CN107381636A - A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application - Google Patents

A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application Download PDF

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CN107381636A
CN107381636A CN201710562517.3A CN201710562517A CN107381636A CN 107381636 A CN107381636 A CN 107381636A CN 201710562517 A CN201710562517 A CN 201710562517A CN 107381636 A CN107381636 A CN 107381636A
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cauliflower
nano
shaped
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solution
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黄剑锋
***
曹丽云
冯亮亮
李瑞梓
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Shaanxi University of Science and Technology
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The present invention relates to a kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application, will be first dissolved in the water after vanadium source and sulphur source uniformly mixing, wherein the mol ratio of vanadium and sulphur is 1:5.80~1:5.88, it is uniformly mixing to obtain solution A;The pH value of solution A is adjusted up to 2.4~2.8, obtains solution B;Solution B is subjected to hydro-thermal reaction, generation precipitation;Terminate after hydro-thermal reaction and take out reaction product after natural cooling, by washing and drying, obtain the vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four.The inventive method is prepared for nano-particles self assemble cauliflower-shaped VS first using a step low-temperature hydrothermal synthetic method4Powder, it is not necessary to add template, whole course of reaction is simple, readily available pure phase, VS prepared by the present invention4Powder has unique radial self-assembled structures, can be applied in lithium ion battery, Magnesium ion battery and photochemical catalyst is prepared.

Description

A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation Methods and applications
Technical field
The present invention relates to battery material field, and in particular to a kind of nano-particles self assemble three dimensional micron cauliflower-shaped four vulcanizes Vanadium powder body and its preparation method and application.
Background technology
Due to low cost and high efficiency of the sodium-ion battery in large scale energy storage system, current research persons are to it Research just gradually becoming extensive and going deep into [Pan H, Hu Y-S, Chen L.Room-temperature stationary sodium-ion batteries for large-scale electric energy storage.Energy& Environmental Science.2013;6:2338-60.].It is related in order to find suitable anode material of lithium-ion battery Explore a collection of compound to researcher's extension.In these negative materials, researchers are generally believed with high theoretical capacity Metal sulfide be it is a kind of have very much promising candidate, and their nanostructured is carried out regulation and control be it is a kind of very The important strategy for further improving its chemical property.However, research in recent years is concentrated mainly on and their low-dimensional is received Rice structure is regulated and controled, such as synthesizing nanocrystalline, nano particle, nano wire and nanometer sheet etc., and correlative study also indicates that When these low-dimensional nano structures are applied to sodium-ion battery, larger superiority can be shown.However, these low-dimensional nano junctions Structure is there is easy the problem of reuniting with easy efflorescence, and which greatly limits their further applying in sodium-ion battery.Therefore, In order to realize high specific surface area and excellent structural stability simultaneously, and then chemical property is further lifted, researcher opens Begin eye focusing on constructing for 3-D nano, structure, and also carried out related work.However, realize three-dimensional self assembly The controlledly synthesis of nanostructured is still a larger challenge.
As a kind of typical material in metal sulfide family, vanadic sulfide (including VS2、VS4And V5S8Deng) there is uniqueness Physical and chemical properties, it is considered to be a kind of high performance electrode material, and having attracted in energy storage field more and more Concern.In these vanadic sulfides, VS4The characteristic such as connect with high sulfur content, one-dimensional chain crystal structure and weak interchain. These characteristics can not only increase VS4Theoretical capacity, while electric charge and electronics can also be accelerated in VS4Biography in chain structure It is defeated.In addition, with regard to patronite (VS present in nature4) abundant reserves and its potential low cost, VS4In actual energy The application of source field of storage also has huge superiority.To sum up, there is S2 2-The VS of double sulphions4More researchers are attracted Interest.However, VS4The synthesis of pure phase needs accurately to control the local pressure of sulphur, and easily generates various non-ization Learn the vanadic sulfide interference phase of metering ratio.Along with the oxyphie characteristic of vanadium so that VS4Since 1970 by since reporting first, the phase Between on its synthesis and application report it is considerably less.In recent years, with the development of science and technology, synthetic technology also becomes increasingly Advanced, this makes VS4Start the visual field of slowly entering part researcher again, and there has also been some and successfully synthesized by hydro-thermal reaction VS4Report.However, in these hydro-thermal reactions, template include graphene, CNT, conducting polymer (polythiophene, Polypyrrole and polyaniline) and tetracarboxylic dianhydride etc. be to be added, they are for VS4Formation play very crucial effect. However, the addition of these templates makes whole VS4Preparation process become more sophisticated, and cost also becomes higher.Therefore, realize Three-dimensional self assembly VS4The controlledly synthesis of nanostructured, then explore their electrochemistry as anode material of lithium-ion battery Performance is very urgent.
The content of the invention
It is an object of the invention to overcome problems of the prior art, there is provided a kind of nano-particles self assemble three-dimensional is micro- Rice vanadic sulfide powder of cauliflower-shaped four and its preparation method and application, without template and the VS of pure phase can be generated4
To achieve these goals, the present invention adopts the following technical scheme that:
Comprise the following steps:
(1) will be first dissolved in the water after vanadium source and sulphur source uniformly mixing, wherein the mol ratio of vanadium and sulphur is 1:5.80~1: 5.88, it is uniformly mixing to obtain solution A;
(2) pH value of solution A is adjusted up to 2.4~2.8, obtains solution B;
(3) solution B is subjected to hydro-thermal reaction, generation precipitation;
(4) terminate after hydro-thermal reaction and take out reaction product after natural cooling, by washing and drying, obtain nanometer The vanadic sulfide powder of grain self assembled three-dimensional micron cauliflower-shaped four.
Further, vanadium source uses sodium metavanadate in step (1), and sulphur source uses thioacetamide.
Further, 10~30min of stirring in step (1).
Further, the concentration in vanadium source is 0.11~0.16mol/L in solution A.
Further, using 2.5~3.5mol/L hydrochloric acid solution regulation pH value in step (2).
Further, the temperature of hydro-thermal reaction is at 175~185 DEG C in step (3), and the time is in 23~25h.
Further, solution B carries out hydro-thermal reaction in hydrothermal reaction kettle in step (3), and packing ratio is 55~65%.
Further, washing is washed alternately 4~10 times using washing and alcohol in step (4), and mode of washing is filtering and washing Or centrifuge washing;Drying is 10~14h of drying under conditions of 60~80 DEG C.
One kind vulcanizes vanadium powder using nano-particles self assemble three dimensional micron cauliflower-shaped four made from preparation method as described above Body, the four vanadic sulfides powder are a diameter of 1~1.5um formed by the nano-particles self assemble that size is 40~60nm three-dimensionals Micron cauliflower-shaped structure.
The vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four as described above prepare lithium ion battery, magnesium from Application in sub- battery and photochemical catalyst.
Relative to prior art, the invention has the advantages that:
The inventive method is prepared for nano-particles self assemble cauliflower-shaped VS first using a step low-temperature hydrothermal synthetic method4Powder Body, and chemical property of this material as anode material of lithium-ion battery is reported first, specifically have the beneficial effect that:
(1) the inventive method overcomes tradition and forged because it using a step hydro-thermal reaction directly synthesizes final product The shortcomings that firing method temperature is high, there is low synthesis temperature, simple synthesis path, it is not necessary to large scale equipment and harsh reaction bar Part, yield is high, without post-processing.Further, since template need not be added, whole course of reaction is simple, readily available pure Phase, raw material is cheap and easy to get, and cost is low, environmentally friendly, can be adapted to mass produce;
(2) the inventive method causes its caused sulphur can be very due to introducing larger amount of sulphur source during the course of the reaction The oxygen in vanadium oxygen radical ion is replaced well.Meanwhile this method also have selected larger packing ratio so that course of reaction can produce Larger and uniform pressure.In addition, during reaction solution is configured, continuously stirring can ensure in whole mixed liquor Vanadium and sulphur are in the state of uniformity.The product that these prepare whole reaction is all relatively more equal in terms of crystal structure and pattern It is even, and purity and crystallinity are also higher;
(3) the inventive method reacts pH by adjusting, the H in solution+VS can be controlled4The growth of nucleus, is especially controlled VS4The differential growth of nucleus crystal face, so as to cause VS in final product4The characteristics of exposure crystal face and the feature of pattern.
Further, the inventive method adjusts pH by the hydrochloric acid of certain concentration and can made in reaction solution at sulphur and vanadium dropwise In specific state, this specific state may be considered a kind of specific precursors, and this will directly determine reaction production Species, purity and the form of thing.
