CN107221646A - A kind of vanadium disulfide nanometer sheet of hydroxide vanadyl cladding and its preparation method and application - Google Patents
A kind of vanadium disulfide nanometer sheet of hydroxide vanadyl cladding and its preparation method and application Download PDFInfo
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- CN107221646A CN107221646A CN201710571056.6A CN201710571056A CN107221646A CN 107221646 A CN107221646 A CN 107221646A CN 201710571056 A CN201710571056 A CN 201710571056A CN 107221646 A CN107221646 A CN 107221646A
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
The invention provides vanadium disulfide nanometer sheet of a kind of hydroxide vanadyl cladding and its preparation method and application, sodium metavanadate and thioacetamide are dissolved in deionized water simultaneously under magnetic agitation state.Then, sealed after above-mentioned solution is poured into reaction liner, then liner is loaded on after being fixed in outer kettle and be placed in homogeneous reaction instrument.Finally, wash, collect, dry after reacted product is cooled down, you can obtain the VS of VOOH claddings2Nanometer sheet.The VS of VOOH claddings prepared by the present invention2Nanometer sheet chemical composition is homogeneous, and purity is higher, and pattern is uniform, and with specific self-assembled structures, excellent chemical property is shown during as sodium ion battery electrode material.In addition, the method overcome the high shortcoming of conventional calcination method temperature, and large scale equipment and harsh reaction condition are not needed, raw material is cheap and easy to get, and cost is low, yield is high, environmentally friendly without post-processing, large-scale production can be adapted to.
Description
【Technical field】
The present invention relates to a kind of preparation method of composite, and in particular to a kind of VS of VOOH claddings2The system of nanometer sheet
Preparation Method and application.
【Background technology】
Sodium is because the characteristics of low widely distributed and cost, therefore, sodium-ion battery is used as large scale energy stores of future generation
System is of increased attention.In order to find suitable anode material of lithium-ion battery, the hand that researcher passes through experiment
Section explores substantial amounts of active material.In these negative materials, because they have the layer structure of suitable interlayer space, mistake
Cross metal disulfides such as MoS2、WS2And VS2Etc. being considered as a kind of very promising candidate.Although nearest research is
Through showing MoS2And WS2It can show excellent storage sodium performance, but electric transmission poor caused by their characteristic of semiconductor
Performance limits it and further developed.As a prototypical member in transition metal dichalcogenide family, possess excellent conduction
The metallic state VS of property2It is expected to show excellent electron-transporting in the cyclic process as sodium cell negative pole material
Energy.VS2Belong to a kind of hexagonal crystal system with layer structure, metallic state V forms S-V-S layers, S-V- between being mixed in two layers of S
S is stacked in space and is formd layer structure, and space length between layers isIt can be provided for the insertion of sodium ion
Sufficient space.It is noted that connected between layers by Van der Waals force, this weak connection contribute to sodium ion/
Electronics is quickly transmitted without causing serious structure to be destroyed in interlayer.In addition, correlative study also indicates that stratiform VS2With high ratio
Capacity, big surface-active, low ion diffusional resistance and low open-circuit voltage, this more makes VS2Becoming one kind has prospect
Sodium ion negative material.However, recently on VS2Research but focus primarily upon electro-catalysis, ferromagnet, biology sensor,
Magnetic electron device, ultracapacitor and lithium electricity.
Although first-principles calculations are further demonstrated that：VS2It can be shown as anode material of lithium-ion battery excellent
Chemical property, but will test prepare VS2The report for being directly used as anode material of lithium-ion battery is seldom.In addition,
In VS2As in the cyclic process of lithium ion battery electrode material, VS2Volumetric expansion will cause its efflorescence, then substantially reduce
Its chemical property.When by VS2During applied to sodium-ion battery, because sodium ion has the radius bigger than lithium ion, this
Volumetric expansion is planted to will become apparent.
