CN108110246B - Ultra-small VS4Super P nano composite powder and preparation method and application thereof - Google Patents

Ultra-small VS4Super P nano composite powder and preparation method and application thereof Download PDF

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CN108110246B
CN108110246B CN201711403838.5A CN201711403838A CN108110246B CN 108110246 B CN108110246 B CN 108110246B CN 201711403838 A CN201711403838 A CN 201711403838A CN 108110246 B CN108110246 B CN 108110246B
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solution
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黄剑锋
***
何枢薇
曹丽云
任一杰
范海鑫
畅珣伟
王娜
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Ultra-small VS4A preparation method and application of/Super P nano composite powder are disclosed, wherein sodium metavanadate, thioacetamide and Super P are added to removeObtaining solution A in the child water; then, dropwise adding ammonia water into the solution A to obtain a solution B with the pH value of 9.8-10.2; pouring the solution B into a reaction lining, and sealing to perform hydrothermal reaction; alternately cleaning the reaction product with water and alcohol, and drying to obtain the ultra-small VS4Super P nano composite powder. VS4The Super P nano composite powder is prepared from VS4The nanospheres and Super P nanospheres are uniformly and alternately distributed, and VS is realized4The nanospheres have consistent appearance, uniform size, diameter of 50-80 nm and VS4The nanosphere is single crystal VS growing along the (110) crystal face orientation with the diameter of 20nm and the length of 60-100 nm4The flexible nano-rod is wound. VS4The Super P nano composite powder is applied to the fields of lithium/sodium ion batteries and photo/electro-catalysis, and shows excellent electrochemical performance and catalytic performance.

Description

Ultra-small VS4Super P nano composite powder and preparation method and application thereof
Technical Field
The invention relates to a VS4A preparation method of Super P composite powder, in particular to ultra small VS4SuperP nano composite powder and its preparation method and use.
Background
VS4Rich V valence state, high sulfur content, one-dimensional chain crystal structure, weak inter-chain connection, large chain spacing and other characteristics, so that the catalyst has extremely high application prospect in the electrochemical and catalytic fields [ Xu X, Jeong S, Rout CS, Oh P, Ko M, Kim H, et al L high reactivity mechanism and high rate capability of VS4-graphene nanocomposite as an anode material for lithium batteries.J MaterChemA. 2014；2:10847-53.]. At the same time, it is the chlorothialite (VS occurring in nature)4) Abundant reserves and their potentially low cost, VS4In industrial application hasHas great commercial value. However, pure phase VS4The synthesis of (2) requires precise control of the partial pressure of sulfur, and is easy to generate various non-stoichiometric vanadium sulfide interference phases, and the oxygen affinity of vanadium is combined, so that VS is realized4Since 1970, the first report on the synthesis and application of the compound has been very little. In recent years, with the development of scientific technology, the synthetic technology has great breakthrough and progress, so that VS is ensured4It began to slowly enter the field of researchers, and there were some successes in synthesizing VS by hydrothermal reaction4The report of (1). However, in these hydrothermal reactions, templates including graphene, carbon nanotubes, conductive polymers (polythiophene, polypyrrole, and polyaniline), perylenetetracarboxylic dianhydride, etc. generally need to be introduced, which has high cost, synthesized VS4Also mostly of one-dimensional structure [ Rout CS, Kim B-H, Xu X, Yang J, Jeong HY, Odkhu D, et al. Synthesis and characterization of palatiniform of vanadium sulfate on graphic layer.J. Chem Soc.2013; 135:8720-5.]. Furthermore, pure phase VS has been reported4Mostly on the micrometer scale, resulting in a smaller specific surface area. As is well known, the high specific surface area greatly improves the electrochemical and catalytic reaction area, and further can obviously improve the electrochemical and catalytic performances. On the other hand, the unique physical confinement effect of the three-dimensional self-assembly structure can effectively inhibit the volume change in the reaction process, and further can obviously enhance the stability of the material. Therefore, synthesizing three-dimensional self-assembled VS with ultra-small scale4And compounding it with low-cost carbon material for VS4Has important significance in practical application.
