CN109264783A - A kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and the preparation method and application thereof - Google Patents

A kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and the preparation method and application thereof Download PDF

Info

Publication number
CN109264783A
CN109264783A CN201811176050.XA CN201811176050A CN109264783A CN 109264783 A CN109264783 A CN 109264783A CN 201811176050 A CN201811176050 A CN 201811176050A CN 109264783 A CN109264783 A CN 109264783A
Authority
CN
China
Prior art keywords
hollow
nanobelt
solution
microballoon
dimensional
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811176050.XA
Other languages
Chinese (zh)
Other versions
CN109264783B (en
Inventor
黄剑锋
***
冯亮亮
曹丽云
何枢薇
石泓彬
马闯
王娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201811176050.XA priority Critical patent/CN109264783B/en
Publication of CN109264783A publication Critical patent/CN109264783A/en
Application granted granted Critical
Publication of CN109264783B publication Critical patent/CN109264783B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • 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
    • 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
    • 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
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • 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
    • 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
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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

A kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and the preparation method and application thereof prepares the hollow VS of polycrystal nanobelt self assembled three-dimensional by simple one step hydro thermal method4Microballoon, and entire reaction process Template-free method auxiliary.When above-mentioned product is applied to lithium/anode material of lithium-ion battery, excellent chemical property can be shown, and lesser powder phenomenon-tion is shown in charge and discharge process.The powder is made of the micron ball that diameter is 0.5~2 μm, micron ball has nanobelt with the three-dimensional hollow structure of canoe self assembly, the diameter of nanobelt is about 50~100nm and is polycrystalline structure, and the interplanar distance of (110) crystal face can reach 0.581nm.By the hollow VS of polycrystal nanobelt self assembled three-dimensional made of preparation method of the invention4Microballoon is applied in lithium/sodium-ion battery field, and unique architectural characteristic can make it show excellent chemical property.