At present, alleviating volumetric expansion then improves VS2The main method of chemical property be with graphene, CNT and
The Material claddings such as organic polymer.However, these materials are to VS2The suppression of volumetric expansion only occurs in the direction of contact point
On, result in inapparent chemical property improves.In addition, these materials need to be manufactured separately or buy, whole synthesis can be made
Process becomes complicated, poorly efficient and high cost.
Therefore, efficient, simple and inexpensive method is explored, to suppress VS2Volumetric expansion, with finally lifted its store up sodium
Performance is to be highly desirable to, and is also significantly.
【The content of the invention】
There is the excellent VS for storing up sodium performance it is an object of the invention to provide a kind of efficient, simple and inexpensive prepare2It is negative
Pole material, more particularly to a kind of VS of VOOH claddings2The preparation method and applications of nanometer sheet, this method uses a step water at low temperature
Heat is in VS2Nanometer sheet surface in situ grown VOOH, and this method course of reaction is simple, and reaction temperature is low, and need not be large-scale
Equipment and harsh reaction condition.
The present invention uses following technical scheme：
A kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding, according to 1:2.5~1:3.5 vanadium sulphur rub
You compare, and sodium metavanadate and thioacetamide are dissolved in deionized water simultaneously, stirring to half clear state；Then hydro-thermal is carried out
Reaction, hydro-thermal reaction is carried out under rotation condition, to ensure homoepitaxial of the hydroxide vanadyl on vanadium disulfide surface.
Before occurring hydro-thermal reaction, pH regulations will be reacted to 10.3~10.5 with ammoniacal liquor.
Regulation pH process, which adds one to adjust dropwise, that is, and drips to stir to pH value of solution after ammoniacal liquor, not to be changed, under then adding
One drop ammoniacal liquor, until the last pH value of solution reaches 10.3~10.5.
Need constantly to carry out magnetic agitation during regulation pH.
The packing ratio of the hydro-thermal reaction is 55~65%, and the detailed process of hydro-thermal reaction is：By configured good mixing
Solution is poured into reaction liner, then by liner after sealing be loaded in outer kettle it is fixed after be placed in homogeneous reaction instrument, then 5~
15r/min, under conditions of 155~165 DEG C, react 23~25h.
The washing is that alternately washing and alcohol is washed after the product cooled down after hydro-thermal reaction is taken out；The drying temperature
For 55~65 DEG C, the time is 10~15h.
A kind of vanadium disulfide nanometer sheet of hydroxide vanadyl cladding, products therefrom is the VS that crystal VOOH is coated2Nanometer sheet.
Before hydro-thermal reaction adjust pH value of solution be 10.3~10.5 after, products therefrom be amorphous VOOH coat VS2Nanometer
Piece.
The nanometer sheet is flower-shaped in self assembly micron, and the thickness of nanometer sheet is 30~50nm.
A kind of application of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding, the nanometer sheet is applied to the negative of sodium-ion battery
Pole material, the anode material of lithium-ion battery shows excellent chemical property, 100,200,500,1000,2000,
5000mAg-1Current density under, show up to 384,364,316,224,140,113mAhg-1Specific capacity；
200mAg-1Current density under, circulation 150 circle after remain in that 330mAhg-1Specific capacity, capability retention is up to 94%.
Relative to prior art, the present invention at least has the advantages that：
The present invention is prepared for the VS of VOOH claddings using a step low-temperature hydrothermal synthetic method first2Nanometer sheet, and report first
Chemical property of this material as anode material of lithium-ion battery.Specifically have the beneficial effect that：
(1) this method directly synthesizes final product because it uses a step hydro-thermal reaction, thus with low synthesis
Temperature, simple synthesis path, it is not necessary to which large scale equipment and harsh reaction condition, raw material are cheap and easy to get, and cost is low, yield
Height, it is environmentally friendly without post-processing, large-scale production can be adapted to.
(2) this method is prepared for VS simultaneously by a step hydro-thermal reaction2With two kinds of materials of VOOH, and VOOH is complete cladding
In VS2Nanometer sheet surface, it can limit volumetric expansion of the VS2 electrode materials in charge and discharge process from more dimensions,
So as to lift its cyclical stability.
