CN106430306A - Preparation method for vanadium dioxide micro-nanometer structure material - Google Patents

Preparation method for vanadium dioxide micro-nanometer structure material Download PDF

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CN106430306A
CN106430306A CN201610776884.9A CN201610776884A CN106430306A CN 106430306 A CN106430306 A CN 106430306A CN 201610776884 A CN201610776884 A CN 201610776884A CN 106430306 A CN106430306 A CN 106430306A
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vanadium
preparation
vanadium dioxide
source
structure material
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CN106430306B (en
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陶占良
李攀
孙维祎
陈军
李海霞
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a preparation method for a vanadium dioxide micro-nanometer structure material. According to the invention, by adopting polyvinylpyrrolidone (PVP) as a surfactant, a pure-phase vanadium dioxide micro-nanometer structure is hydrothermally prepared. The invention has the following advantages: VS2 lamellas prepared by using the method provided by the invention have regular sizes and uniform stacking thickness, so controllable preparation of vanadium dioxide is successfully realized; the preparation method has the advantages of simple operation, strong controllability, cheap and easily-available raw materials, and facilitation to mass production; and the vanadium dioxide prepared by using the method provided by the invention can reinforce structure stability and exposes more active sites, thereby facilitating to application in a plurality of fields like electrochemistry, oxygen reduction and hydrogen evolution.

