CN109264783B - Polycrystal nanobelt self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof - Google Patents
Polycrystal nanobelt self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof Download PDFInfo
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Abstract
Polycrystal sodiumRice-stripe self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof, and polycrystalline nanobelt self-assembled three-dimensional hollow VS prepared by simple one-step hydrothermal method4Microspheres and no template agent is used for assisting the whole reaction process. When the product is applied to a lithium/sodium ion battery negative electrode material, excellent electrochemical performance can be shown, and a small pulverization phenomenon is shown in the charging and discharging process. The powder consists of microspheres with the diameter of 0.5-2 mu m, the microspheres have a three-dimensional hollow structure formed by self-assembling nanobelts in a winding mode, the diameter of the nanobelts is about 50-100 nm, the nanobelts are of a polycrystalline structure, and the interplanar spacing of a crystal face (110) can reach 0.581 nm. Polycrystalline nanoribbon self-assembled three-dimensional hollow VS prepared by preparation method of invention4The microspheres are applied to the field of lithium/sodium ion batteries, and have unique structural characteristics, so that the microspheres can show excellent electrochemical performance.
Description
Technical Field
The invention relates to a VS4Nano powder and its preparation method and application, in the concrete, it relates to a polycrystal nano belt self-assembled three-dimensional hollow VS4Microspheres and a preparation method and application thereof.
Background
Lithium/sodium ion batteries have the advantages of low cost and high efficiency in large-scale energy storage system applications, and have been widely used in various electronic devices and power tools [ Pan H, Hu Y-S, Chen L&Environmental Science.2013；6:2338-60.]. With the continuous deepening of the application, higher requirements are put on the performance of the lithium/sodium ion battery. As a very important part of lithium/sodium ion batteries, negative electrode materialsTheir low performance limits their further applications. In order to find a negative electrode material with better performance, researchers have conducted a lot of research. Among the negative electrode materials that have been reported, researchers generally believe that the mineral VS with high theoretical capacity4Is a very potential candidate, and the adjustment of the nano structure of the nano-porous membrane can further improve the electrochemical performance of the nano-porous membrane. However, the pure phase VS reported so far4Exhibits poor electrochemical properties and has a problem of easy pulverization, which greatly limits its application. At the same time, the VS reported at present4Mostly exhibit a nanorod dispersion structure and a self-assembled solid structure.
Disclosure of Invention
The invention aims to provide a polycrystalline nanoribbon self-assembled three-dimensional hollow VS4Microspheres and a preparation method and application thereof, namely, the polycrystalline nanobelt self-assembled three-dimensional hollow VS is prepared by a simple one-step hydrothermal method4Microspheres and no template agent is used for assisting the whole reaction process. When the product is applied to a lithium/sodium ion battery negative electrode material, excellent electrochemical performance can be shown, and a small pulverization phenomenon is shown in the charging and discharging process.
In order to achieve the above purpose, the preparation method of the invention comprises the following steps:
the method comprises the following steps: simultaneously adding 0.9-1.1 g of sodium metavanadate and 3.5-3.7 g of thioacetamide into 58-62 ml of deionized water, and carrying out magnetic stirring or ultrasonic dispersion to obtain a semi-clear solution A;
preparing a sodium hydroxide solution B of 2.8-3.2 mol/L, and adding the solution B into the solution A to enable the pH value of the solution B to reach 10.1-10.3 to obtain a solution C;
step three: pouring the solution C into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and then reacting for 17.5-18.5 h at 95-105 ℃ under the condition of a rotating speed of 5-10 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out a cooled product after the reaction, and collecting the product after alternately cleaning by water and alcohol;
step five: placing the collected product in a cold well of a freeze dryer for freezing, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 10-20 Pa, drying for 12-18 h, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
The step 1) of magnetic stirring or ultrasonic dispersion is carried out at room temperature, and the rotating speed of the magnetic stirring is 400-600 r/min.
And 2) in the step 2), the solvent of the sodium hydroxide solution is deionized water, and the sodium hydroxide solution B is dropwise added into the solution A under the condition of continuous magnetic stirring, namely after 1 drop of the sodium hydroxide solution is added, stirring is carried out until the pH value of the solution is stable, and the steps are repeated continuously until the pH value of the solution is adjusted to 10.1-10.3.
