CN108726571A - A kind of VS4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule and preparation method thereof - Google Patents
A kind of VS4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule and preparation method thereof Download PDFInfo
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- CN108726571A CN108726571A CN201810708733.9A CN201810708733A CN108726571A CN 108726571 A CN108726571 A CN 108726571A CN 201810708733 A CN201810708733 A CN 201810708733A CN 108726571 A CN108726571 A CN 108726571A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
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- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
A kind of VS4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule and preparation method thereof, the present invention is using ethyl alcohol as solvent, it is respectively vanadium source and sulphur source with sodium metavanadate and thioacetamide, by parameters such as their concentration of Collaborative Control and proportioning, reaction temperature, reaction time, pH value in reaction, packing ratios, realizes a step solvent-thermal method in-situ preparation and be uniformly distributed VS4The VS of nanometer rods2The hollow rod-shape structure of nanometer sheet self assembly.This method reaction process is simple, temperature is low, reaction condition that is easily-controllable and not needing large scale equipment and harshness, can realize the structure that two kinds of substances combine in a specific way simultaneously in a reaction process.When by above-mentioned product using being lithium/anode material of lithium-ion battery and optical electrical catalyst, it can show excellent chemical property and catalytic performance.
Description
Technical field
The present invention relates to a kind of vanadium system sulfide composite granules and preparation method thereof, and in particular to a kind of VS4Nanometer rods/VS2
Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule and preparation method thereof.
Background technology
With big chain spacingThe one-dimensional chain of weak interchain interaction, high S contents and low development cost is green
Sulphur navajoite VS4[Xu X,Jeong S,Rout CS,Oh P,Ko M,Kim H,et al.Lithium reaction
mechanism and high rate capability of VS4-graphene nanocomposite as an anode
material for lithium batteries.J Mater Chem A.2014；2:10847-53.] be considered depositing in the energy
Storage and optical electrical catalytic field have extensive development prospect, and they are electric in photocatalysis, ultracapacitor, lithium/sodium ion
It is applied in the fields such as pond.Possess the metallic state VS of superior electrical conductivity2With excellent electronic transmission performance, and VS2Layer and layer
Between have big space lengthIt is connected with weak Van der Waals force, makes VS2Also become a kind of has application to have very much
Foreground energy storage and optical electrical catalysis material [Jun F, Xu S, Changzheng W, et al.Metallic few-
layered VS2 ultrathin nanosheets:high two-dimensional conductivity for in-
plane supercapacitors.[J].Journal of the American Chemical Society,2011,133
(44):17832-17838].If can high efficiency composition be carried out the two, by respective advantage and between synergistic effect carry out
Fusion, it will there is superior energy storage and optical electrical catalytic performance.It is well known, however, that report relate generally to pure phase VS4With
VS2Synthesis, the two is not carried out to compound report, needless to say be about VS4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly
The report of hollow rod-shape composite granule.
Invention content
The purpose of the present invention is to provide a kind of VS4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule
And preparation method thereof.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
Step 1：It takes 0.4~0.6g sodium metavanadates and 2.6~2.8g thioacetamides while to be added to 56~60ml anhydrous
In ethyl alcohol, it is uniformly mixing to obtain half clear solution A；
Step 2：Solution A is poured into sealing after reacting in liner, is then placed on liner homogeneously loaded on fixed in outer kettle
It reacts in instrument, then under the rotating speed of 5~10r/min, 26~28h is reacted at 155~165 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, is then taken out the product for reacting postcooling, warp
Washing, alcohol collect product after washing alternately cleaning；
Step 4：The product of collection is placed in the cold well of freeze drier and is freezed, then by the product after freezing
It is placed in pallet, covers seal closure, be evacuated down to 10~20Pa, product is collected after dry 12~18h to get VS4Nanometer rods/VS2
Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule.
The stirring of the step 1) is magnetic agitation or ultrasonic disperse under room temperature, and the rotating speed of magnetic agitation is 400~600r/
min。
The packing ratio that the step 2) solution A pours into reaction liner is 56~60%.
Step 3) the washing and alcohol are washed using suction filtration or eccentric cleaning.
The freezing conditions of the step 4) are：It -60~-40 DEG C, freezes 2~5 hours.
Step 4) the product is sealed before being put into pallet and being dried with preservative film, and pricks hole processing to preservative film
Ensure to its abundant drying under lower pressure.
VS made of preparation method by the present invention4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule,
Composite granule is made of irregular micron bar, and the inside of micron bar is by VS2The hollow member that nanometer sheet is barricaded as, nanometer sheet
Thickness be 10~20nm, outside is distributed across the VS on nanometer sheet surface4The diameter of nanometer rods, nanometer rods is 20~50nm,
And nanometer sheet and nanometer rods all show single crystal characteristics.
VS made of preparation method by the present invention4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule,
Applied to lithium/sodium-ion battery field or optical electrical catalytic field.
The present invention is respectively vanadium source and sulphur source with sodium metavanadate and thioacetamide using ethyl alcohol as solvent, passes through collaboration
The parameters such as their concentration and proportioning, reaction temperature, reaction time, pH value in reaction, packing ratio are controlled, a step solvent heat is realized
Method in-situ preparation is uniformly distributed VS4The VS of nanometer rods2The hollow rod-shape structure of nanometer sheet self assembly.This method reaction process is simple,
Temperature is low, reaction condition that is easily-controllable and not needing large scale equipment and harshness, can realize two kinds simultaneously in a reaction process
The structure that substance combines in a specific way.It is lithium/anode material of lithium-ion battery and optical electrical catalyst when applying above-mentioned product
When, it can show excellent chemical property and catalytic performance.
Specifically have the beneficial effect that：
(1) present invention using a step solvent thermal reaction due to directly synthesizing final product, thus has low synthesis
Temperature, simple synthesis path do not need large scale equipment and harsh reaction condition；
(2) vanadium source used in the present invention is sodium metavanadate, sulphur source is thioacetamide, both raw materials are common materials,
It is cheap and easy to get, at low cost, yield is high, reaction is easily-controllable, be not necessarily to post-processing, it is environmentally friendly, can be suitble to mass produce；
(3) it can be showed when product prepared by the present invention being used as lithium/anode material of lithium-ion battery and optical electrical catalyst
Go out excellent performance；
(4) present invention passes through stringent Collaborative Control vanadium source, the concentration of sulphur source and proportioning, reaction temperature, reaction time, reaction
The parameters such as pH value, packing ratio, realize reaction in vanadium sulphur existence control, to rise make high concentration sulphur source under the action of
Preferentially in NaVO3Micron bar Surface Creation VS4Nanometer rods make then under the action of low concentration sulphur source inside micron bar
NaVO3It is transformed into VS2Nanometer sheet, and make VS2Nanometer sheet forms internal hollow structure in a manner of self assembly, finally realizes
High-purity and uniform VS4Nanometer rods/VS2The preparation of nanometer sheet three-dimensional self assembly hollow rod-shape composite material.In entire reaction process
In, reaction temperature plays a key role the formation of the unique texture, and excessively high and too low temperature is all unfavorable for the structure
Formation.
(5) present invention does not introduce any template or surfactant during synthesis three-dimensional self-assembled structures,
Entire self assembling process is based on reaction starting material NaVO3The slightly soluble characteristic of micron bar is acted on by the self-template of reaction raw materials
Control, thus entirely react simple, easily-controllable, efficient and inexpensive；
(6) combination product prepared by the present invention has unique composite construction, wherein VS2The hollow structure of nanometer sheet composition
The effect of rock-steady structure in electrochemical reaction process can be functioned well as, and a large amount of lithium/sodium ion storage site can be provided.
VS2The VS on nanometer sheet surface4A large amount of lithium/sodium ion storage site can be further provided for, to enable final composite material
Enough show excellent cyclical stability and high rate performance and higher capacity.In addition, VS4Nanorod surfaces are largely catalyzed
Active site and metallic state VS2Excellent electric conductivity makes composite material finally show excellent catalytic performance.
Description of the drawings
Fig. 1 is the X-ray diffractogram that the embodiment of the present invention 1 prepares product.
Fig. 2 is the low power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 3 is the high power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 4 is the super-high power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.
Fig. 5 is the transmission electron microscope picture that the embodiment of the present invention 1 prepares product.
Fig. 6 is the high-resolution-ration transmission electric-lens figure that the embodiment of the present invention 1 prepares nanometer rods outside product micron bar.
Fig. 7 is the high-resolution-ration transmission electric-lens figure that the embodiment of the present invention 1 prepares nanometer sheet inside product micron bar.
Fig. 8 is (other conditions and 1 complete phase of embodiment after the reaction temperature in the embodiment of the present invention 1 is adjusted to 120 DEG C
Together), the scanning electron microscope (SEM) photograph of products therefrom.
Fig. 9 be by the reaction temperature in the embodiment of the present invention 1 it is whole be 180 DEG C after (other conditions and 1 complete phase of embodiment
Together), the scanning electron microscope (SEM) photograph of products therefrom.
Specific implementation mode
Invention is further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1：
Step 1：It takes 0.5g sodium metavanadates and 2.6g thioacetamides while being added in 60ml absolute ethyl alcohols, in room temperature
Under half clear solution A uniformly obtained with 400r/min magnetic agitations；
Step 2：Sealing after pouring into solution A in reaction liner by 58% packing ratio, then by liner loaded in outer kettle
Fixation is placed in homogeneous reaction instrument, then under the rotating speed of 8r/min, reacts 26h at 155 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, then the product for reacting postcooling is taken out, is adopted
Product is collected after alternately being cleaned 3 times in a manner of filtering with water and alcohol；
Step 4：The product of collection is placed in the cold well of freeze drier at -60 DEG C, is freezed 2 hours, it then will freezing
Product afterwards is placed in pallet, is sealed with preservative film, and it is abundant under lower pressure to it to prick hole processing guarantee to preservative film
It is dry, then seal closure is covered, it is evacuated down to 15Pa, product is collected after dry 12h to get VS4Nanometer rods/VS2Nanometer sheet three-dimensional is certainly
Assemble hollow rod-shape composite granule.
From in Fig. 1 it can be found that there is VS in lower diffraction angular region4Diffraction maximum, in the higher angle of diffraction
Occurs VS in range2Diffraction maximum implies that the product of the preparation method synthesis provided by embodiment 1 is VS4And VS2Answer
Close object.
From figure 2 it can be seen that products therefrom is made of the rodlike three-dimensional construct of irregular class, the length of the construct
Degree and width are all in the micron-scale.
From figure 3, it can be seen that gained micron bar presents hollow structure
Figure 4, it is seen that the inside of gained micron bar is by VS2The hollow member that nanometer sheet is barricaded as, nanometer sheet
Thickness is 10~20nm, and outside is distributed across the VS on nanometer sheet surface4The diameter of nanometer rods, nanometer rods is 20~50nm.
From figure 5 it can be seen that micron bar presents uniform hollow structure, and the size of cavity will be far longer than wall
Size.
As can be seen from Figure 6 the lattice fringe of regular arrangement corresponds to VS4(110) crystal face, on the one hand confirm
Nanometer rods are VS4, on the other hand illustrate VS4Nanometer rods show single crystal characteristics.
As can be seen from Figure 7 the lattice fringe of more regular arrangement, wherein big spacing lattice fringe corresponds to VS2's
(001) crystal face, small spacing lattice fringe correspond to VS2(011) crystal face, on the one hand confirm nanometer sheet be VS2, on the other hand
Also illustrate VS2Nanometer sheet shows single crystal characteristics.
From figure 8, it is seen that products therefrom is solid construction, it is meant that under the conditions of too low reaction temperature, be unfavorable for
The formation of hollow structure.
From in Fig. 9 it can be found that without VS in product4Nanorod shaped is at, it is meant that excessively high reaction temperature condition
Under, it is unfavorable for VS4/VS2The formation of combination product.
Embodiment 2：
Step 1：It takes 0.4g sodium metavanadates and 2.7g thioacetamides while being added in 56ml absolute ethyl alcohols, in room temperature
Under half clear solution A uniformly obtained with 500r/min magnetic agitations；
Step 2：Sealing after pouring into solution A in reaction liner by 56% packing ratio, then by liner loaded in outer kettle
Fixation is placed in homogeneous reaction instrument, then under the rotating speed of 5r/min, reacts 27h at 160 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, then the product for reacting postcooling is taken out, is adopted
Product is collected after alternately being cleaned 4 times in a manner of filtering with water and alcohol；
Step 4：The product of collection is placed in the cold well of freeze drier at -50 DEG C, is freezed 3 hours, it then will freezing
Product afterwards is placed in pallet, is sealed with preservative film, and it is abundant under lower pressure to it to prick hole processing guarantee to preservative film
It is dry, then seal closure is covered, it is evacuated down to 12Pa, product is collected after dry 16h to get VS4Nanometer rods/VS2Nanometer sheet three-dimensional is certainly
Assemble hollow rod-shape composite granule.
Embodiment 3：
Step 1：It takes 0.55g sodium metavanadates and 2.8g thioacetamides while being added in 58ml absolute ethyl alcohols, in room temperature
Under half clear solution A uniformly obtained with 600r/min magnetic agitations；
Step 2：Sealing after pouring into solution A in reaction liner by 60% packing ratio, then by liner loaded in outer kettle
Fixation is placed in homogeneous reaction instrument, then under the rotating speed of 10r/min, reacts 28h at 165 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, then the product for reacting postcooling is taken out, is adopted
Product is collected after alternately being cleaned 5 times in a manner of filtering with water and alcohol；
Step 4：The product of collection is placed in the cold well of freeze drier at -45 DEG C, is freezed 4 hours, it then will freezing
Product afterwards is placed in pallet, is sealed with preservative film, and it is abundant under lower pressure to it to prick hole processing guarantee to preservative film
It is dry, then seal closure is covered, it is evacuated down to 18Pa, product is collected after dry 14h to get VS4Nanometer rods/VS2Nanometer sheet three-dimensional is certainly
Assemble hollow rod-shape composite granule.
Embodiment 4：
Step 1：It takes 0.45g sodium metavanadates and 2.65g thioacetamides while being added in 57ml absolute ethyl alcohols, normal
The lower ultrasonic disperse of temperature uniformly obtains half clear solution A；
Step 2：Sealing after pouring into solution A in reaction liner by 57% packing ratio, then by liner loaded in outer kettle
Fixation is placed in homogeneous reaction instrument, then under the rotating speed of 7r/min, reacts 28h at 158 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, then the product for reacting postcooling is taken out, is adopted
Product is collected after alternately being cleaned 4 times in eccentric fashion with water and alcohol；
Step 4：The product of collection is placed in the cold well of freeze drier at -55 DEG C, is freezed 4 hours, it then will freezing
Product afterwards is placed in pallet, is sealed with preservative film, and it is abundant under lower pressure to it to prick hole processing guarantee to preservative film
It is dry, then seal closure is covered, it is evacuated down to 10Pa, product is collected after dry 18h to get VS4Nanometer rods/VS2Nanometer sheet three-dimensional is certainly
Assemble hollow rod-shape composite granule.
Embodiment 5：
Step 1：It takes 0.6g sodium metavanadates and 2.75g thioacetamides while being added in 59ml absolute ethyl alcohols, in room temperature
Lower ultrasonic disperse uniformly obtains half clear solution A；
Step 2：Sealing after pouring into solution A in reaction liner by 59% packing ratio, then by liner loaded in outer kettle
Fixation is placed in homogeneous reaction instrument, then under the rotating speed of 9r/min, reacts 26h at 162 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, then the product for reacting postcooling is taken out, is adopted
Product is collected after alternately being cleaned 5 times in eccentric fashion with water and alcohol；
Step 4：The product of collection is placed in the cold well of freeze drier at -40 DEG C, is freezed 5 hours, it then will freezing
Product afterwards is placed in pallet, is sealed with preservative film, and it is abundant under lower pressure to it to prick hole processing guarantee to preservative film
It is dry, then seal closure is covered, it is evacuated down to 20Pa, product is collected after dry 15h to get VS4Nanometer rods/VS2Nanometer sheet three-dimensional is certainly
Assemble hollow rod-shape composite granule.
Claims (8)
1. a kind of VS4Nanometer rods/VS2The preparation method of nanometer sheet three-dimensional self assembly hollow rod-shape composite granule, it is characterised in that：
Step 1：It takes 0.4~0.6g sodium metavanadates and 2.6~2.8g thioacetamides while being added to 56~60ml absolute ethyl alcohols
In, it is uniformly mixing to obtain half clear solution A；
Step 2：Liner is then placed on homogeneous reaction by sealing after solution A is poured into reaction liner loaded on fixation in outer kettle
In instrument, then under the rotating speed of 5~10r/min, 26~28h is reacted at 155~165 DEG C；
Step 3：Reaction kettle is naturally cooled into room temperature after reaction, is then taken out the product for reacting postcooling, through water
It washes, alcohol is washed after alternately cleaning and collects product；
Step 4：The product of collection is placed in the cold well of freeze drier and is freezed, is then placed in the product after freezing
In pallet, seal closure is covered, is evacuated down to 10~20Pa, product is collected after dry 12~18h to get VS4Nanometer rods/VS2Nanometer
Piece three-dimensional self assembly hollow rod-shape composite granule.
2. VS according to claim 14Nanometer rods/VS2The preparation side of nanometer sheet three-dimensional self assembly hollow rod-shape composite granule
Method, it is characterised in that：The stirring of the step 1) is magnetic agitation or ultrasonic disperse under room temperature, and the rotating speed of magnetic agitation is 400
~600r/min.
3. VS according to claim 14Nanometer rods/VS2The preparation side of nanometer sheet three-dimensional self assembly hollow rod-shape composite granule
Method, it is characterised in that：The packing ratio that the step 2) solution A pours into reaction liner is 56~60%.
4. VS according to claim 14Nanometer rods/VS2The preparation side of nanometer sheet three-dimensional self assembly hollow rod-shape composite granule
Method：It is characterized in that：Step 3) the washing and alcohol are washed using suction filtration or eccentric cleaning.
5. VS according to claim 14Nanometer rods/VS2The preparation side of nanometer sheet three-dimensional self assembly hollow rod-shape composite granule
Method, it is characterised in that：The freezing conditions of the step 4) are：It -60~-40 DEG C, freezes 2~5 hours.
6. VS according to claim 14Nanometer rods/VS2The preparation side of nanometer sheet three-dimensional self assembly hollow rod-shape composite granule
Method, it is characterised in that：Step 4) the product is sealed before being put into pallet and being dried with preservative film, and is pricked to preservative film
Hole processing ensures to its abundant drying under lower pressure.
7. VS made of a kind of preparation method as described in claim 14Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape
Composite granule, it is characterised in that：Composite granule is made of irregular micron bar, and the inside of micron bar is by VS2Nanometer sheet
The thickness of the hollow member being barricaded as, nanometer sheet is 10~20nm, and outside is distributed across the VS on nanometer sheet surface4Nanometer rods, nanometer
The diameter of stick is 20~50nm, and nanometer sheet and nanometer rods all show single crystal characteristics.
8. VS made of a kind of preparation method as described in claim 14Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape
Composite granule, it is characterised in that：VS4Nanometer rods/VS2Nanometer sheet three-dimensional self assembly hollow rod-shape composite granule be applied to lithium/sodium from
Sub- field of batteries or optical electrical catalytic field.
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| CN201810708733.9A CN108726571B (en) | 2018-07-02 | 2018-07-02 | VS (virtual switch)4nanorod/VS2Nano sheet three-dimensional self-assembly hollow rod-shaped composite powder and preparation method thereof |
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| CN201810708733.9A CN108726571B (en) | 2018-07-02 | 2018-07-02 | VS (virtual switch)4nanorod/VS2Nano sheet three-dimensional self-assembly hollow rod-shaped composite powder and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110282660A (en) * | 2019-07-03 | 2019-09-27 | 中国计量大学 | A kind of four vanadic sulfide powder of nano bar-shape and its preparation method and application |
| CN111732124A (en) * | 2020-06-22 | 2020-10-02 | 陕西师范大学 | Preparation method of cluster-shaped vanadium tetrasulfide nano short rod |
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| CN107902697A (en) * | 2017-11-02 | 2018-04-13 | 陕西科技大学 | A kind of nanometer sheet self assembled three-dimensional VS of (001) orientation2Micron bar and preparation method thereof |
| CN108126712A (en) * | 2017-12-22 | 2018-06-08 | 陕西科技大学 | A kind of VOOH/VS4Micron composite granule and preparation method and application |
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| CN107902697A (en) * | 2017-11-02 | 2018-04-13 | 陕西科技大学 | A kind of nanometer sheet self assembled three-dimensional VS of (001) orientation2Micron bar and preparation method thereof |
| CN108126712A (en) * | 2017-12-22 | 2018-06-08 | 陕西科技大学 | A kind of VOOH/VS4Micron composite granule and preparation method and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282660A (en) * | 2019-07-03 | 2019-09-27 | 中国计量大学 | A kind of four vanadic sulfide powder of nano bar-shape and its preparation method and application |
| CN110282660B (en) * | 2019-07-03 | 2022-02-11 | 中国计量大学 | Nano rod-shaped vanadium tetrasulfide powder and preparation method and application thereof |
| CN111732124A (en) * | 2020-06-22 | 2020-10-02 | 陕西师范大学 | Preparation method of cluster-shaped vanadium tetrasulfide nano short rod |
| CN111732124B (en) * | 2020-06-22 | 2022-11-08 | 陕西师范大学 | Preparation method of cluster-shaped vanadium tetrasulfide nano short rod |
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