Disclosure of Invention
The invention aims to provide the ultra-small VS which has simple reaction process, low temperature, easy control and no need of large-scale equipment and harsh reaction conditions4Super P nano composite powder and a preparation method and application thereof.
In order to achieve the above object, the preparation method of the present invention comprises the steps of:
the method comprises the following steps: simultaneously adding 0.8-1.2 g of sodium metavanadate, 3.4-3.8 g of thioacetamide and 0.2-0.4 g of Super P into 55-65 ml of deionized water, and performing magnetic stirring or ultrasonic dispersion to obtain a semi-clear solution A;
dropwise adding 1.0-1.2 mol/L ammonia water solution into the solution A until the pH value of the solution reaches 9.8-10.2 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to a filling ratio of 55-65%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating the reaction kettle to 175-185 ℃ from room temperature in a rotating state to perform hydrothermal reaction;
step four: naturally cooling the reaction kettle to room temperature after the hydrothermal reaction is finished, alternately cleaning the reaction kettle by water and alcohol, collecting the product, and drying the product at the temperature of 60-80 ℃ to obtain the ultra-small VS4Super P nano composite powder.
In the first step, the rotating speed of magnetic stirring is 800-1000 r/min, and the stirring time is 55-65 min.
The ultrasonic dispersion time in the first step is 30-45 min.
And the pH adjusting process in the second step is that under the condition of continuous magnetic stirring, 1.0-1.2 mol/L of ammonia water solution is dropwise added into the solution A, the dropwise adding speed of the ammonia water solution is controlled to be 0.03-0.05 ml/min, one drop of ammonia water solution is dropwise added, after the solution is stirred until the pH value of the solution is stable, the next drop of ammonia water solution is dropwise added until the pH value of the reaction solution is adjusted to be 9.8-10.2.
And the rotation speed of the step three is 5-10 r/min, and the hydrothermal reaction lasts for 23.5-24.5 h.
And the cleaning in the fourth step is carried out for 3-6 times by adopting suction filtration or centrifugation.
And the collection of the fourth step is carried out by suction filtration or centrifugation.
And drying in the fourth step is carried out in a vacuum drying oven for 10-14 h.
ultra-Small VS synthesized according to preparation method of the invention4The Super P nano composite powder is prepared from VS4The nanospheres and the SuperP nanospheres are uniformly and alternately distributed, and VS is realized4The nanospheres have consistent appearance, uniform size, diameter of 50-80 nm and VS4The nanospheres are 20nm in diameter and 60-100 nm in lengthSingle crystal VS grown in (110) crystal plane orientation4The flexible nano-rod is wound.
VS4The Super P nano composite powder shows excellent electrochemical performance and catalytic performance when applied to a sodium/lithium ion battery cathode material and a photo/electro-catalyst in the fields of lithium/sodium ion batteries and photo/electro-catalysis.
The method has the following specific beneficial effects:
(1) the invention adopts one-step hydrothermal reaction to directly synthesize the final product, 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 method is sodium metavanadate, the sulfur source is thioacetamide, and the carbon source is Super P, and the three raw materials are common substances, are cheap and easy to obtain, have low cost, high yield of synthesized composite powder, easy to control reaction, free of post-treatment, environment-friendly, and suitable for large-scale production;
(3) the invention synthesizes the ultra-small three-dimensional self-assembly VS4In the process of Super P nano composite powder, no template agent or surfactant is introduced, and the whole self-assembly process is controlled by the self-template action of reaction raw materials, so that the whole reaction is simple, easy to control, high-efficiency and low in cost;
(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 sodium/lithium ion battery cathode material and a photo/electro catalyst;
(5) addition of Super P in the present invention for ultra-small self-assembly VS4Plays a decisive role in the formation of (B). Addition of Super P affects VS4Nucleation and growth rates of4Easy to nucleate and difficult to grow, resulting in large amounts of ultra-small VS4Flexible rod simultaneous VS4The flexible rods are self-assembled and wound into nanospheres by the rotary one-dimensional chain crystal structure;
(6) regulation of pH in the present invention for ultra Small VS4Also plays a key role, too high a pH tends to cause the reaction to form VS2Rather than VS4Too low a pH is liable toIn promoting VS4Growing into a self-assembly body with a larger scale;