Description

A kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and the preparation method and application thereof
Technical field
The present invention relates to a kind of VS4Nano-powder and the preparation method and application thereof, and in particular to a kind of polycrystal nanobelt from Assemble three-dimensional hollow VS4Microballoon and the preparation method and application thereof.
Background technique
Lithium/sodium-ion battery has many advantages, such as low cost and high efficiency, in the application of large scale energy storage system It is widely used in various electronic equipments and electric tool [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.].With deepening continuously for application, people To lithium/sodium-ion battery performance, more stringent requirements are proposed.As a very important part in lithium/sodium-ion battery, The low performance of negative electrode material limits further applying for they.In order to find performance more preferably negative electrode material, researcher is carried out A large amount of exploration.It has been reported that negative electrode material in, researchers generally believe the mineral VS with high theoretical capacity4It is A kind of very potential candidate, and its nanostructure is regulated and controled further improve its chemical property. However, the pure phase VS reported at present4Poor chemical property is shown, and the problem of there is easy dusting, this is significantly Limit its application.Meanwhile the VS reported at present4Nanometer rods dispersed structure and self assembly solid construction are mostly shown.
Summary of the invention
The purpose of the present invention is to provide a kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and preparation method thereof with Using preparing the hollow VS of polycrystal nanobelt self assembled three-dimensional by simple one step hydro thermal method4Microballoon, and entirely reacted Journey Template-free method auxiliary.When above-mentioned product is applied to lithium/anode material of lithium-ion battery, excellent electrification can be shown Performance is learned, and shows lesser powder phenomenon-tion in charge and discharge process.
In order to achieve the above objectives, of the invention the preparation method is as follows:
Step 1: taking 0.9~1.1g sodium metavanadate and 3.5~3.7g thioacetamide at the same be added to 58~62ml go from Magnetic agitation or ultrasonic disperse obtain half clear solution A in sub- water；
Step 2: the sodium hydroxide solution B of 2.8~3.2mol/L of configuration, solution B, which is added in solution A, reaches its pH To 10.1~10.3, solution C is obtained；
Solution C: being poured into sealing after reacting in liner by step 3, is then placed on liner homogeneously loaded on fixed in outer kettle It reacts in instrument, then under the speed conditions of 5~10r/min, 17.5~18.5h is reacted at 95~105 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes the product cooled down after reaction Out, product is collected after water, alcohol alternately clean；
Step 5: the product of collection being placed in the cold well of freeze drier and freezed, then by the product after freezing Be placed in pallet, cover seal closure, be evacuated down to 10~20Pa, collected after dry 12~18h product to get polycrystal nanobelt from Assemble three-dimensional hollow VS4Microballoon.
Step 1) the magnetic agitation or ultrasonic disperse carry out at room temperature, and the revolving speed of magnetic agitation is 400~600r/ min。
The solvent of sodium hydroxide solution is deionized water in the step 2), and sodium hydroxide solution B is in continuous magnetic force It under conditions of stirring, is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution is added, stirring is until pH value of solution reaches steady It is fixed, it is constantly repeated with this, until pH value of solution is adjusted to 10.1~10.3.
The packing ratio that the step 3) solution C pours into reaction liner is 58~62%.
Step 4) the water, alcohol alternately clean each 2~5 times, and product is collected by way of filtering or being centrifuged.
The freezing conditions of the step 5) are as follows: -60~-40 DEG C, freeze 2~5 hours.
Step 5) the product is sealed it before being put into pallet and being dried, with preservative film, and to preservative film It carries out pricking hole processing.
By the hollow VS of polycrystal nanobelt self assembled three-dimensional made of preparation method of the invention4Microballoon, the powder are by straight The micron ball that diameter is 0.5~2 μm forms, and micron ball has nanobelt with the three-dimensional hollow structure of canoe self assembly, nanometer The diameter of band is about 50~100nm and is polycrystalline structure, and the interplanar distance of (110) crystal face can reach 0.581nm.
By the hollow VS of polycrystal nanobelt self assembled three-dimensional made of preparation method of the invention4Microballoon apply lithium/sodium from Sub- field of batteries, unique architectural characteristic can make it show excellent chemical property.
Specifically have the beneficial effect that:
(1) final product is directly synthesized using a step hydro-thermal reaction due to the present invention, thus there is low synthesis temperature Degree, 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.
(3) present invention is added without any template, is reacted easily-controllable, is not necessarily to post-processing, environmentally friendly, can be suitble to big Large-scale production；
(4) product chemistry composition prepared by the present invention is uniform, with high purity, pattern is uniform, negative as lithium/sodium-ion battery Excellent performance can be shown when the material of pole；