Description

A kind of preparation method of vanadium dioxide micro-nano structure material
Technical field
The present invention relates to nano material and novel energy resource material technology, more particularly, to a kind of vanadium dioxide micro-nano structure material Preparation method.
Background technology
Environmental pollution and energy shortage problem become one of Tough questions of facing mankind, find regenerative resource and peace Entirely, reliable energy storage technologies have been changed to very important problem.Lithium ion battery has that voltage is high, capacity is big, no remembers Recalling the advantages of effect and life-span length is widely used in the electronic products such as mobile phone, digital camera and notebook, becomes battery The emphasis of industry development.One of key of exploitation lithium ion battery is to find suitable electrode material, so that battery is had sufficiently high Lithium-inserting amount and good lithium deintercalation ability, to ensure big specific capacity, high circulation life-span and the good security performance of battery, because This, need preparation to have the electrode material of high-efficiency energy-storage characteristic, to meet above-mentioned requirements.
In recent years, transient metal chalcogenide compound (TMDs) is because having electrical properties and catalytic property etc. of uniqueness, as The very important material of one class can be widely applied to energy field, is used for example as electrode of lithium cell, catalyst etc..Wherein two sulfur Change vanadium (VS2) possess the layer structure of class Graphene, there is larger interlamellar spacing, weak Van der Waals force between layers makes material easy In peeling off layering, electrode can be significantly improved as electrode material with metal ions such as the lithiums of reversible embedded different proportion Property.Additionally, vanadium disulfide is in metallic state, there is good electric conductivity, charge density wave (Charge can occur near 30 DEG C Density Wave, CDW) phase transformation, therefore it has in numerous areas such as electrochemistry, hydrogen evolution, optics, magnetic material, phase-change materials Standby good application prospect.With people vanadium disulfide property is understood further deeply, its application and range of application Will significantly be widened, produced significant Social and economic benef@.
Because vanadium has multivalent state (II, III, IV, V etc.), vanadium disulfide is difficult to by the direct chemical combination of element, how organic Synthesize in solvent, the valence state of preparation method complex operation and very difficult control vanadium is it is difficult to obtain VS2Pure phase and controllable standby, cause Structure and performance unstable.For example, in electrochemical field, VS2As lithium ion battery electrode material due to material granule Larger lead to stability of material poor, structure is easy to cave in, and causes capacity attenuation serious；In the research about hydrogen evolution, pattern Irregular vanadium disulfide granule cannot expose more avtive spots, causes catalytic performance not good enough.Therefore, obtain VS2Pure phase, reality The controllable standby of existing vanadium disulfide, becomes the key studying its performance.
Content of the invention
The purpose of the present invention is for above-mentioned the deficiencies in the prior art, provides a kind of system of vanadium dioxide micro-nano structure material Preparation Method, by being used as surfactant using Polyvinylpyrrolidone (PVP), hydro-thermal prepares the curing of pure phase to the method Vanadium micro-nano structure, the VS of preparation2Lamella size rule, ulking thickness are homogeneous, are successfully realized the controllable standby of vanadium disulfide.
Technical scheme：
A kind of preparation method of vanadium dioxide micro-nano structure material, comprises the following steps：
1) add Polyvinylpyrrolidone (PVP) to being completely dissolved in ultra-pure water, obtain polyvinylpyrrolidonesolution solution；
2) add vanadium source, sulphur source in above-mentioned polyvinylpyrrolidonesolution solution, stir to dissolving, then with concentration be It is 8-10 that the ammonia of 12mol/L adjusts pH value；
3) gained mixed solution is placed in hydrothermal device and reacts 10h-20h at 120-200 DEG C；
4), after reacting completely, naturally cool to room temperature, products therefrom is scrubbed, centrifugation, vacuum drying, collect and had The homogeneous vanadium disulfide micro-nano structure of lamella size rule, ulking thickness.
The weight average molecular weight range of described Polyvinylpyrrolidone (PVP) be 6000-150000, Polyvinylpyrrolidone with The amount ratio of ultra-pure water is 0.1-2g：15mL.
Described vanadium source is ammonium metavanadate, sodium orthovanadate, vanadic anhydride, vanadium oxytrichloride, vanadium tetrachloride, vanadium oxysulfate or three Vanadium chloride；Sulphur source is thioacetamide, thiourea or sulphur simple substance；The amount ratio of Polyvinylpyrrolidone, vanadium source and sulphur source is 0.1g- 2g：1mol：2-5mol.
It is an advantage of the invention that：The method adopts Polyvinylpyrrolidone (PVP) as surfactant, successfully plays control Products therefrom pattern processed and the effect of size, prepare the vanadium disulfide micro-nano structure of pure phase, VS under hydrothermal conditions2Lamella is big Little rule, ulking thickness are homogeneous, are successfully realized the controllable standby of vanadium disulfide.The vanadium disulfide of the method preparation can strengthen knot Structure stability, exposes more avtive spots, is conducive to it in electrochemistry, hydrogen reduction, the application of the numerous areas such as hydrogen evolution；This system Preparation Method is simple to operate, controllability is strong, raw material is cheap and easy to get, is conducive to producing in enormous quantities.