(3) this method is used, by adjusting pH value in reaction, VS can be made2Surface coating crystal VOOH and unformed
Two kinds of VOOH of VOOH material, and the VOOH of both claddings can lift VS2The chemical property of nanometer sheet.And due to crystal
The structure of VOOH steady ordereds, it is to VS2VS2The lifting of nanometer sheet chemical property is more notable.When not adjusting solution ph
When, the VOOH of cladding is crystal structure, when adjusting pH value of solution to 10.3~10.5 with ammoniacal liquor, and the VOOH of cladding is unformed knot
Structure.
(4) VOOH is except to VS2Play the role of outside protection, also activate VS2The effect on nanometer sheet surface, enables VS2 surfaces
Enough absorption/desorption sodium ions faster and more.
(5) this method technique is simple and easy to control, main control parameters be sodium metavanadate and thioacetamide concentration and proportioning,
Reaction temperature, time, packing ratio, pH value and stirring, core control parameter are pH value in reaction, and the control of these parameters is all easy
In realization.This method takes full advantage of the characteristic of vanadium oxyphie in aqueous, by controlling reactant concentration and proportioning, reaction
The parameters such as temperature, time and pH, successfully synthesize VS2Afterwards, it grown VOOH in its surface in situ.
(6) VS for the VOOH claddings that prepared by this method2Nanometer sheet forms micro-flowers by way of self assembly, i.e., by thickness
Degree is about that 30~50nm nanometer sheet is self-assembled into the micro-flowers that diameter is about 3~5um, VS2The surface coated VOOH of nanometer sheet
Thickness is less than 10nm.The electrolyte that this self assembly mode is very beneficial for carrying sodium ion is freed in and out, while also very
Be conducive to electrolyte and VS2The abundant contact of nanometer sheet, can then greatly enhance its chemical property.
(7) the product chemistry composition that prepared by this method is homogeneous, and purity is high, and pattern is uniform, and it is used as sodium-ion battery electrode
Excellent chemical property can be shown during material.
(8) in the building-up process of material, VS2Nanometer sheet surface VOOH formation, fully inhibits VS2Nanometer sheet is entered
One step growth, thus the nanometer sheet of synthesis has less thickness, its be conducive to sodium ion enter the inside of nanometer sheet there is provided
More storage sodium sites, are also beneficial to the smooth turnover of sodium ion and electronics, so as to substantially improve chemical property.
【Brief description of the drawings】
Fig. 1 is the VS of crystal VOOH claddings prepared by the embodiment of the present invention 12X-ray diffraction (XRD) collection of illustrative plates of nanometer sheet；
Fig. 2 is the VS coated by crystal VOOH prepared by the embodiment of the present invention 12Nanometer sheet is self-assembled into the scanning of micro-flowers
Electronic Speculum (SEM) photo.
Fig. 3 is the VS coated by crystal VOOH prepared by the embodiment of the present invention 12Nanometer sheet is self-assembled into the amplification of micro-flowers
ESEM (SEM) photo.
Fig. 4 is the VS coated by crystal VOOH prepared by the embodiment of the present invention 12Nanometer sheet is self-assembled into the transmission of micro-flowers
Electronic Speculum (TEM) photo
Fig. 5 is the VS coated by crystal VOOH prepared by the embodiment of the present invention 12The high-resolution-ration transmission electric-lens of nanometer sheet
(HRTEM) photo.
Fig. 6 is the VS coated by crystal VOOH prepared by the embodiment of the present invention 12Nanometer sheet transmission element energy spectrum diagram (STEM-
) and scan element energy spectrum diagram (SEM-EDS) EDS.
【Embodiment】
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
A kind of VS of VOOH claddings2The preparation method of nanometer sheet, comprises the following steps：
Step one：Weigh sodium metavanadate and thioacetamide and while be added in 55~65ml deionized waters, control vanadium
Sulphur mol ratio is 1:2.5~1:3.5,20~40min of magnetic agitation obtain half settled solution A, and now the concentration of sodium metavanadate is
0.1~0.15mol/L.