(5) present invention passes through Collaborative Control vanadium source, the concentration and proportion, reacting solution pH value, reaction temperature, reaction of sulphur source The parameters such as time, reaction-filling ratio and drying mode, realize the hollow VS of polycrystal nanobelt self assembled three-dimensional4The controllable conjunction of microballoon At control precision with higher.Particularly, the structure of two parameters on product of pH value in reaction and reaction temperature has decisive Influence.
(6) under excessively high and too low pH value condition, all it is unable to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon knot Structure.
(7) under the conditions of excessively high and too low reaction temperature, also it is unable to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4It is micro- Spherical structure.
(8) concentration that the sodium hydroxide solution of pH value of solution is adjusted in the present invention must be strictly controlled in 2.8~3.2mol/L, Excessively high concentration is unfavorable for the formation of uniform hollow structure, and too low concentration can seriously affect reaction-filling ratio, equally also not Conducive to the formation of hollow structure.
(9) product prepared by the present invention has unique self-assembled structures, wherein in self assembly construct between nanobelt Unique physics confinement effect and the unique volume buffering effect of hollow structure, can effectively inhibit charge and discharge process VS4Knot Structure collapses, so as to promote the cyclical stability of material.
(10) there is product prepared by the present invention unique hollow structure it to be made to show lesser mass density, thus It can be made to show high specific capacity.
(11) VS in product prepared by the present invention4Nanobelt has unique polycrystalline structure, can be in charge and discharge process Li+/Na+Storage more active sites are provided, also can be Li+/Na+Transmission more infiltration lanes are provided, so as to It is enough set to show higher capacity and rate capability.
(12)VS4The big chain pitch structure of nanobelt, can not only store more Li+/Na+, additionally it is possible to it is Li+/Na+? The disengaging of interchain provides more smoothly channel, can finally cooperate with and improve VS4Capacity and high rate performance.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram that the embodiment of the present invention 1 prepares product.Diffraction maximum can be very as can be observed from Figure Matching criteria card PDF#72-1294 well illustrates that the product of synthesis is monoclinic phase VS4.It is worth noting that, entire diffraction pattern Spectrum has more burr, it is meant that lower crystallinity.
Fig. 2 is the low power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.It can be seen from the figure that products therefrom is It is made of the three-dimensional self assembly micron ball that diameter is about 0.5~2 μm.
Fig. 3 is the high power scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares product.It can be seen from the figure that micron ball has Nanobelt is about 50~100nm with the three-dimensional structure of canoe self assembly, the diameter of nanobelt.
Fig. 4 is the transmission electron microscope picture of product prepared by the embodiment of the present invention 1.Products therefrom VS can be determined from figure4It is micro- Rice ball has hollow structure.
Fig. 5 is that the embodiment of the present invention 1 prepares VS4The selective electron diffraction figure of nanobelt.Being able to observe that from figure has The diffraction ring of different radii shows that nanobelt is polycrystalline structure.
Specific embodiment
Embodiment 1:
Step 1: 1g sodium metavanadate and 3.6g thioacetamide are taken while being added in 60ml deionized water, at room temperature Half clear solution A is obtained with 500r/min magnetic agitation；
Step 2: configuring the sodium hydroxide solution B of 3mol/L with deionized water, under conditions of continuous magnetic agitation, by It is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution B is added, stirring reaches stable up to pH value of solution, it is constantly repeated with this, Until pH value of solution is adjusted to 10.2, solution C is obtained；
Step 3: sealing after pouring into solution C in reaction liner by 60% packing ratio, then by liner loaded in outer kettle Fixation is placed in homogeneous reaction instrument, then under the speed conditions of 10r/min, reacts 18h at 100 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes the product cooled down after reaction Out, replace each cleaning 3 times by water, alcohol and collect product in a manner of suction filtration；
Step 5: the product of collection being placed in the cold well of -50 DEG C of freeze drier and freezed 3 hours, then will freezing Product afterwards is placed in pallet, is sealed with preservative film to it, and carries out pricking hole processing to preservative film, is covered seal closure, is taken out Vacuum collects product after drying 12h to 16Pa to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon.
It can be observed that diffraction maximum can be well matched with standard card PDF#72-1294 from Fig. 1, illustrate the production of synthesis Object is monoclinic phase VS4.It is worth noting that, entire diffracting spectrum has more burr, it is meant that lower crystallinity.
From figure 2 it can be seen that products therefrom is made of the three-dimensional self assembly micron ball that diameter is about 0.5~2 μm.
From figure 3, it can be seen that micron ball has nanobelt with the three-dimensional structure of canoe self assembly, nanobelt it is straight Diameter is about 50~100nm.
Products therefrom VS can be determined from Fig. 44Micron ball has hollow structure.