The filling ratio of the solution C poured into the reaction lining in the step 3) is 58-62%.
And 4) alternately cleaning with water and alcohol for 2-5 times respectively, and collecting the product in a suction filtration or centrifugation mode.
The freezing conditions of the step 5) are as follows: freezing for 2-5 hours at-60 to-40 ℃.
And (3) before the product in the step 5) is placed into a tray for drying, sealing the product by using a preservative film, and pricking the preservative film.
Polycrystalline nanoribbon self-assembled three-dimensional hollow VS prepared by preparation method of invention4The microsphere comprises microspheres with the diameter of 0.5-2 mu m, wherein the microspheres have a three-dimensional hollow structure formed by self-assembling nanobelts in a winding mode, the diameter of each nanobelt is about 50-100 nm, each nanobelt is of a polycrystalline structure, and the interplanar spacing of a crystal face (110) can reach 0.581 nm.
Polycrystalline nanoribbon self-assembled three-dimensional hollow VS prepared by preparation method of invention4The microspheres are applied to the field of lithium/sodium ion batteries, and have unique structural characteristics, so that the microspheres can show excellent electrochemical performance.
The method has the following specific beneficial effects:
(1) because the invention adopts one-step hydrothermal reaction to directly synthesize the final product, the invention has low synthesis temperature, simple synthesis path and no need of large-scale equipment and harsh reaction conditions;
(2) the vanadium source used in the invention is sodium metavanadate, the sulfur source is thioacetamide, and the two raw materials are common materials, and have the advantages of low price, easy obtainment, low cost and high yield.
(3) The method has the advantages of no template agent addition, easily controlled reaction, no need of post treatment, environmental friendliness and suitability for large-scale production;
(4) the product prepared by the method has the advantages of uniform chemical composition, high purity and uniform appearance, and can show excellent performance when being used as a negative electrode material of a lithium/sodium ion battery;
(5) the invention realizes the self-assembly of the polycrystalline nanobelt into the three-dimensional hollow VS through the cooperative control of the concentration and the proportion of the vanadium source and the sulfur source, the pH value of the reaction solution, the reaction temperature, the reaction time, the reaction filling ratio, the drying mode and other parameters4The controllable synthesis of the microspheres has higher control precision. In particular, both the parameters of reaction pH and reaction temperature have a decisive influence on the structure of the product.
(6) Under the conditions of overhigh and overlow pH values, the self-assembled three-dimensional hollow VS of the polycrystalline nanobelt cannot be obtained4A microsphere structure.
(7) Under the conditions of excessively high and excessively low reaction temperature, the self-assembled three-dimensional hollow VS of the polycrystalline nanobelt cannot be obtained4A microsphere structure.
(8) The concentration of the sodium hydroxide solution for adjusting the pH value of the solution in the invention must be strictly controlled at 2.8-3.2 mol/L, too high concentration is not beneficial to the formation of a uniform hollow structure, too low concentration can seriously affect the reaction filling ratio, and also is not beneficial to the formation of the hollow structure.
(9) The product prepared by the invention has a unique self-assembly structure, wherein the unique physical confinement effect between nanobelts in the self-assembly structure and the unique volume buffer effect of a hollow structure can effectively inhibit VS in the charge-discharge process4The structure of (2) is collapsed, so that the cycle stability of the material can be improved.
(10) The product prepared by the invention has a unique hollow structure, so that the product shows smaller mass density, and can show high specific capacity.
(11) VS in the products prepared according to the invention4The nanobelt has a unique polycrystalline structure and can be L i in the charge and discharge process+/Na+Can also provide L i as more active sites+/Na+Provides more permeation channels, enabling it to exhibit higher capacity and rate capability.
(12)VS4The nanobelt has a large chain pitch structure, so that more L i can be stored+/Na+Can also be L i+/Na+Provides smoother access between chains, and can improve VS synergistically4Capacity and rate capability.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1 of this invention. It can be observed that the diffraction peaks match well with standard card PDF #72-1294, indicating that the synthesized product is monoclinic phase VS4. Notably, the overall diffraction pattern has more fringes, meaning lower crystallinity.
FIG. 2 is a scanning electron micrograph of a product prepared according to example 1 of the present invention. As can be seen from the figure, the obtained product is composed of three-dimensional self-assembled microspheres with the diameter of about 0.5-2 μm.
FIG. 3 is a high power scanning electron micrograph of the product prepared in example 1 of the present invention. As can be seen from the figure, the microsphere has a three-dimensional structure in which nanobelts are self-assembled in a winding manner, and the diameter of the nanobelts is about 50-100 nm.
FIG. 4 is a transmission electron micrograph of the product prepared in example 1 of the present invention. From the figure, the resulting product VS can be determined4The micro-spheres have a hollow structure.
FIG. 5 is a schematic representation of the preparation of VS in example 1 of the present invention4Selected area electron diffraction patterns of the nanoribbons. Diffraction rings with different radii can be observed from the figure, indicating that the nanoribbons are polycrystalline structures.
Detailed Description
Example 1:
the method comprises the following steps: simultaneously adding 1g of sodium metavanadate and 3.6g of thioacetamide into 60ml of deionized water, and magnetically stirring at room temperature at 500r/min to obtain a semi-clear solution A;
step two, preparing 3 mol/L sodium hydroxide solution B by deionized water, dropwise adding the sodium hydroxide solution B into the solution A under the condition of continuous magnetic stirring, namely adding 1 drop of sodium hydroxide solution B, stirring until the pH value of the solution is stable, and repeating the steps until the pH value of the solution is adjusted to 10.2 to obtain solution C;
step three: pouring the solution C into a reaction inner liner according to the filling ratio of 60%, sealing, then placing the inner liner into an outer kettle, fixing, placing into a homogeneous reactor, and then reacting for 18h at 100 ℃ under the condition of the rotating speed of 10 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the cooled product after the reaction, alternately cleaning for 3 times by water and alcohol, and collecting the product in a suction filtration mode;
step five: placing the collected product in a cold well of a freeze dryer at-50 ℃ for freezing for 3 hours, then placing the frozen product in a tray, sealing the tray by using a preservative film, pricking the preservative film, covering a sealing cover, vacuumizing to 16Pa, drying for 12 hours, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
From FIG. 1, it can be observed that the diffraction peaks match well with standard card PDF #72-1294, indicating that the synthesized product is monoclinic phase VS4. Notably, the overall diffraction pattern has more fringes, meaning lower crystallinity.
As can be seen from FIG. 2, the obtained product is composed of three-dimensional self-assembled microspheres with a diameter of about 0.5-2 μm.
As can be seen from FIG. 3, the microspheres have a three-dimensional structure in which nanobelts are self-assembled in a winding manner, and the diameter of the nanobelts is about 50-100 nm.
From FIG. 4, the resulting product VS was determined4The micro-spheres have a hollow structure.
From fig. 5, diffraction rings with different radii can be observed, indicating that the nanoribbons are polycrystalline structures.