Brief description
Fig. 1 is the XRD figure of the vanadium disulfide product of embodiment 1 preparation.
Fig. 2 is the SEM figure of the vanadium disulfide product of embodiment 1 preparation.
Fig. 3 is the SEM figure of the vanadium disulfide product of embodiment 2 preparation.
Fig. 4 is not added with the vanadium disulfide granule SEM figure of PVP preparation for embodiment 3.
Specific embodiment
Below by embodiment and combine accompanying drawing the invention will be further described, these embodiments be only intended to explanation this Invention, is not intended to limit the present invention.
Embodiment 1：
A kind of preparation method of vanadium dioxide micro-nano structure material, comprises the following steps：
1) under room temperature, with measuring 15mL ultra-pure water in 50mL beaker, by 0.5g PVP K30 (PVP-K30) It is placed in beaker, stir 30 minutes to being completely dissolved through magnetic stirrer in 800r/min；
2) 0.2mmol ammonium metavanadate and 0.1mmol thioacetamide is added to continue stirring to completely molten in above-mentioned solution Solution, waits to be completely dissolved and dissolve color to dark-brown, be added dropwise over the ammonia that concentration is 12mol/L to adjust to pH value is 9；
3) mixed solution is placed in 25ml polytetrafluoroethylliner liner, and inner bag is placed in high pressure water heating kettle.At 160 DEG C Room temperature is naturally cooled to after reaction 15h；
4) take out black suspension be placed in 50ml centrifuge tube, using centrifuge under the rotating speed of 9800r/min through ultrapure The lower washing of water and dehydrated alcohol 6 times, taking precipitate matter, dried under conditions of 110 DEG C, 0.1MPa pressure using vacuum drying oven 8h, collects product.
X-ray powder diffraction analysis is carried out to product manufactured in the present embodiment, as shown in figure 1, all peak positions and two sulfur The diffraction peak match of change vanadium is good and peak shape is sharp, illustrates to be obtained the pure phase vanadium disulfide of high-crystallinity.Fig. 2 is vanadium disulfide Scanning electron microscope (SEM) figure of product, therefrom visible vanadium disulfide pattern is homogeneous, the nanoscale twins knot piled up for height Structure, and size uniform distribution.
Embodiment 2：
A kind of preparation method of vanadium dioxide micro-nano structure material, comprises the following steps：
1) under room temperature, with measuring 15mL ultra-pure water in 50mL beaker, by 0.5g Polyvinylpyrrolidone K60 (PVP-K60) It is placed in beaker, stir 30 minutes to being completely dissolved through magnetic stirrer in 800r/min；
2) 0.2mmol ammonium metavanadate and 0.1mmol thioacetamide is added to continue stirring to completely molten in above-mentioned solution Solution, waits to be completely dissolved and dissolve color to dark-brown, be added dropwise over the ammonia that concentration is 12mol/L to adjust to pH value is 9；
3) mixed solution is placed in 25mL polytetrafluoroethylliner liner, and inner bag is placed in high pressure water heating kettle.At 160 DEG C Room temperature is naturally cooled to after reaction 20h；
4) take out black suspension to be placed in 50m centrifuge tube, using under the rotating speed of centrifuge 9800r/min through ultra-pure water and The lower washing of dehydrated alcohol 6 times, taking precipitate matter, dry 8h using vacuum drying oven under conditions of 110 DEG C, 0.1MPa pressure, Collect product.
Fig. 3 is scanning electron microscope (SEM) figure of the vanadium disulfide product according to the preparation of this example it can be seen that two sulfur Change vanadium pattern homogeneous, assume the nano-lamellar structure of high dispersive, and size uniform distribution.The prolongation in response time promotes product Dispersibility, so that vanadium disulfide nanoparticle size is reduced further, individual particle piece number of layers reduce.
Embodiment 3：
This example is not added with Polyvinylpyrrolidone, and example has synthesized flower ball-shaped vanadium disulfide granule, step as a comparison As follows：
1) under room temperature, with measuring 15mL ultra-pure water in 50mL beaker, add 0.2mmol ammonium metavanadate and 0.1mmol thio Acetamide, stirs to being completely dissolved, and waits to be completely dissolved and dissolve color to dark-brown, is added dropwise over the ammonia that concentration is 12mol/L It is 9 that water is adjusted to pH value；
2) mixed solution is placed in 25mL polytetrafluoroethylliner liner, and inner bag is placed in high pressure water heating kettle.At 160 DEG C Room temperature is naturally cooled to after reaction 20h；
3) take out black suspension be placed in 50mL centrifuge tube, using under the rotating speed of centrifuge 9800r/min through ultra-pure water And the lower washing of dehydrated alcohol 6 times, taking precipitate matter, dried under conditions of 110 DEG C, 0.1MPa pressure using vacuum drying oven 8h, collects product.
Fig. 4 is scanning electron microscope (SEM) figure of the vanadium disulfide product according to the preparation of this example it is seen that being not added with gathering The product of vinylpyrrolidone is in flower ball-shaped, and between particle diameter is about 30-40 μm, local shape is irregular.
Embodiment described above is only that embodiments of the present invention are described, without departing from design concept of the present invention On the premise of, various modifications and improvement that the R＆D personnel in this area is made to technical scheme, all should fall Enter protection scope of the present invention.