It is able to observe that the diffraction ring with different radii from Fig. 5, shows that nanobelt is polycrystalline structure.
Embodiment 2:
Step 1: 1.1g sodium metavanadate and 3.7g thioacetamide are taken while being added in 58ml deionized water, in room temperature Under half clear solution A obtained with 400r/min magnetic agitation；
Step 2: configuring the sodium hydroxide solution B of 2.8mol/L with deionized water, under conditions of continuous magnetic agitation, It is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution B is added, stirring is until pH value of solution reaches stable, with this continuous weight It is multiple, until pH value of solution is adjusted to 10.1, obtain solution C；
Step 3: sealing after pouring into solution C in reaction liner by 58% packing ratio, then by liner loaded in outer kettle Fixation is placed in homogeneous reaction instrument, then under the speed conditions of 5r/min, reacts 18.5h at 95 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes the product cooled down after reaction Out, product is collected in eccentric fashion by water, each cleaning of alcohol alternating 2 times；
Step 5: the product of collection being placed in the cold well of -60 DEG C of freeze drier and freezed 5 hours, then will freezing Product afterwards is placed in pallet, is sealed with preservative film to it, and carries out pricking hole processing to preservative film, is covered seal closure, is taken out Vacuum collects product after drying 18h to 10Pa to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon.
Embodiment 3:
Step 1: 0.9g sodium metavanadate and 3.5g thioacetamide are taken while being added in 62ml deionized water, in room temperature Under half clear solution A obtained with 600r/min magnetic agitation；
Step 2: configuring the sodium hydroxide solution B of 3.2mol/L with deionized water, under conditions of continuous magnetic agitation, It is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution B is added, stirring is until pH value of solution reaches stable, with this continuous weight It is multiple, until pH value of solution is adjusted to 10.3, obtain solution C；
Step 3: sealing after pouring into solution C in reaction liner by 61% packing ratio, then by liner loaded in outer kettle Fixation is placed in homogeneous reaction instrument, then under the speed conditions of 8r/min, reacts 17.5h at 105 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes the product cooled down after reaction Out, replace each cleaning 5 times by water, alcohol and collect product in a manner of suction filtration；
Step 5: the product of collection being placed in the cold well of -40 DEG C of freeze drier and freezed 2 hours, then will freezing Product afterwards is placed in pallet, is sealed with preservative film to it, and carries out pricking hole processing to preservative film, is covered seal closure, is taken out Vacuum collects product after drying 12h to 20Pa to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon.
Embodiment 4:
Step 1: 1.05g sodium metavanadate and 3.7g thioacetamide are taken while being added in 59ml deionized water, in room temperature Lower ultrasonic disperse obtains half clear solution A；
Step 2: configuring the sodium hydroxide solution B of 2.9mol/L with deionized water, under conditions of continuous magnetic agitation, It is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution B is added, stirring is until pH value of solution reaches stable, with this continuous weight It is multiple, until pH value of solution is adjusted to 10.2, obtain solution C；
Step 3: sealing after pouring into solution C in reaction liner by 59% packing ratio, then by liner loaded in outer kettle Fixation is placed in homogeneous reaction instrument, then under the speed conditions of 9r/min, reacts 18h at 98 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes the product cooled down after reaction Out, product is collected in eccentric fashion by water, each cleaning of alcohol alternating 4 times；
Step 5: the product of collection being placed in the cold well of -55 DEG C of freeze drier and freezed 3 hours, then will freezing Product afterwards is placed in pallet, is sealed with preservative film to it, and carries out pricking hole processing to preservative film, is covered seal closure, is taken out Vacuum collects product after drying 16h to 13Pa to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon.
Embodiment 5:
Step 1: 0.95g sodium metavanadate and 3.6g thioacetamide are taken while being added in 61ml deionized water, in room temperature Lower ultrasonic disperse obtains half clear solution A；
Step 2: configuring the sodium hydroxide solution B of 3.1mol/L with deionized water, under conditions of continuous magnetic agitation, It is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution B is added, stirring is until pH value of solution reaches stable, with this continuous weight It is multiple, until pH value of solution is adjusted to 10.1, obtain solution C；
Step 3: sealing after pouring into solution C in reaction liner by 62% packing ratio, then by liner loaded in outer kettle Fixation is placed in homogeneous reaction instrument, then under the speed conditions of 7r/min, reacts 18h at 103 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes the product cooled down after reaction Out, replace each cleaning 3 times by water, alcohol and collect product in a manner of suction filtration；
Step 5: the product of collection being placed in the cold well of -45 DEG C of freeze drier and freezed 4 hours, then will freezing Product afterwards is placed in pallet, is sealed with preservative film to it, and carries out pricking hole processing to preservative film, is covered seal closure, is taken out Vacuum collects product after drying 15h to 18Pa to get the hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon.