Example 2:
the method comprises the following steps: simultaneously adding 1.1g of sodium metavanadate and 3.7g of thioacetamide into 58ml of deionized water, and magnetically stirring at room temperature at 400r/min to obtain a semi-clear solution A;
step two, preparing 2.8 mol/L sodium hydroxide solution B by deionized water, dropwise adding the sodium hydroxide solution B into the solution A under the condition of continuous magnetic stirring, namely adding 1 drop of sodium hydroxide solution B, stirring until the pH value of the solution is stable, and continuously repeating the steps until the pH value of the solution is adjusted to 10.1 to obtain solution C;
step three: pouring the solution C into a reaction inner liner according to a filling ratio of 58%, sealing, then placing the inner liner into an outer kettle, fixing, placing into a homogeneous reactor, and then reacting at 95 ℃ for 18.5h under the condition of a rotating speed of 5 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the cooled product after the reaction, alternately washing the product for 2 times by water and alcohol, and collecting the product in a centrifugal mode;
step five: placing the collected product in a cold well of a freeze dryer at-60 ℃ for freezing for 5 hours, then placing the frozen product in a tray, sealing the tray by using a preservative film, pricking the preservative film, covering a sealing cover, vacuumizing to 10Pa, drying for 18 hours, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
Example 3:
the method comprises the following steps: simultaneously adding 0.9g of sodium metavanadate and 3.5g of thioacetamide into 62ml of deionized water, and magnetically stirring at room temperature at 600r/min to obtain a semi-clear solution A;
step two, preparing 3.2 mol/L sodium hydroxide solution B by deionized water, dropwise adding the sodium hydroxide solution B into the solution A under the condition of continuous magnetic stirring, namely adding 1 drop of sodium hydroxide solution B, stirring until the pH value of the solution is stable, and continuously repeating the steps until the pH value of the solution is adjusted to 10.3 to obtain solution C;
step three: pouring the solution C into a reaction inner liner according to a filling ratio of 61%, sealing, then placing the inner liner into an outer kettle, fixing, placing into a homogeneous reactor, and then reacting for 17.5 hours at 105 ℃ under the condition of a rotating speed of 8 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the cooled product after the reaction, alternately washing the product for 5 times by water and alcohol, and collecting the product in a suction filtration mode;
step five: placing the collected product in a cold well of a freeze dryer at the temperature of-40 ℃ for freezing for 2 hours, then placing the frozen product in a tray, sealing the tray by using a preservative film, pricking the preservative film, covering a sealing cover, vacuumizing to 20Pa, drying for 12 hours, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
Example 4:
the method comprises the following steps: simultaneously adding 1.05g of sodium metavanadate and 3.7g of thioacetamide into 59ml of deionized water, and performing ultrasonic dispersion at room temperature to obtain a semi-clear solution A;
step two, preparing 2.9 mol/L sodium hydroxide solution B by deionized water, dropwise adding the sodium hydroxide solution B into the solution A under the condition of continuous magnetic stirring, namely adding 1 drop of sodium hydroxide solution B, stirring until the pH value of the solution is stable, and continuously repeating the steps until the pH value of the solution is adjusted to 10.2 to obtain solution C;
step three: pouring the solution C into a reaction inner liner according to a filling ratio of 59%, sealing, then placing the inner liner into an outer kettle, fixing, placing into a homogeneous reactor, and then reacting at 98 ℃ for 18h under the condition of a rotating speed of 9 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the cooled product after the reaction, alternately washing the product for 4 times by water and alcohol, and collecting the product in a centrifugal mode;
step five: putting the collected product into a cold well of a freeze dryer at the temperature of-55 ℃ for freezing for 3 hours, then putting the frozen product into a tray, sealing the tray by using a preservative film, pricking the preservative film, covering a sealing cover, vacuumizing to 13Pa, drying for 16 hours, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
Example 5:
the method comprises the following steps: simultaneously adding 0.95g of sodium metavanadate and 3.6g of thioacetamide into 61ml of deionized water, and performing ultrasonic dispersion at room temperature to obtain a semi-clear solution A;
step two, preparing 3.1 mol/L sodium hydroxide solution B by deionized water, dropwise adding the sodium hydroxide solution B into the solution A under the condition of continuous magnetic stirring, namely adding 1 drop of sodium hydroxide solution B, stirring until the pH value of the solution is stable, and continuously repeating the steps until the pH value of the solution is adjusted to 10.1 to obtain solution C;
step three: pouring the solution C into a reaction inner liner according to the filling ratio of 62%, sealing, then placing the inner liner into an outer kettle, fixing, placing into a homogeneous reactor, and then reacting for 18h at 103 ℃ under the condition of the rotating speed of 7 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the cooled product after the reaction, alternately cleaning for 3 times by water and alcohol, and collecting the product in a suction filtration mode;
step five: placing the collected product in a cold well of a freeze dryer at-45 ℃ for freezing for 4 hours, then placing the frozen product in a tray, sealing the tray by using a preservative film, pricking the preservative film, covering a sealing cover, vacuumizing to 18Pa, drying for 15 hours, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
Claims (9)
1. Polycrystal nanobelt self-assembly three-dimensional hollow VS4The preparation method of the microsphere is characterized by comprising the following steps:
the method comprises the following steps: simultaneously adding 0.9-1.1 g of sodium metavanadate and 3.5-3.7 g of thioacetamide into 58-62 ml of deionized water, and carrying out magnetic stirring or ultrasonic dispersion to obtain a semi-clear solution A;
preparing a sodium hydroxide solution B of 2.8-3.2 mol/L, and adding the solution B into the solution A to enable the pH value of the solution B to reach 10.1-10.3 to obtain a solution C;
step three: pouring the solution C into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and then reacting for 17.5-18.5 h at 95-105 ℃ under the condition of a rotating speed of 5-10 r/min;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out a cooled product after the reaction, and collecting the product after alternately cleaning by water and alcohol;
step five: placing the collected product in a cold well of a freeze dryer for freezing, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 10-20 Pa, drying for 12-18 h, and collecting the product to obtain the polycrystalline nanobelt self-assembled three-dimensional hollow VS4And (3) microspheres.
