa.
8. The preparation method of the self-assembly hollow tubular tungsten disulfide nano material according to claim 1, wherein in the fifth step, the calcination time is 1-4 h, and the temperature rise rate is 5-20 ℃/min.
9. The self-assembly hollow tubular tungsten disulfide nano material obtained by the preparation method of any one of claims 1 to 8, wherein the tungsten disulfide is in a hollow structure.
10. Use of the self-assembled hollow tubular tungsten disulfide nanomaterial of claim 9 as an anode material in a battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114784244A (en) * | 2022-04-21 | 2022-07-22 | 陕西科技大学 | Three-dimensional hollow WS2/C composite electrode material and preparation method and application thereof |
-
2019
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Non-Patent Citations (1)
| Title |
|---|
| JIANBIAO WANG ET AL.: ""Template-free synthesis of metallic WS2 hollow microspheres as an anode for the sodium-ion battery"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114784244A (en) * | 2022-04-21 | 2022-07-22 | 陕西科技大学 | Three-dimensional hollow WS2/C composite electrode material and preparation method and application thereof |
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