VS prepared by the present invention4Powder has unique radial self-assembled structures, and this structure can effectively overcome it Reunion, efflorescence and expansion, and then can further improve the cyclical stability of such material certainly in charge and discharge process.This Invent the VS prepared4Powder is formed by substantial amounts of nanocone self assembly, the self-assembly of this extra small yardstick, plus small yardstick Cauliflower-shaped ball, larger specific surface area (13.53g/m can be shown2), this big specific surface area is easy to increase Electrolyte and VS4Contact between electrode material, so as to greatly promote its specific capacity.VS prepared by the inventive method4Homogeneous Chemical composition, high purity is high, the self-assembly of uniform pattern, especially nanoscale so that sodium ion easily enters reality Internal portion, more avtive spots can be then provided and participate in electrochemical reaction, the final specific capacity for improving material, reduce ion Transport resistance.
When by materials application of the present invention in anode material of lithium-ion battery, it can show high capacity, excellent Cyclical stability and high rate performance, VS of the present invention4The first charge-discharge capacity of powder can reach 268 and 319mAhg-1, first Coulombic efficiency has reached 84%, and after the 5th circle, coulombic efficiency can reach and maintain 99%.In 0.5Ag-1Electric current it is close Under degree, after the circle of circulation 200, its reversible capacity remains able to reach 192mAhg-1, capability retention reached 71%.In addition, And 5.0Ag 0.2,0.5,1.0,2.0-1Current density under, reversible capacity can reach 265,229,203,168 and 122mAhg-1.After above-mentioned high current density circulation is undergone, when current density returns to 0.2Ag-1When, its reversible capacity remains able to reach 236mAhg-1, recovery rate reached 89%.
Summary, VS of the present invention4Powder application equally can also when lithium/Magnesium ion battery and photocatalysis field Show excellent performance.
Brief description of the drawings
Fig. 1 is cauliflower-shaped VS prepared by the embodiment of the present invention 14X-ray diffraction (XRD) collection of illustrative plates of nano-powder;
Fig. 2 is cauliflower-shaped VS prepared by the embodiment of the present invention 14The low power ESEM (SEM) of nano-powder outer surface shines Piece.
Fig. 3 is cauliflower-shaped VS prepared by the embodiment of the present invention 14The high power ESEM (SEM) of nano-powder outer surface shines Piece.
Fig. 4 is cauliflower-shaped VS prepared by the embodiment of the present invention 14Low power ESEM (SEM) photo inside nano-powder.
Fig. 5 is cauliflower-shaped VS prepared by the embodiment of the present invention 14High power ESEM (SEM) photo inside nano-powder.
Fig. 6 is cauliflower-shaped VS prepared by the embodiment of the present invention 14Low power projection Electronic Speculum (TEM) photo of nano-powder.
Fig. 7 is cauliflower-shaped VS prepared by the embodiment of the present invention 14High power projection Electronic Speculum (TEM) photo of nano-powder.
Fig. 8 is cauliflower-shaped VS prepared by the embodiment of the present invention 14The HRTEM photos and SAED photos photo of nano-powder are (right Inferior horn).
Embodiment
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
A kind of nano-particles self assemble three dimensional micron cauliflower-shaped VS4Powder and preparation method thereof, comprise the following steps:
Step 1:Sodium metavanadate and thioacetamide material are weighed, 55~65mL will be dissolved in behind they uniformly mixing In ionized water, it is 1 to control the mol ratio of vanadium and sulphur:5.80~1:Solution A, inclined vanadium are obtained after 5.88,10~30min of magnetic agitation The concentration of sour sodium is 0.11~0.16mol/L.
Sulphur in the present invention needs excess, and excessive sulphur is for VS4Formation be very important.Because excessive sulphur one Aspect is easy to form larger sulphur difference in oxygen concentration with vanadium oxygen root, and this concentration difference will give VS4Formation larger concentration be provided moved Power, on the other hand excessive sulphur will produce more hydrogen sulfide gas during the course of the reaction, so as to be produced in the reactor of sealing Raw larger pressure, is also VS4Formation provide powerful power.
Step 2:2.5~3.5mol/L hydrochloric acid solution is added dropwise dropwise to solution A, until the pH value of solution A reaches 2.4 ~2.8, obtain solution B.During whole pH regulations, solution will be constantly in magnetic agitation state, and to adjust dropwise, i.e., Stir after the drop hydrochloric acid solution of addition one and do not change to pH value of solution, then add next drop hydrochloric acid, until the last pH value of solution reaches To 2.4~2.8.
Step 3:Solution B is transferred in hydro-thermal reaction liner, is placed in after installing outer kettle additional in homogeneous reaction instrument, controls water The packing ratio of thermal response is 55~65%, and 23~25h is reacted under the conditions of 175~185 DEG C of synthesis temperature.
Step 4:Terminate after hydro-thermal reaction and take out reaction product after natural cooling, successively with deionized water and anhydrous Ethanol carries out cross washing, to remove caused impurity in hydrothermal reaction process, is received wherein washing alcohol is washed after replacing 4~10 times Collection, and 10~14h is dried under conditions of 60~80 DEG C, you can obtain nano-particles self assemble three dimensional micron cauliflower-shaped VS4Powder Body.Mode of washing is filtering and washing or centrifuge washing, and collection mode is collected by suction or is collected by centrifugation.
The configuration of whole solution of the invention is all carried out under continuously stirring.VS produced by the present invention4 With larger specific surface area, reunion and the efflorescence certainly of nano particle can be alleviated well, can effectively lift VS4Electrification Learn performance.It is i.e. available by a step hydro-thermal meanwhile this method is simple to operate, and reaction temperature is low, reaction time is short, is made VS4Chemical constituent is homogeneous, and purity is high.
Embodiment 1
Step 1:Sodium metavanadate and thioacetamide material are weighed, 60mL deionizations will be dissolved in behind they uniformly mixing In water, it is 1 to control the mol ratio of vanadium and sulphur:Solution A is obtained after 5.84, magnetic agitation 30min, the concentration of sodium metavanadate is 0.137mol/L。
Step 2:3mol/L hydrochloric acid solution is added dropwise dropwise to solution A, until the pH value of solution A reaches 2.7, obtains molten Liquid B.During whole pH regulations, solution will be constantly in magnetic agitation state.
Step 3:Solution B is transferred in hydro-thermal reaction liner, is placed in after installing outer kettle additional in homogeneous reaction instrument, controls water The packing ratio of thermal response is 60%, reacts 24h under the conditions of 180 DEG C of synthesis temperature.
Step 4:Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing alcohol is washed alternately after 4~10 times Collect, and 12h is dried under conditions of 60 DEG C, you can obtain nano-particles self assemble three dimensional micron cauliflower-shaped VS4Powder.Washing Mode is filtering and washing, and collection mode is collected by suction.
From figure 1 it appears that all X-ray powder diffraction peaks can index be VS4Nano-powder, and almost do not have There is the appearance of other impurities peak, therefore embodiment 1 is the high-purity VS of synthesis4Nano-powder.In addition, by these diffraction maximum meters Calculate, we have obtained cauliflower-shaped VS4The average grain size of powder is 145nm.Meanwhile the interplanar distance of (110) crystal face can To reach 0.563nm, more than the 0.561nm corresponding to standard card, this can accommodate more Na+, capacity is improved, also can Enough accelerate Na+In the transmission of interlayer, then improve its high rate performance.
It is clear from figure 2 that the VS4The uniform cauliflower-shaped ball that powder is about 1~1.5um by diameter forms.
The powder appearance from Fig. 3 is, it is apparent that the cauliflower-shaped ball is by substantial amounts of irregular nano-particles self assemble Form, 40~60nm of size of nano particle.
The internal structure of the cauliflower ball crushed from Fig. 4 can be seen that the VS4The inside of cauliflower-shaped ball is by not advising largely Radially (radial) self assembly forms nanocone then.
From figure 5 it can be seen that the length of nanocone is about 100~150nm, and the nano particle of outer surface is nanometer The outer end of cone.
From fig. 6 it can be seen that the VS4Powder is made up of a diameter of 1~1.5um uniform cauliflower-shaped ball.
It can be seen from figure 7 that the cauliflower-shaped ball is formed by substantial amounts of irregular nano-particles self assemble, nano particle Size about 70~150nm.
As can be seen from Figure 8, the VS4Polycrystalline state, the VS is presented in powder4Nano particle exposure in self-assembled structures Mainly (- 224) and (- 204) crystal face, and the particle mainly shows polycrystalline state.And nanocone exposure is mainly (110) crystal face.
Embodiment 2
Step 1:Sodium metavanadate and thioacetamide material are weighed, 60mL deionizations will be dissolved in behind they uniformly mixing In water, it is 1 to control the mol ratio of vanadium and sulphur:Solution A is obtained after 5.80, magnetic agitation 10min, the concentration of sodium metavanadate is 0.11mol/L。
Step 2:2.5mol/L hydrochloric acid solution is added dropwise dropwise to solution A, until the pH value of solution A reaches 2.4, obtains Solution B.During whole pH regulations, solution will be constantly in magnetic agitation state.
Step 3:Solution B is transferred in hydro-thermal reaction liner, is placed in after installing outer kettle additional in homogeneous reaction instrument, controls water The packing ratio of thermal response is 55%, reacts 25h under the conditions of 175 DEG C of synthesis temperature.
Step 4:Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing alcohol, which is washed, alternately to be received after 4 times Collection, and dry 14h under conditions of 70 DEG C, you can obtain nano-particles self assemble three dimensional micron cauliflower-shaped VS4Powder.Washing side Formula is filtering and washing, and collection mode is collected by suction.
Embodiment 3
Step 1:Sodium metavanadate and thioacetamide material are weighed, 65mL deionizations will be dissolved in behind they uniformly mixing In water, it is 1 to control the mol ratio of vanadium and sulphur:Solution A is obtained after 5.88, magnetic agitation 20min, the concentration of sodium metavanadate is 0.16mol/L。
Step 2:3.5mol/L hydrochloric acid solution is added dropwise dropwise to solution A, until the pH value of solution A reaches 2.8, obtains Solution B.During whole pH regulations, solution will be constantly in magnetic agitation state.
Step 3:Solution B is transferred in hydro-thermal reaction liner, is placed in after installing outer kettle additional in homogeneous reaction instrument, controls water The packing ratio of thermal response is 65%, reacts 23h under the conditions of 185 DEG C of synthesis temperature.
Step 4:Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing alcohol is washed alternately after 4~10 times Collect, and 10h is dried under conditions of 80 DEG C, you can obtain nano-particles self assemble three dimensional micron cauliflower-shaped VS4Powder.Washing Mode is filtering and washing, and collection mode is collected by suction.
Embodiment 4
Step 1:Sodium metavanadate and thioacetamide material are weighed, 55mL deionizations will be dissolved in behind they uniformly mixing In water, it is 1 to control the mol ratio of vanadium and sulphur:Solution A is obtained after 5.85, magnetic agitation 25min, the concentration of sodium metavanadate is 0.15mol/L。
Step 2:3.2mol/L hydrochloric acid solution is added dropwise dropwise to solution A, until the pH value of solution A reaches 2.5, obtains Solution B.During whole pH regulations, solution will be constantly in magnetic agitation state.
Step 3:Solution B is transferred in hydro-thermal reaction liner, is placed in after installing outer kettle additional in homogeneous reaction instrument, controls water The packing ratio of thermal response is 60%, reacts 24.5h under the conditions of 182 DEG C of synthesis temperature.
Step 4:Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing alcohol is washed alternately after 4~10 times Collect, and 13h is dried under conditions of 75 DEG C, you can obtain nano-particles self assemble three dimensional micron cauliflower-shaped VS4Powder.Washing Mode is filtering and washing, and collection mode is collected by suction.
When by materials application of the present invention in anode material of lithium-ion battery, it can show high capacity, excellent Cyclical stability and high rate performance.Specifically, VS of the present invention4The first charge-discharge capacity of powder can reach 268 and 319mAhg-1, first coulombic efficiency reached 84%, after the 5th circle, coulombic efficiency can reach and maintain 99%.In 0.5Ag-1 Current density under, circulation 200 circle after, its reversible capacity remains able to reach 192mAhg-1, capability retention reached 71%. In addition, in 0.2,0.5,1.0,2.0 and 5.0Ag-1Current density under, reversible capacity can reach 265,229,203,168 Hes 122mAhg-1.After above-mentioned high current density circulation is undergone, when current density returns to 0.2Ag-1When, its reversible capacity is still 236mAhg can be reached-1, recovery rate reached 89%.
More nano particle self assembled three-dimensional micron cauliflower-shaped VS prepared by the present invention4Powder can be applied not only to sodium ion Battery, it is also applied to lithium/Magnesium ion battery and photocatalysis field.

Claims (10)

  1. A kind of 1. vanadic sulfide raw powder's production technology of nano-particles self assemble three dimensional micron cauliflower-shaped four, it is characterised in that:Including Following steps:
    (1) will be first dissolved in the water after vanadium source and sulphur source uniformly mixing, wherein the mol ratio of vanadium and sulphur is 1:5.80~1:5.88 It is uniformly mixing to obtain solution A;
    (2) pH value of solution A is adjusted up to 2.4~2.8, obtains solution B;
    (3) solution B is subjected to hydro-thermal reaction, generation precipitation;
    (4) terminate after hydro-thermal reaction and take out reaction product after natural cooling, by washing and drying, obtain nano particle certainly Assemble the vanadic sulfide powder of three dimensional micron cauliflower-shaped four.
  2. A kind of 2. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:Vanadium source uses sodium metavanadate in step (1), and sulphur source uses thioacetamide.
  3. A kind of 3. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:10~30min of stirring in step (1).
  4. A kind of 4. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:The concentration in vanadium source is 0.11~0.16mol/L in solution A.
  5. A kind of 5. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:Using 2.5~3.5mol/L hydrochloric acid solution regulation pH value in step (2).
  6. A kind of 6. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:The temperature of hydro-thermal reaction is at 175~185 DEG C in step (3), and the time is in 23~25h.
  7. A kind of 7. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:Solution B carries out hydro-thermal reaction in hydrothermal reaction kettle in step (3), and packing ratio is 55~65%.
  8. A kind of 8. preparation side of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four according to claim 1 Method, it is characterised in that:Washing is washed alternately 4~10 times using washing and alcohol in step (4), mode of washing be filtering and washing or from The heart washs;Drying is 10~14h of drying under conditions of 60~80 DEG C.
  9. 9. one kind utilizes the vanadic sulfide of nano-particles self assemble three dimensional micron cauliflower-shaped four made from preparation method described in claim 1 Powder, it is characterised in that:The four vanadic sulfides powder is a diameter of 1 formed by the nano-particles self assemble that size is 40~60nm ~1.5um three dimensional micron cauliflower-shaped structure.
  10. 10. the vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four as claimed in claim 9 is preparing lithium-ion electric Application in pond, Magnesium ion battery and photochemical catalyst.
CN201710562517.3A 2017-07-11 2017-07-11 A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application Pending CN107381636A (en)

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CN108316008A (en) * 2018-01-15 2018-07-24 华中科技大学 A kind of vanadic sulfide/vanadium carbide composite nano plate assembly, it is prepared and application
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
CN109264783A (en) * 2018-10-10 2019-01-25 陕西科技大学 A kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and the preparation method and application thereof
CN109534402A (en) * 2018-10-23 2019-03-29 北京航空航天大学 Chain structure transition metal polysulfide positive electrode for lithium-sulfur cell
CN109599560A (en) * 2018-12-11 2019-04-09 广东工业大学 Four vanadic sulfide anode material of lithium-ion batteries of one kind and preparation method thereof
CN109755553A (en) * 2019-03-20 2019-05-14 北京航空航天大学 A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system
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CN110571417A (en) * 2019-08-22 2019-12-13 齐鲁工业大学 Solvothermal preparation of VS4Polyaniline sodium ion battery cathode material
CN112490438A (en) * 2020-11-27 2021-03-12 青岛科技大学 Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof
CN112678870A (en) * 2020-12-28 2021-04-20 北京理工大学 Aluminum secondary battery and aluminum storage active material thereof
CN113413906A (en) * 2021-07-30 2021-09-21 陕西科技大学 Vanadium trisulfide/graphite phase carbon nitride photocatalyst and preparation method thereof
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CN109755553A (en) * 2019-03-20 2019-05-14 北京航空航天大学 A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system
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CN112490438A (en) * 2020-11-27 2021-03-12 青岛科技大学 Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof
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Application publication date: 20171124