2. The polycrystalline nanoribbon self-assembled three-dimensional hollow VS of claim 14The preparation method of the microsphere is characterized by comprising the following steps: the step 1) of magnetic stirring or ultrasonic dispersion is carried out at room temperature, and the rotating speed of the magnetic stirring is 400-600 r/min.
3. The polycrystalline nanoribbon self-assembled three-dimensional hollow VS of claim 14The preparation method of the microsphere is characterized by comprising the following steps: and 2) in the step 2), the solvent of the sodium hydroxide solution is deionized water, and the sodium hydroxide solution B is dropwise added into the solution A under the condition of continuous magnetic stirring, namely after 1 drop of the sodium hydroxide solution is added, stirring is carried out until the pH value of the solution is stable, and the steps are repeated continuously until the pH value of the solution is adjusted to 10.1-10.3.
4. The polycrystalline nanoribbon self-assembled three-dimensional hollow VS of claim 14The preparation method of the microsphere is characterized by comprising the following steps: the filling ratio of the solution C poured into the reaction lining in the step 3) is 58-62%.
5. The polycrystalline nanoribbon self-assembled three-dimensional hollow VS of claim 14The preparation method of the microsphere is characterized by comprising the following steps: and 4) alternately cleaning with water and alcohol for 2-5 times respectively, and collecting the product in a suction filtration or centrifugation mode.
6. The polycrystalline nanoribbon self-assembled tris of claim 1Dimensional hollow VS4The preparation method of the microsphere is characterized by comprising the following steps: the freezing conditions of the step 5) are as follows: freezing for 2-5 hours at-60 to-40 ℃.
7. The polycrystalline nanoribbon self-assembled three-dimensional hollow VS of claim 14The preparation method of the microsphere is characterized by comprising the following steps: and (3) before the product in the step 5) is placed into a tray for drying, sealing the product by using a preservative film, and pricking the preservative film.
8. Polycrystalline nanoribbon self-assembled three-dimensional hollow VS prepared by the preparation method of claim 14A microsphere, characterized in that: the powder consists of microspheres with the diameter of 0.5-2 mu m, the microspheres have a three-dimensional hollow structure formed by self-assembling nanobelts in a winding mode, the diameter of the nanobelts is about 50-100 nm, the nanobelts are of a polycrystalline structure, and the interplanar spacing of a crystal face (110) can reach 0.581 nm.
9. Polycrystalline nanoribbon self-assembled three-dimensional hollow VS prepared by the preparation method of claim 14The microspheres are applied to the field of lithium/sodium ion batteries, and have unique structural characteristics, so that the microspheres can show excellent electrochemical performance.
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| CN105923652A (en) * | 2016-04-29 | 2016-09-07 | 陕西科技大学 | Multilevel-structured VS4 nano-powder, and preparation method and application thereof |
| CN106960955A (en) * | 2017-05-31 | 2017-07-18 | 中南大学 | Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof |
| CN107381636A (en) * | 2017-07-11 | 2017-11-24 | 陕西科技大学 | A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application |
| CN108598432A (en) * | 2018-05-02 | 2018-09-28 | 电子科技大学 | A kind of preparation method of four vanadic sulfides/graphene composite material for sodium-ion battery electrode |
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