Claims (9)

1. a kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4The preparation method of microballoon, it is characterised in that:
Step 1: 0.9~1.1g sodium metavanadate and 3.5~3.7g thioacetamide are taken while being added to 58~62ml deionized water Middle magnetic agitation or ultrasonic disperse obtain half clear solution A；
Step 2: the sodium hydroxide solution B of 2.8~3.2mol/L of configuration, solution B, which is added in solution A, reaches its pH 10.1~10.3, obtain solution C；
Step 3: liner is then placed on homogeneous reaction loaded on fixation in outer kettle by sealing after solution C is poured into reaction liner In instrument, then under the speed conditions of 5~10r/min, 17.5~18.5h is reacted at 95~105 DEG C；
Step 4: hydro-thermal reaction terminates, and reaction kettle is naturally cooled to room temperature, then takes out the product cooled down after reaction, warp It crosses after water, alcohol alternately clean and collects product；
Step 5: the product of collection is placed in the cold well of freeze drier and is freezed, be 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 polycrystal nanobelt self assembly Three-dimensional hollow VS4Microballoon.
2. the hollow VS of polycrystal nanobelt self assembled three-dimensional according to claim 14The preparation method of microballoon, it is characterised in that: Step 1) the magnetic agitation or ultrasonic disperse carry out at room temperature, and the revolving speed of magnetic agitation is 400~600r/min.
3. the hollow VS of polycrystal nanobelt self assembled three-dimensional according to claim 14The preparation method of microballoon, it is characterised in that: The solvent of sodium hydroxide solution is deionized water in the step 2), and sodium hydroxide solution B is the item in continuous magnetic agitation It under part, is added dropwise in solution A, that is, after 1 drop sodium hydroxide solution is added, stirring is until pH value of solution reaches stable, not with this It is disconnected to repeat, until pH value of solution is adjusted to 10.1~10.3.
4. a kind of hollow VS of polycrystal nanobelt self assembled three-dimensional according to claim 14The preparation method of microballoon, feature Be: the packing ratio that the step 3) solution C pours into reaction liner is 58~62%.
5. the hollow VS of polycrystal nanobelt self assembled three-dimensional according to claim 14The preparation method of microballoon, it is characterised in that: Step 4) the water, alcohol alternately clean each 2~5 times, and product is collected by way of filtering or being centrifuged.
6. the hollow VS of polycrystal nanobelt self assembled three-dimensional according to claim 14The preparation method of microballoon, it is characterised in that: The freezing conditions of the step 5) are as follows: -60~-40 DEG C, freeze 2~5 hours.
7. the hollow VS of polycrystal nanobelt self assembled three-dimensional according to claim 14The preparation method of microballoon, it is characterised in that: Step 5) the product is sealed it before being put into pallet and being dried, with preservative film, and carries out bundle hole to preservative film Processing.
8. the hollow VS of polycrystal nanobelt self assembled three-dimensional made of a kind of preparation method as described in claim 14Microballoon, it is special Sign is: the powder is made of the micron ball that diameter is 0.5~2 μm, and micron ball has nanobelt with canoe self assembly Three-dimensional hollow structure, the diameter of nanobelt is about 50~100nm and for polycrystalline structure, and the interplanar distance of (110) crystal face can Reach 0.581nm.
9. the hollow VS of polycrystal nanobelt self assembled three-dimensional made of a kind of preparation method as described in claim 14Microballoon is applied Lithium/sodium-ion battery field, unique architectural characteristic can make it show excellent chemical property.
CN201811176050.XA 2018-10-10 2018-10-10 Polycrystal nanobelt self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof Active CN109264783B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811176050.XA CN109264783B (en) 2018-10-10 2018-10-10 Polycrystal nanobelt self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811176050.XA CN109264783B (en) 2018-10-10 2018-10-10 Polycrystal nanobelt self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109264783A true CN109264783A (en) 2019-01-25
CN109264783B CN109264783B (en) 2020-07-14

Family

ID=65196068

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811176050.XA Active CN109264783B (en) 2018-10-10 2018-10-10 Polycrystal nanobelt self-assembly three-dimensional hollow VS4Microsphere and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109264783B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888223A (en) * 2019-02-26 2019-06-14 陕西科技大学 A kind of preparation method and application of four vanadic sulfides@redox graphene composite granule
CN109904422A (en) * 2019-02-26 2019-06-18 陕西科技大学 A kind of preparation method and application of four vanadic sulfides@Super P composite granule
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105923652A (en) * 2016-04-29 2016-09-07 陕西科技大学 Multilevel-structured VS4 nano-powder, and preparation method and application thereof
CN106960955A (en) * 2017-05-31 2017-07-18 中南大学 Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof
CN107381636A (en) * 2017-07-11 2017-11-24 陕西科技大学 A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application
CN108598432A (en) * 2018-05-02 2018-09-28 电子科技大学 A kind of preparation method of four vanadic sulfides/graphene composite material for sodium-ion battery electrode