(7) process of pH adjustment of the invention for pure phase VS4Plays an important role in the formation of (c). The inappropriate ammonia water concentration, the inappropriate dropping speed and the selection of the strong alkaline solution are easy to cause the local reaction to generate VOxOr S simple substance heterogeneous phase;
(8) regulation of fill ratio in the present invention for pure phase VS4Also plays an important role. Higher fill ratios will promote S2-Ion displacement of oxygen in vanadate to produce VS2. Lower fill ratio is detrimental to S2 2-Displacing oxygen in vanadyl leading to VOxGenerating;
(9) ultra-small VS in VS4/Super P nano composite powder prepared by the invention4The nano-rod not only can generate larger specific surface area, but also can provide more surface active sites, thereby improving the electrochemical performance and the catalytic performance. In addition, the ultra-small scale can not only shorten a charge transfer path, but also provide more active sites for the storage of sodium/lithium ions, so that the specific capacity and rate capability of the material can be improved;
(10) VS prepared by the invention4The structure of the nano-rods wound into the nano-spheres in the Super P nano-composite powder can play a good role in physical confinement in the charging and discharging processes. On one hand, the nano-rod can play a good role in restraining, and on the other hand, a buffer space is provided for the expansion and contraction of the nano-rod, so that the volume change of the nano-rod can be greatly relieved, and the circulation stability of the nano-rod is finally obviously improved;
(11) VS prepared by the invention4VS in Super P nano composite powder4The nanorod has the single crystal characteristic of growing along the (110) crystal plane orientation, and is used as an inlet for charge to enter and exit a crystal lattice, and the larger crystal plane spacing of the nanorod is favorable for charge transmission, so that the nanorod has an important effect on the improvement of electrochemical and catalytic performances. Meanwhile, the structural stability of the material is improved by the single crystal characteristics, so that the stability of charge de-intercalation and catalysis processes is facilitated, and the service life of the material can be prolonged;
(12) VS prepared by the invention4Super P uniformly distributed in the Super P nano composite powder can not only improve the conductivity of the material, but also play a role in fixing VS4The volume change of the electrochemical reaction device is relieved, so that the power and the stability of the electrochemical reaction can be synergistically improved.
Drawings
FIG. 1 is a low-power scan of the product of example 1 of the present invention.
FIG. 2 is a high-magnification scan of the product of example 1 of the present invention.
FIG. 3 is a super-high scan of the product of example 1 of the present invention.
FIG. 4 is a high resolution TEM image of the product prepared in example 1 of the present invention.
FIG. 5 is a scanning electron micrograph of a product obtained after removing the raw material Super P in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
the method comprises the following steps: simultaneously adding 1.0g of sodium metavanadate, 3.6g of thioacetamide and 0.3g of Super P into 60ml of deionized water, and magnetically stirring at 800r/min for 65min to obtain a semi-clear solution A;
dropwise adding 1.0 mol/L ammonia water solution into the solution A under magnetic stirring, controlling the dropping speed of the ammonia water solution to be 0.03ml/min, stirring until the pH value of the solution is stable, and then adding the next drop of ammonia water solution until the pH value of the reaction solution is adjusted to 10 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to the filling ratio of 60%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating the reaction kettle to 180 ℃ from room temperature at 8r/min for hydrothermal reaction for 24 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, alternately filtering with water and alcohol for 3 times, collecting the product by adopting the filtering, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the ultra-small VS4Super P nano composite powder.
As can be seen in FIG. 1, VS4The Super P nano composite powder is prepared from VS4The nanospheres and Super P nanospheres are uniformly and alternately distributed.
As can be seen in FIG. 2, VS4The shapes of the nanospheres are consistent, the sizes of the nanospheres are uniform, and the nanospheres are 50-80 nm.
As can be seen in FIG. 3, VS4The nanosphere is formed by VS with the diameter of about 20nm and the length of about 60-100 nm4The flexible nano-rod is wound.
As can be seen in FIG. 4, VS4The nanorods exhibit a single crystal structure grown in a (110) crystal plane orientation.
As can be seen from FIG. 5, when Super P was not introduced in the reaction, VS was synthesized4The dimensions of the flexible rod and the balls formed by winding it are enlarged.