Claims (3)

1. a kind of preparation method of vanadium dioxide micro-nano structure material is it is characterised in that comprise the following steps：
1) add Polyvinylpyrrolidone to being completely dissolved in ultra-pure water, obtain polyvinylpyrrolidonesolution solution；
2) add vanadium source, sulphur source in above-mentioned polyvinylpyrrolidonesolution solution, stir to dissolving, be then 12mol/L with concentration Ammonia adjust pH value be 8-10；
3) gained mixed solution is placed in hydrothermal device and reacts 10h-20h at 120-200 DEG C；
4), after reacting completely, naturally cool to room temperature, products therefrom is scrubbed, centrifugation, vacuum drying, collect and obtain with lamella The homogeneous vanadium disulfide micro-nano structure of size rule, ulking thickness.
2. according to claim 1 vanadium dioxide micro-nano structure material preparation method it is characterised in that：Described polyethylene pyrrole The weight average molecular weight range of pyrrolidone is 6000-150000, and Polyvinylpyrrolidone is 0.1-2g with the amount ratio of ultra-pure water： 15mL.
3. according to claim 1 vanadium dioxide micro-nano structure material preparation method it is characterised in that：Described vanadium source is inclined Ammonium vanadate, sodium orthovanadate, vanadic anhydride, vanadium oxytrichloride, vanadium tetrachloride, vanadium oxysulfate or vanadium trichloride；Sulphur source is thio second Amide, thiourea or sulphur simple substance；The amount ratio of Polyvinylpyrrolidone, vanadium source and sulphur source is 0.1g-2g：1mol：2-5mol.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107452631A (en) * 2017-05-08 2017-12-08 北京大学 A kind of method that electronic device electrode is prepared using metallic transition metals chalcogen compound
CN108862381A (en) * 2018-06-26 2018-11-23 中国科学院宁波材料技术与工程研究所 Four vanadic sulfide electrode materials of one kind and its preparation method and application
CN109280938A (en) * 2018-09-30 2019-01-29 陕西科技大学 A kind of Ni of the V doping of flower ball-shaped3S2/ NF self-supporting electrode material and preparation method thereof
CN112158883A (en) * 2020-10-16 2021-01-01 成都先进金属材料产业技术研究院有限公司 Process for preparing vanadium dioxide nano powder
CN113247951A (en) * 2021-05-13 2021-08-13 陕西科技大学 Self-assembly sheet VS2Preparation method of/S nanosheet

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KR20140117189A (en) * 2013-03-26 2014-10-07 국립대학법인 울산과학기술대학교 산학협력단 Synthesis method of hybrid consisting of vanadium sulfide and reduced graphite oxide and lithium ion battery comprising the hybrid
CN105819507A (en) * 2016-04-29 2016-08-03 陕西科技大学 Preparation method and application of nanosheet self-assembled microflower-shaped VS2

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* Cited by examiner, † Cited by third party
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CN102010004A (en) * 2010-12-27 2011-04-13 中国科学技术大学 Method for preparing vanadium disulphide nano powder
KR20140117189A (en) * 2013-03-26 2014-10-07 국립대학법인 울산과학기술대학교 산학협력단 Synthesis method of hybrid consisting of vanadium sulfide and reduced graphite oxide and lithium ion battery comprising the hybrid
CN105819507A (en) * 2016-04-29 2016-08-03 陕西科技大学 Preparation method and application of nanosheet self-assembled microflower-shaped VS2

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107452631A (en) * 2017-05-08 2017-12-08 北京大学 A kind of method that electronic device electrode is prepared using metallic transition metals chalcogen compound
CN108862381A (en) * 2018-06-26 2018-11-23 中国科学院宁波材料技术与工程研究所 Four vanadic sulfide electrode materials of one kind and its preparation method and application
CN109280938A (en) * 2018-09-30 2019-01-29 陕西科技大学 A kind of Ni of the V doping of flower ball-shaped3S2/ NF self-supporting electrode material and preparation method thereof
CN112158883A (en) * 2020-10-16 2021-01-01 成都先进金属材料产业技术研究院有限公司 Process for preparing vanadium dioxide nano powder
CN113247951A (en) * 2021-05-13 2021-08-13 陕西科技大学 Self-assembly sheet VS2Preparation method of/S nanosheet

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