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105923652A (en) * 2016-04-29 2016-09-07 陕西科技大学 Multilevel-structured VS4 nano-powder, and preparation method and application thereof
CN106960955A (en) * 2017-05-31 2017-07-18 中南大学 Ternary cathode material of lithium ion battery of vanadium sulfide cladding and preparation method thereof
CN107381636A (en) * 2017-07-11 2017-11-24 陕西科技大学 A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application
CN108598432A (en) * 2018-05-02 2018-09-28 电子科技大学 A kind of preparation method of four vanadic sulfides/graphene composite material for sodium-ion battery electrode

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109888223A (en) * 2019-02-26 2019-06-14 陕西科技大学 A kind of preparation method and application of four vanadic sulfides@redox graphene composite granule
CN109904422A (en) * 2019-02-26 2019-06-18 陕西科技大学 A kind of preparation method and application of four vanadic sulfides@Super P composite granule
CN109888223B (en) * 2019-02-26 2021-08-10 陕西科技大学 Preparation method and application of vanadium tetrasulfide @ reduced graphene oxide composite powder
CN109904422B (en) * 2019-02-26 2022-05-20 陕西科技大学 Preparation method and application of vanadium tetrasulfide @ Super P composite powder
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

Also Published As

Publication number Publication date
CN109264783B (en) 2020-07-14

Similar Documents

Publication Publication Date Title
Deng et al. First exploration of ultrafine Na7V3 (P2O7) 4 as a high-potential cathode material for sodium-ion battery
CN107840368B (en) A kind of nanometer sheet self assembly sub-micrometer flower-shape M-phase vanadium dioxide powder and preparation method thereof
CN107381636A (en) A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application
CN109264783A (en) A kind of hollow VS of polycrystal nanobelt self assembled three-dimensional4Microballoon and the preparation method and application thereof
CN107221646B (en) A kind of vanadium disulfide nanometer sheet and its preparation method and application of hydroxide vanadyl cladding
CN105098151A (en) Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof
CN108126712A (en) A kind of VOOH/VS4Micron composite granule and preparation method and application
CN109449402A (en) A kind of nano carbon microsphere supports preparation and its application method of MXene composite material
CN108423711B (en) Tetragonal phase NaV2O5·H2O nano flaky powder and preparation method and application thereof
CN106450204B (en) A kind of high circulation performance SnS2/TiO2The preparation method of anode material of lithium-ion battery
Lei et al. Template-free synthesis of hollow core–shell MoO2 microspheres with high lithium-ion storage capacity
CN109748319B (en) Preparation method and application of vanadium tetrasulfide @ carbon nanotube composite powder
CN103991899A (en) Preparation method of porous flowerlike stannic oxide micro-nano structure
CN108585042A (en) A kind of extra small flower-shaped VS of nanometer sheet self assembly2Powder and preparation method thereof
CN107902697A (en) A kind of nanometer sheet self assembled three-dimensional VS of (001) orientation2Micron bar and preparation method thereof
CN109888223A (en) A kind of preparation method and application of four vanadic sulfides@redox graphene composite granule
CN108110246A (en) A kind of extra small VS4/ Super P composite nano-powders and preparation method and application
CN102544457B (en) Method for preparing graphene oxide-iron sesquioxide nanotube composite material by using in-situ method
Yang et al. Synthesis of flower-like nickel oxide/nickel silicate nanocomposites and their enhanced electrochemical performance as anode materials for lithium batteries
CN109935819A (en) A kind of preparation method of the negative electrode material for lithium ion battery
CN103560237A (en) Nanometer iron-lithium oxide composite negative electrode material and preparation method thereof
CN101764217A (en) Method for preparing nano-scale lithium iron phosphate
CN108793251A (en) A kind of rodlike VS of thin slice self assembly micron2Nano-powder and preparation method thereof
Liu et al. Structure and electrochemical performance of LiV3O8 synthesized by solid-state routine with quenching in freezing atmosphere
CN106374090A (en) Preparation method of core-shell structured carbon coated SnS2 lithium ion battery negative electrode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant