CN109904422B - Preparation method and application of vanadium tetrasulfide @ Super P composite powder - Google Patents
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Abstract
A preparation method of vanadium tetrasulfide @ Super P composite powder comprises the following steps; weighing 48-52 mg of Super P, adding into 58-62 ml of deionized water, and carrying out ultrasonic treatment for 1.5-2.5 h to obtain a uniformly dispersed black solution A; weighing 0.9-1.1 g of sodium metavanadate and 3.5-3.7 g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring for 30-60 min to obtain a solution B; pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and then reacting at 175-185 ℃ for 23-25 h under the condition of a rotating speed of 5-10 r/min; after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, and collecting the product after alternately cleaning the product by 2-5 times of water and 2-5 times of alcohol; and 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, and drying for 12-18 h and then collecting the product.
Description
Technical Field
The invention relates to the technical field of vanadium tetrasulfide @ Super P composite powder, in particular to a preparation method and application of the vanadium tetrasulfide @ Super P composite powder.
Background
As a typical transition metal sulfide, VS4Has a one-dimensional chain structure. Wherein two S2 2-The group (four S) tightly surrounds V and expands in the c direction to form VS4Molecular chain, two adjacent VS4The molecular chains are connected through weak van der Waals force, and the chain spacing can reach
(Rout CS, Kim B-H, et al.J. Am Chem Soc.2013,135: 8720-8725.). Similar to FeS2，VS4Derived from the natural mineral, chlorothiolite, and has a valence state of-1 for S and a valence state of +4 for V. The above structural characteristics make VS4The method is applied to the fields of photocatalysis, hydrofining reaction, lithium ion batteries, supercapacitors, aluminum ion batteries, magnesium ion batteries and the like. However, since 1970 VS due to the very oxophilic nature of V, the precise partial pressure of S required for the reaction process, and the presence of various non-stoichiometric ratios of vanadium sulfide4It was first reported that their synthesis was greatly hindered (Xu X, Jeong S, et al.J. Mater Chem A.2014,2: 10847-10853.). And, for VS4The synthesis of (a) generally requires the introduction of a templating agent. Sun R et al prepared VS grown on the surface of reduced graphene by hydrothermal method4(Sun R, Wei Q, et al. ACS Appl Mater Inter.2015,7: 20902-20908.). Li S et al synthesized VS by a flexible hydrothermal method4Nanocomposites stacked on reduced graphene oxide (Li S, He W, et al. Mater Lett.2017,205: 52-55.). Pang Q et al prepared uniform graphene sheet anchored VS by CTAB cationic surfactant assisted hydrothermal method4Nanoparticles, followed by varying the amount of graphene sheets added, control VS4Size of nanoparticles (Pang Q, Zhao Y, et al. ChemSus chem.2018,11: 735-. Wang S et al prepared uniform cuboid VS by controlling the content of graphene oxide template using an in situ graphene oxide template hydrothermal method4Nanoparticles (Wang S, Gong F, et al. adv Funct Mater.2018,28: 1801806.). Rout CS et al successfully obtained oxidized graphene, carboxylated carbon nanotubes, pyrene rich in locking machine, perylene tetracarboxylic dianhydride, graphite and other carbon materials and VS in a hydrothermal system4The complex of (Rout CS, Kim B-H, et al.J Am Chem Soc.2013,135: 8720-8725.). However, in the above-described composite materials that have been reported, a part of VS4Not grown on the surface of the carbon material, but only VS4The other part of the composite with the carbon material grows on the surface of the carbon material, but the distribution is sparse and irregular, and VS is4The appearance of the alloy is also irregular and uniform. This inadequate and inefficient compounding causes VS4The high performance of (2) is not well performed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method and application of vanadium tetrasulfide @ Super P composite powder4The method has simple reaction process, low temperature, easy control and no need of large-scale equipment and harsh reaction conditions, and can directly realize VS in one reaction process4And in-situ winding on the surface of the Super P nano-spheres. When the product is applied to a lithium/sodium ion battery negative electrode material and a photo/electro catalyst, the product can show excellent electrochemical performance and catalytic performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of vanadium tetrasulfide @ Super P composite powder comprises the following steps;
the method comprises the following steps: weighing 48-52 mg of Super P, adding into 58-62 ml of deionized water, and carrying out ultrasonic treatment for 1.5-2.5 h to obtain a uniformly dispersed black solution A;
step two: weighing 0.9-1.1 g of sodium metavanadate and 3.5-3.7 g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring for 30-60 min to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and then reacting at 175-185 ℃ for 23-25 h 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, taking out a cooled product after the reaction, and collecting the product after alternately cleaning the product by 2-5 times of water and 2-5 times of alcohol;
step five: and 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 vanadium tetrasulfide @ Super P composite powder.
The ultrasonic power in the first step is 400-600W, and the ultrasonic treatment is carried out at normal temperature.
And in the second step, the rotating speed of magnetic stirring is 400-600 r/min, and the stirring is carried out at normal temperature.
And in the third step, the filling ratio of the solution B poured into the reaction lining is 58-62%.
In the fourth step, water and alcohol are alternately cleaned mainly in a suction filtration or centrifugation mode, and the collection is also mainly performed in a suction filtration or centrifugation mode.
The refrigeration conditions of the step five are as follows: freezing for 2-5 h at-60 to-40 ℃.
And before the product obtained in the fifth step is placed into a tray for drying, sealing the product by using a preservative film, and pricking the preservative film to ensure that the product is sufficiently dried under a low-pressure condition.
The composite powder consists of sub-microspheres with uniform diameter of about 200nm, the sub-microspheres are in a core-shell structure, wherein the core is Super P with diameter of about 30nm, and the shell is flexible VS4Formed by winding nanorods and VS4The nanorods have high crystallinity and orientation arrangement along the (110) crystal plane direction.
The bond between the vanadium tetrasulfide and the Super P is a chemical bond, not a physical bond.
The application of the vanadium sulfide @ Super P composite powder can be in the field of lithium/sodium ion batteries and also can be in the field of photo/electro-catalysis.
The invention has the beneficial effects that:
(1) the invention adopts one-step template-free hydrothermal reaction to directly synthesize the final composite structure, thereby having 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, the solvent is water, the three substances are common raw materials, the raw materials are cheap and easy to obtain, the cost is low, the whole reaction yield is high, easy to control and environment-friendly, the product does not need post-treatment, and the method is suitable for large-scale production;
(3) when the product prepared by the method is used as a lithium/sodium ion battery negative electrode material and a photo/electro catalyst, excellent performance can be shown;
(4) the method disclosed by the invention has the advantages that parameters such as the concentration and the proportion of the vanadium source and the sulfur source, the reaction temperature, the reaction time, the filling ratio and the like are strictly and cooperatively controlled, and the adsorption of the vanadium source and the sulfur source on the surface of Super P is fully utilized, so that VS is realized4Nucleation is uniformly carried out on the surface of the Super P nanosphere, and the growth is depended on, so that VS is formed4The nano-rods are wound on the Super P nanospheres in situ to form a composite structure;
(5) addition of Super P for Uniform VS4The formation of the structure of the nanorod wound Super P nanospheres plays a key role. Neither too much nor too little introduction of Super P for VS4Provide suitable sites for nucleation and thus do not yield a uniform composite structure;
(6) reaction time for homogeneous VS4The formation of the structure of the nanorod wound Super P nanospheres plays a key role. Too long and too short reaction times are detrimental to better VS4Constructing a Super P nano-sphere structure wound by nano-rods;
(7) in the process of synthesizing vanadium tetrasulfide @ Super P, no template agent or surfactant is introduced, and the rich oxygen-containing functional groups on the surface of the Super P are taken as active sites in the whole in-situ growth process, so that the whole reaction is simple, easy to control, high-efficiency and low in cost;
(8)VS4in the process of in-situ growth on the surface of the Super P nano-sphere, VS is caused by the synergistic effect of rich oxygen-containing functional groups on the surface of the Super P and a temperature field and a pressure field generated by hydrothermal4And Super P are chemically bonded;
(9) the composite product prepared by the invention has a unique composite structure, wherein VS is wound on the outer surface of Super P4Mainly plays a role in storing Na+The Super P not only can provide a good conductive path for the charge and discharge process, but also can inhibit VS4Volume change during charge and discharge. VS4Fully exposes the crystal structure arranged along the (110) crystal face orientation, and is very favorable for the metal ions to pass in and out of the chain at VS because the (110) crystal face has the maximum crystal face spacing4Inter-chain storage and transmission. Under the synergistic effect of the structural advantages, the vanadium tetrasulfide @ Super P can show excellent cycle performance and rate performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1 of this invention.
FIG. 2 is a scanning electron micrograph of a product prepared according to example 1 of the present invention.
FIG. 3 is a high power scanning electron micrograph of the product prepared in example 1 of the present invention.
FIG. 4 is a transmission electron micrograph of a product prepared in example 1 of the present invention.
FIG. 5 is a scanning electron micrograph of the product prepared in example 1 of the present invention.
FIG. 6 is a low-power high-resolution transmission electron micrograph of a product prepared in example 1 of the present invention.
FIG. 7 is a high resolution TEM image of the product prepared in example 1 of the present invention.
FIG. 8 is a scanning electron micrograph of the product obtained after reducing the addition of Super P in example 1 of the present invention to 20 mg.
FIG. 9 is a scanning electron micrograph of a product obtained after increasing the addition amount of Super P to 80mg in example 1 of the present invention.
FIG. 10 is a scanning electron micrograph of a product obtained after the reaction time in example 1 of the present invention is shortened to 12 hours.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
the method comprises the following steps: and weighing 50mg of Super P, adding into 60ml of deionized water, and carrying out ultrasonic treatment for 2 hours at the ultrasonic power of 400-600W to obtain a uniformly dispersed black solution A.
Step two: and weighing 1.0g of sodium metavanadate and 3.6g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring the solution A for 50min at the rotating speed of 400-600 r/min to obtain a solution B.
Step three: pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor with a filling ratio of 59%, and then reacting at 180 ℃ for 24h under the condition of a rotation speed of 10 r/min.
Step four: and after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, taking out a cooled product after the reaction, and collecting the product after alternately cleaning the product by using water and alcohol for 3 times.
Step five: and (3) freezing the collected product in a cold well of a freeze dryer under the following freezing conditions: freezing at the temperature of minus 50 ℃ for 4h, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 20Pa, drying for 18h, and collecting the product to obtain the vanadium tetrasulfide @ Super P composite powder.
Example 2:
the method comprises the following steps: weighing 48mg of Super P, adding into 58ml of deionized water, and carrying out ultrasonic treatment for 1.5h with the ultrasonic power of 400W to obtain a uniformly dispersed black solution A;
step two: weighing 0.9g of sodium metavanadate and 3.5g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring the solution A for 30min at the rotating speed of 400r/min to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor with a filling ratio of 58%, and then reacting at 175 ℃ for 23h 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 a cooled product after the reaction, and collecting the product after alternately cleaning with 2 times of water and 2 times of alcohol;
step five: and (3) freezing the collected product in a cold well of a freeze dryer under the following freezing conditions: freezing for 2h at minus 60 ℃, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 10Pa, drying for 12h, and collecting the product to obtain the vanadium tetrasulfide @ Super P composite powder.
Example 3:
the method comprises the following steps: weighing 52mg of Super P, adding into 62ml of deionized water, and carrying out ultrasonic treatment for 2.5h with the ultrasonic power of 600W to obtain a uniformly dispersed black solution A;
step two: weighing 1.1g of sodium metavanadate and 3.7g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring the solution A for 60min at the rotating speed of 600r/min to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor with a filling ratio of 62%, and then reacting at 185 ℃ for 25h under the condition of a 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 a cooled product after the reaction, and collecting the product after alternately cleaning the product by 5 times of water and 5 times of alcohol;
step five: and (3) freezing the collected product in a cold well of a freeze dryer under the following freezing conditions: freezing at the temperature of minus 40 ℃ for 5h, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 20Pa, drying for 18h, and collecting the product to obtain the vanadium tetrasulfide @ Super P composite powder.
Example 4:
the method comprises the following steps: weighing 50mg of Super P, adding into 60ml of deionized water, and carrying out ultrasonic treatment for 2 hours at the ultrasonic power of 500W to obtain a uniformly dispersed black solution A;
step two: weighing 1g of sodium metavanadate and 3.6g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring the mixture for 45min at the rotating speed of 500r/min to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor with a filling ratio of 60%, and then reacting at 180 ℃ for 24h 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 a cooled product after the reaction, and collecting the product after alternately cleaning the reaction kettle by water and alcohol for 3 times;
step five: and (3) freezing the collected product in a cold well of a freeze dryer under the following freezing conditions: freezing at the temperature of minus 50 ℃ for 3h, then placing the frozen product in a tray, covering a sealing cover, vacuumizing to 15Pa, drying for 15h, and collecting the product to obtain the vanadium tetrasulfide @ Super P composite powder.
As shown in FIG. 1, all diffraction peaks match VS well4Standard card PDF # 72-1294. The diffraction peak of Super P cannot be observed in fig. 1 because of its small content and low crystallinity.
As shown in fig. 2, vanadium tetrasulfide @ Super P is composed of uniform sub-microspheres.
As shown in FIG. 3, the diameter of the resulting submicrospheres was about 200nm and the exterior was composed of a flexible VS4The nano-rod is wound.
As shown in FIG. 4, the obtained submicrospheres exhibit a core-shell structure, the shell being formed by flexible VS4The nano-rod is wound.
As shown in FIG. 5, the resulting submicrospheres exhibit a core-shell structure, wherein the core is Super P with a diameter of about 30nm and the shell is composed of flexible VS4The nano-rod is wound.
As shown in fig. 6. VS can be clearly seen from the figure4The regular lattice stripes of the nanorods indicate its high crystallinity.
As shown in fig. 7. VS can be clearly seen from the figure4The (110) crystal plane lattice fringes of the nanorod indicate a crystal structure in which the nanorod is oriented and arranged along the direction of the (110) crystal plane.
Su in embodiment 1 of the present invention is shown in FIG. 8Scanning electron micrographs of the product obtained after the per P addition was reduced to 20 mg. From the figure, many small VS's that were not combined into nanorods were observed4Particles, indicating VS4And Super P do not combine well.
Scanning electron micrograph of the product obtained after increasing the addition amount of Super P in example 1 of the present invention to 80mg as shown in FIG. 9. From the figure, many small VS's that were not combined into nanorods were also observed4Particles, indicating VS4And Super P also do not complex well together.
FIG. 10 is a scanning electron micrograph of the product obtained after the reaction time in example 1 of the present invention is shortened to 12 hours. From the figure, it can be seen that many small VS were not combined into nanorods4Particles, showing that in a shorter time, VS4And Super P do not compound well together.
Claims (9)
1. A preparation method of vanadium tetrasulfide @ Super P composite powder is characterized by comprising the following steps;
the method comprises the following steps: weighing 48-52 mg of Super P, adding into 58-62 ml of deionized water, and carrying out ultrasonic treatment for 1.5-2.5 h to obtain a uniformly dispersed black solution A;
step two: weighing 0.9-1.1 g of sodium metavanadate and 3.5-3.7 g of thioacetamide, simultaneously adding the sodium metavanadate and the thioacetamide into the solution A, and magnetically stirring for 30-60 min to obtain a solution B;
step three: pouring the solution B into a reaction inner liner, sealing, then placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and then reacting at 175-185 ℃ for 23-25 h 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, taking out a cooled product after the reaction, and collecting the product after alternately cleaning the product by 2-5 times of water and 2-5 times of alcohol;
step five: and 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 vanadium tetrasulfide @ Super P composite powder.
2. The preparation method of vanadium tetrasulfide @ Super P composite powder according to claim 1, wherein in the first step, the ultrasonic power is 400-600W, and the preparation method is carried out at normal temperature.
3. The preparation method of vanadium tetrasulfide @ Super P composite powder according to claim 1, wherein the rotation speed of magnetic stirring in the second step is 400-600 r/min, and the stirring is performed at normal temperature.
4. The preparation method of vanadium tetrasulfide @ Super P composite powder according to claim 1, wherein the filling ratio of the solution B poured into the reaction lining in the third step is 58-62%.
5. The preparation method of vanadium tetrasulfide @ Super P composite powder according to claim 1, characterized in that in the step four, the water and alcohol are alternately cleaned mainly by suction filtration or centrifugation, and the collection is also mainly performed by suction filtration or centrifugation.
6. The preparation method of vanadium tetrasulfide @ Super P composite powder according to claim 1, characterized in that the freezing conditions of the fifth step are as follows: freezing for 2-5 h at-60 to-40 ℃.
7. The preparation method of vanadium tetrasulfide @ Super P composite powder according to claim 1, characterized in that the product obtained in the fifth step is sealed by a preservative film before being placed in a tray for drying, and the preservative film is perforated to ensure sufficient drying under low pressure.
8. The method for preparing vanadium tetrasulfide @ Super P composite powder according to claim 1, wherein the composite powder is composed of uniform submicrospheres with a diameter of about 200nm, the submicrospheres have a core-shell structure, and a core of the submicrospheres isIs Super P with a diameter of about 30nm, and the shell is formed by flexible VS4Formed by winding nanorods and VS4The nanorods have high crystallinity and orientation arrangement along the (110) crystal plane direction.
9. The method for preparing vanadium tetrasulfide @ Super P composite powder according to claim 1, characterized in that the combination between the vanadium tetrasulfide and the Super P is a chemical bond combination, not a physical combination.
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| CN108110246A (en) * | 2017-12-22 | 2018-06-01 | 陕西科技大学 | A kind of extra small VS4/ Super P composite nano-powders and 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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