Example 2:
the method comprises the following steps: simultaneously adding 0.8g of sodium metavanadate, 3.5g of thioacetamide and 0.2g of Super P into 58ml of deionized water, and magnetically stirring for 55min at 1000r/min to obtain a semi-clear solution A;
dropwise adding 1.15 mol/L ammonia water solution into the solution A under magnetic stirring, controlling the dropping speed of the ammonia water solution to be 0.04ml/min, stirring until the pH value of the solution is stable, and then adding the next drop of ammonia water solution until the pH value of the reaction solution is adjusted to 9.9 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to the filling ratio of 55%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous phase reactor, and heating the reaction kettle to 178 ℃ from room temperature at 5r/min for hydrothermal reaction for 24.5 h;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, alternately centrifuging for 5 times by water and alcohol, collecting the product by centrifugation, and drying in a vacuum drying oven at 65 ℃ for 10h to obtain the ultra-small VS4Super P nano composite powder.
Example 3:
the method comprises the following steps: simultaneously adding 1.1g of sodium metavanadate, 3.7g of thioacetamide and 0.4g of Super P into 63ml of deionized water, and magnetically stirring at 900r/min for 60min to obtain a semi-clear solution A;
dropwise adding 1.1 mol/L ammonia water solution into the solution A under magnetic stirring, controlling the dropping speed of the ammonia water solution to be 0.05ml/min, after dropwise adding one drop of the ammonia water solution, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of the ammonia water solution until the pH value of the reaction solution is adjusted to 10.1 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to a filling ratio of 58%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating the reaction kettle to 185 ℃ from room temperature at 10r/min for hydrothermal reaction for 23.5 h;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, alternately filtering for 6 times by using water and alcohol, collecting a product by adopting the filtering, and drying in a vacuum drying oven at 75 ℃ for 13 hours to obtain the ultra-small VS4Super P nano composite powder.
Example 4:
the method comprises the following steps: simultaneously adding 0.9g of sodium metavanadate, 3.8g of thioacetamide and 0.25g of Super P into 65ml of deionized water, and performing ultrasonic dispersion for 45min to obtain a semi-clear solution A;
dropwise adding 1.05 mol/L ammonia water solution into the solution A under magnetic stirring, controlling the dropping speed of the ammonia water solution to be 0.045ml/min, dropwise adding a drop of ammonia water solution, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of ammonia water solution until the pH value of the reaction solution is adjusted to 10.2 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to a filling ratio of 65%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating the reaction kettle to 183 ℃ from room temperature at 9r/min for hydrothermal reaction for 24 hours;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, alternately centrifuging for 4 times by water and alcohol, collecting the product by centrifugation, and drying in a vacuum drying oven at 80 ℃ for 11h to obtain the ultra-small VS4Super P nano composite powder.
Example 5:
the method comprises the following steps: simultaneously adding 1.2g of sodium metavanadate, 3.4g of thioacetamide and 0.35g of Super P into 55ml of deionized water, and performing ultrasonic dispersion for 45min to obtain a semi-clear solution A;
dropwise adding 1.2 mol/L ammonia water solution into the solution A under magnetic stirring, controlling the dropping speed of the ammonia water solution to be 0.035ml/min, after the dropwise adding of the ammonia water solution is completed, stirring until the pH value of the solution is stable, and then dropwise adding the next drop of ammonia water solution until the pH value of the reaction solution is adjusted to 9.8 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to a filling ratio of 63%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating the reaction kettle to 175 ℃ from room temperature at 7r/min for hydrothermal reaction for 24.5 h;
step four: after the hydrothermal reaction is finished, naturally cooling the reaction kettle to room temperature, alternately filtering with water and alcohol for 5 times, collecting the product by centrifugation, and drying in a vacuum drying oven at 70 ℃ for 14h to obtain the ultra-small VS4Super P nano composite powder.