Step 2：Sealed after solution A is poured into reaction liner, it is then that liner is homogeneous loaded on being placed in after being fixed in outer kettle
React in instrument, then under conditions of 5~15r/min, in 23~25h of reaction at 155~165 DEG C.Wherein reaction-filling is than answering
The control is 55~65%.The progress of the reaction must be carried out under rotation condition, so be conducive to the full and uniform of reactant
Contact, thereby may be ensured that VOOH in VS2The homoepitaxial on surface.
Step 3：Hydro-thermal reaction terminates, and reactor is naturally cooled into room temperature, then takes the product cooled down after reaction
Go out, product collected after 2~5 washings and 2~5 alcohol are alternately cleaned, and under the conditions of 55~65 DEG C, dry 10~15h,
It can obtain the VS of VOOH claddings2Nanometer sheet.
A kind of VS of the VOOH claddings prepared by the above method2The application of nanometer sheet, the nanometer sheet is self-assembled into micron
It is flower-shaped be applied to sodium/lithium ion battery when, show excellent chemical property, it exists as anode material of lithium-ion battery
100,200,500,1000,2000,5000mAg-1Current density under, show up to 384,364,316,224,140,
113mAhg-1Specific capacity.In 200mAg-1Current density under, its first charge-discharge capacity can reach 364 Hes
330mAhg still can be kept after 442mAhg-1, the circle of circulation 150-1Specific capacity, capability retention is up to 94%.
Embodiment 1
Step one：Weigh sodium metavanadate and thioacetamide and while being added in 60ml deionized waters, control vanadium sulphur rubs
You are than being 1:3.0, magnetic agitation 30min obtain half settled solution A, and now the concentration of sodium metavanadate is 0.137mol/L.
Step 2：Sealed after solution A is poured into reaction liner, it is then that liner is homogeneous loaded on being placed in after being fixed in outer kettle
React in instrument, then under conditions of 10r/min, in reacting 24h at 160 DEG C.Wherein reaction-filling ratio should be controlled 60%.
Step 3：Hydro-thermal reaction terminates, and reactor is naturally cooled into room temperature, then takes the product cooled down after reaction
Go out, collect product after 3 washings and 3 alcohol are alternately cleaned, and under the conditions of 60 DEG C, dry 12h, you can obtain VOOH bags
The VS covered2Nanometer sheet.
From figure 1 it appears that X-ray powder diffraction peak has pointed to VS simultaneously2And VOOH, therefore embodiment 1 is synthesis
VOOH cladding VS2Nanometer sheet.
Can understand from Fig. 2 must see the VS of VOOH claddings2It is flower-shaped that nanometer sheet has been self-assembled into micron, and micro-flowers
Diameter be about 3um.
This it appears that the VS of VOOH claddings from Fig. 32The thickness of nanometer sheet is about 30~50nm.
Can be with it is also seen that the VS coated by VOOH from Fig. 42Nanometer sheet self assembly micron flower-like structure.
Can more intuitively it find out from Fig. 5, VS2One layer crystal body VOOH of nanometer sheet Surface coating.
From fig. 6, it can be seen that element S the peak intensity that SEM-EDS is composed apparently higher than its STEM-EDS spectrum in peak intensity, meaning
Taste material that STEM-EDS detected not VS2But VOOH, it is with reference to STEM-EDS investigative range<10nm, therefore
It is coated on VS2The crystal VOOH on nanometer sheet surface thickness is less than 10nm.
Embodiment 2
Step one：Weigh sodium metavanadate and thioacetamide and while being added in 55ml deionized waters, control vanadium sulphur rubs
You are than being 1:2.5, magnetic agitation 20min obtain half settled solution A, and now the concentration of sodium metavanadate is 0.1mol/L.
Step 2：Sealed after solution A is poured into reaction liner, it is then that liner is homogeneous loaded on being placed in after being fixed in outer kettle
React in instrument, then under conditions of 5r/min, in reacting 23h at 155 DEG C.
Step 3：Hydro-thermal reaction terminates, and reactor is naturally cooled into room temperature, then takes the product cooled down after reaction
Go out, collect product after 2 washings and 5 alcohol are alternately cleaned, and under the conditions of 55 DEG C, dry 10h, you can obtain VOOH bags
The VS covered2Nanometer sheet.
Embodiment 3
Step one：Weigh sodium metavanadate and thioacetamide and while be added in 55~65ml deionized waters, control vanadium
Sulphur mol ratio is 1:3.2, magnetic agitation 35min obtain half settled solution A, and now the concentration of sodium metavanadate is 0.12mol/L.
Step 2：Sealed after solution A is poured into reaction liner, it is then that liner is homogeneous loaded on being placed in after being fixed in outer kettle
React in instrument, then under conditions of 12r/min, in reacting 24.5h at 162 DEG C.
Step 3：Hydro-thermal reaction terminates, and reactor is naturally cooled into room temperature, then takes the product cooled down after reaction
Go out, collect product after 4 washings and 4 alcohol are alternately cleaned, and under the conditions of 62 DEG C, dry 14h, you can obtain VOOH bags
The VS covered2Nanometer sheet.
Embodiment 4
Step one：Weigh sodium metavanadate and thioacetamide and while be added in 55~65ml deionized waters, control vanadium
Sulphur mol ratio is 1:3.5, magnetic agitation 40min obtain half settled solution A, and now the concentration of sodium metavanadate is 0.15mol/L.
Step 2：Sealed after solution A is poured into reaction liner, it is then that liner is homogeneous loaded on being placed in after being fixed in outer kettle
React in instrument, then under conditions of 15r/min, in reacting 25h at 165 DEG C.
Step 3：Hydro-thermal reaction terminates, and reactor is naturally cooled into room temperature, then takes the product cooled down after reaction
Go out, collect product after 5 washings and 5 alcohol are alternately cleaned, and under the conditions of 65 DEG C, dry 15h, you can obtain VOOH bags
The VS covered2Nanometer sheet.
Claims (10)
1. a kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding, it is characterised in that according to 1:2.5~1:
3.5 vanadium sulphur mol ratio, sodium metavanadate and thioacetamide is dissolved in deionized water simultaneously, stirring to half clear state；
Then hydro-thermal reaction is carried out, hydro-thermal reaction is carried out under rotation condition, to ensure hydroxide vanadyl in the equal of vanadium disulfide surface
Even growth.
2. a kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 1, its feature
It is, before occurring hydro-thermal reaction, pH regulations will be reacted to 10.3~10.5 with ammoniacal liquor.
3. a kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 2, its feature
It is, regulation pH process, which adds one to adjust dropwise, that is, and drips to stir to pH value of solution after ammoniacal liquor, not to be changed, and then adds next drop
Ammoniacal liquor, until the last pH value of solution reaches 10.3~10.5.
4. a kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 2, its feature
It is, needs constantly to carry out magnetic agitation during regulation pH.
5. a kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 1 or 2, it is special
Levy and be, the packing ratio of the hydro-thermal reaction is 55~65%, and the detailed process of hydro-thermal reaction is：Configured good mixing is molten
Liquid is poured into reaction liner, then by liner after sealing be loaded in outer kettle it is fixed after be placed in homogeneous reaction instrument, then 5~
15r/min, under conditions of 155~165 DEG C, react 23~25h.
6. a kind of preparation method of the vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 1 or 2, it is special
Levy and be, the washing is that alternately washing and alcohol is washed after the product cooled down after hydro-thermal reaction is taken out；The drying temperature
For 55~65 DEG C, the time is 10~15h.
7. a kind of a kind of vanadium disulfide nanometer sheet of the hydroxide vanadyl cladding prepared based on claim 1 methods described, it is special
Levy and be, products therefrom is the VS that crystal VOOH is coated2Nanometer sheet.
8. a kind of vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 7, it is characterised in that：In hydro-thermal
Reaction before regulation pH value of solution be 10.3~10.5 after, products therefrom be amorphous VOOH coat VS2Nanometer sheet.
9. a kind of vanadium disulfide nanometer sheet of hydroxide vanadyl cladding according to claim 7 or 8, it is characterised in that：Institute
State nanometer sheet flower-shaped in self assembly micron, and the thickness of nanometer sheet is 30~50nm.
10. a kind of application of the vanadium disulfide nanometer sheet of the hydroxide vanadyl cladding prepared according to the method described in claim 1,
Characterized in that, the nanometer sheet is applied to the negative material of sodium-ion battery, the anode material of lithium-ion battery shows excellent
Chemical property, 100,200,500,1000,2000,5000mAg-1Current density under, show up to 384,
364,316,224,140,113mAhg-1Specific capacity；In 200mAg-1Current density under, circulation 150 circle after remain in that
330mAhg-1Specific capacity, capability retention is up to 94%.
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| CN108046320A (en) * | 2017-12-19 | 2018-05-18 | 重庆大学 | A kind of preparation method of electrode material for super capacitor vanadic sulfide nano flower |
| 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 |
| CN109201083A (en) * | 2018-10-29 | 2019-01-15 | 陕西科技大学 | A kind of nano flower-like vanadium disulfide/difunctional composite electrocatalyst of hydroxyl vanadium oxide and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010004A (en) * | 2010-12-27 | 2011-04-13 | 中国科学技术大学 | Method for preparing vanadium disulphide nano powder |
| CN105810942A (en) * | 2016-04-29 | 2016-07-27 | 陕西科技大学 | Preparation method of vanadium tetrasulfide nano-powder and application |
| 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 |
-
2017
- 2017-07-13 CN CN201710571056.6A patent/CN107221646B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010004A (en) * | 2010-12-27 | 2011-04-13 | 中国科学技术大学 | Method for preparing vanadium disulphide nano powder |
| CN105810942A (en) * | 2016-04-29 | 2016-07-27 | 陕西科技大学 | Preparation method of vanadium tetrasulfide nano-powder and application |
| 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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| CN108046320A (en) * | 2017-12-19 | 2018-05-18 | 重庆大学 | A kind of preparation method of electrode material for super capacitor vanadic sulfide nano flower |
| 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 |
| CN108126712B (en) * | 2017-12-22 | 2020-11-13 | 陕西科技大学 | VOOH/VS4Micron composite powder and its prepn and application |
| CN109295475A (en) * | 2018-10-10 | 2019-02-01 | 陕西科技大学 | A kind of preparation method of selenium doping selenizing vanadium composite material |
| CN109295475B (en) * | 2018-10-10 | 2020-01-21 | 陕西科技大学 | Preparation method of selenium-doped vanadium selenide composite material |
| CN109201083A (en) * | 2018-10-29 | 2019-01-15 | 陕西科技大学 | A kind of nano flower-like vanadium disulfide/difunctional composite electrocatalyst of hydroxyl vanadium oxide and preparation method thereof |
| CN109772366A (en) * | 2019-03-18 | 2019-05-21 | 陕西科技大学 | A kind of preparation method of cuprous sulfide/vanadium trioxide as full PH elctro-catalyst |
| CN110227493A (en) * | 2019-07-05 | 2019-09-13 | 陕西科技大学 | The preparation method of one type round pie vanadium disulfide elctro-catalyst |
| CN110459745A (en) * | 2019-08-11 | 2019-11-15 | 五邑大学 | A kind of Ni3S2@VO2The preparation method of nanocomposite |
| CN114665078A (en) * | 2022-03-30 | 2022-06-24 | 安徽师范大学 | Lamellar self-assembly structure vanadium disulfide @ vanadium tetrasulfide nano material, preparation method thereof and rechargeable battery with excellent rate performance |
| CN115092961A (en) * | 2022-07-14 | 2022-09-23 | 贵州大学 | Preparation method and application of hydroxyl vanadium oxide with hollow spherical shell structure |
| CN115092961B (en) * | 2022-07-14 | 2023-12-22 | 贵州大学 | Preparation method and application of hollow spherical shell structured vanadium oxyhydroxide |
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