Claims (9)

1. Ultra-small VS4The preparation method of the Super P nano composite powder is characterized by comprising the following steps:
the method comprises the following steps: simultaneously adding 0.8-1.2 g of sodium metavanadate, 3.4-3.8 g of thioacetamide and 0.2-0.4 g of Super P into 55-65 ml of deionized water, and performing magnetic stirring or ultrasonic dispersion to obtain a semi-clear solution A;
dropwise adding 1.0-1.2 mol/L ammonia water solution into the solution A until the pH value of the solution reaches 9.8-10.2 to obtain a solution B;
step three: pouring the solution B into a reaction inner liner according to a filling ratio of 55-65%, sealing, placing the inner liner in an outer kettle, fixing, placing in a homogeneous reactor, and heating the reaction kettle to 175-185 ℃ from room temperature in a rotating state to perform hydrothermal reaction;
step four: naturally cooling the reaction kettle to room temperature after the hydrothermal reaction is finished, alternately cleaning the reaction kettle by water and alcohol, collecting the product, and drying the product at the temperature of 60-80 DEG CObtaining the ultra-small VS4Super P nano composite powder;
and the pH adjusting process in the second step is that under the condition of continuous magnetic stirring, 1.0-1.2 mol/L of ammonia water solution is dropwise added into the solution A, the dropwise adding speed of the ammonia water solution is controlled to be 0.03-0.05 ml/min, one drop of ammonia water solution is dropwise added, after the solution is stirred until the pH value of the solution is stable, the next drop of ammonia water solution is dropwise added until the pH value of the reaction solution is adjusted to be 9.8-10.2.
2. The ultra-small VS of claim 14The preparation method of the Super P nano composite powder is characterized by comprising the following steps: in the first step, the rotating speed of magnetic stirring is 800-1000 r/min, and the stirring time is 55-65 min.
3. The ultra-small VS of claim 14The preparation method of the Super P nano composite powder is characterized by comprising the following steps: the ultrasonic dispersion time in the first step is 30-45 min.
4. The ultra-small VS of claim 14The preparation method of the Super P nano composite powder is characterized by comprising the following steps: and the rotation speed of the step three is 5-10 r/min, and the hydrothermal reaction lasts for 23.5-24.5 h.
5. The ultra-small VS of claim 14The preparation method of the Super P nano composite powder is characterized by comprising the following steps: and the cleaning in the fourth step is carried out for 3-6 times by adopting suction filtration or centrifugation.
6. The ultra-small VS of claim 14The preparation method of the Super P nano composite powder is characterized by comprising the following steps: and the collection of the fourth step is carried out by suction filtration or centrifugation.
7. The ultra-small VS of claim 14The preparation method of the Super P nano composite powder is characterized by comprising the following steps: and drying in the fourth step is carried out in a vacuum drying oven for 10-14 h.
8. Ultra-small VS synthesized by preparation method according to claim 14The Super P nano composite powder is characterized in that: VS4The Super P nano composite powder is prepared from VS4The nanospheres and Super P nanospheres are uniformly and alternately distributed, and VS is realized4The nanospheres have consistent appearance, uniform size, diameter of 50-80 nm and VS4The nanosphere is single crystal VS growing along the (110) crystal face orientation with the diameter of 20nm and the length of 60-100 nm4The flexible nano-rod is wound.
9. A VS as claimed in claim 84Application of/Super P nano composite powder in the fields of lithium/sodium ion batteries and photo/electro-catalysis.
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CN109904422B (en) * 2019-02-26 2022-05-20 陕西科技大学 Preparation method and application of vanadium tetrasulfide @ Super P composite powder
CN109748319B (en) * 2019-02-26 2021-02-09 陕西科技大学 Preparation method and application of vanadium tetrasulfide @ carbon nanotube composite powder
CN112786845A (en) * 2019-11-07 2021-05-11 广州汽车集团股份有限公司 VS4Hierarchical pore graphitized carbon composite material, preparation method thereof, positive electrode material, positive plate, lithium-sulfur battery cell and lithium-sulfur battery pack
CN112490438B (en) * 2020-11-27 2022-03-11 青岛科技大学 Mo-VS4Positive electrode material of/N-GNTs magnesium ion battery
CN113130863A (en) * 2021-03-22 2021-07-16 郑州大学 VS (virtual switch)4/rGO composite material, preparation method thereof and application in zinc ion battery

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