CN105923652A - Multilevel-structured VS4 nano-powder, and preparation method and application thereof - Google Patents
Multilevel-structured VS4 nano-powder, and preparation method and application thereof Download PDFInfo
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- 239000011858 nanopowder Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 24
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- 239000011593 sulfur Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 241000186216 Corynebacterium Species 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 11
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NGTSQWJVGHUNSS-UHFFFAOYSA-N bis(sulfanylidene)vanadium Chemical compound S=[V]=S NGTSQWJVGHUNSS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/23—
-
- B01J35/39—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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 a multilevel-structured VS4 nano-powder, and a preparation method and an application thereof. According to the invention, a vanadium source solution and a sulfur source solution are mixed under stirring, wherein the molar ratio of vanadium to sulfur is controlled at 1:1-1:2, such that a mixed liquid is obtained; the mixed liquid is subjected to a hydrothermal reaction; when the reaction is finished, cooling, washing, collecting and drying are carried out, such that the multilevel-structured VS4 nano-powder is obtained. The process is simple and is easy to control. The prepared VS4 nano-powder has uniform chemical composition and relatively high purity. The nano-powder shows excellent electrochemical performance when used as a lithium/sodium ion battery electrode material. Also, the method overcomes a defect of high temperature of a traditional calcination method, and does not need large equipment and harsh reaction conditions. The raw materials are cheap and are easy to obtain; cost is low; yield is high; no post treatment is needed; and the method is environment-friendly. The method is suitable for large-scale production.
Description
[technical field]
The present invention relates to the preparation method of a kind of four vanadic sulfide nano materials, be specifically related to a kind of multilevel hierarchy VS4Nano-powder and
Preparation method and application.
[background technology]
Lithium ion battery is widely used in just owing to having the advantages such as running voltage is high, capacity is high, self discharge is little and has extended cycle life
Take formula electronic market.But, the lithium resource in the whole world will be unable to effectively to meet the great demand of power lithium-ion battery [Tarascon J M,
Armand M.Issues and challenges facing rechargeable lithium batteries[J].Nature,2001,414(6861):
359-367].Sodium-ion battery owing to having the feature such as aboundresources, with low cost, environmental friendliness it is considered to be substitute lithium ion
Battery as electric powered motor power supply of future generation and the ideal chose of the extensive supporting power supply of energy-accumulating power station, therefore seek high power capacity and
The storage sodium electrode material of excellent cycling performance has become study hotspot [the Slater M D, Kim D, Lee E, et al. in current battery field
Sodium‐Ion Batteries[J].Advanced Functional Materials,2013,23(8):947-958]。。
At present, the research of anode material of lithium-ion battery is concentrated mainly on hard carbon/soft carbon, alloy material, compound and Organic substance
Material etc..The transient metal sulfides such as molybdenum, tungsten and vanadium are the comparatively ideal lithium ion of analogy and anode material of lithium-ion batteries, because
This kind of sulfide typically has layer structure, and their interlamellar spacing is the biggest, with in lithium and sodium electrochemical reaction process, lithium from
Son and sodium ion can be embedded into layer structure.And this kind of sulfide another one important feature is to there is Van der Waals force between layer gap, it
The embedded space of lithium ion or sodium ion can be provided.When lithium ion or sodium ion generation insertion reaction, a complete charging
In reaction generating process, existing lithium ion or sodium ion are by being diffused into lamellar spacing storage lithium (sodium), and same also generation metal ion is also
Originally it was lower valency storage lithium (sodium).The most nearest grind to make internal disorder or usurp show, transition metal dichalcogenide is combined by the material with carbon element with high connductivity,
Form MoS2、WS2And VS2The composite such as carbon fiber and Graphene show fabulous storage lithium or storage sodium performance [Zhai Baihua.
The synthesis of sulfide composite and storage lithium (sodium) performance study [D] thereof. Hunan University, 2014].
But grinding of molybdenum sulfide and tungsten sulfide it is concentrated mainly on as the report of anode material of lithium-ion battery about transient metal sulfide
Study carefully.Also being concentrated mainly on vanadium disulfide about reporting for work of vanadic sulfide, many researcheres report to be prepared by hydro-thermal method has nanometer
Sheet, the vanadium disulfide of nanometer flower structure.Owing to the synthesis condition of four vanadic sulfides is harsh, reaction is difficult to control to, result in and it is ground
Study carefully progress the most slowly always.The most rare as the report of lithium/sodium ion battery electrode material about it.
[summary of the invention]
It is an object of the invention to provide a kind of multilevel hierarchy VS4Nano-powder and its preparation method and application, it is simple to operate, logical
Cross that a step hydro-thermal is i.e. available and reaction temperature is low, reaction time is short, the VS prepared4Chemical constituent is homogeneous, and purity is high.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of multilevel hierarchy VS4The preparation method of nano-powder, first under agitation mixes vanadium source solution and sulfur source solution, controls vanadium
Being 1:1～1:2 with the mol ratio of sulfur, obtain mixed liquor, the concentration in vanadium source is 0.06～0.6mol/L；Then mixed liquor is carried out hydro-thermal
Reaction, after reaction terminates, cooling, wash, collect, dry, i.e. can get multilevel hierarchy VS4Nano-powder；Described hydro-thermal is anti-
The temperature answered is 160～200 DEG C, and the time is 12～36h.
Further, the packing ratio of described hydro-thermal reaction is 40～80%.
Further, described mode of washing is filtering and washing or centrifuge washing, and collection mode is collected by suction or centrifugal collection.
Further, after hydro-thermal reaction completes, reacted solution is carried out sucking filtration, successively carries out with deionized water and dehydrated alcohol
Washing, to remove the impurity produced in hydrothermal reaction process.
Further, described dry temperature is 60～120 DEG C, and the time is 6～24h.
Further, described alr mode is magnetic agitation or ultrasonic disperse.
Further, described vanadium source is the one in sodium metavanadate, vanadic acid sodium, ammonium metavanadate, vanadic anhydride and potassium metavanadate
Or it is several.
Further, one or more during described sulfur source is thioacetamide, sodium oiethyl dithiocarbamate and sulfur simple substance.
A kind of multilevel hierarchy VS4Nano-powder, this multilevel hierarchy VS4Nano-powder is for having hollow corynebacterium VS4And it is carried on short
Rod be wound in spherical on, wherein, a diameter of 50nm of hollow stub, a length of 200nm.One is prepared by said method
Multilevel hierarchy VS4The application of nano-powder, this multilevel hierarchy VS4Application of nanopowder is urged in sodium/lithium/Magnesium ion battery and light
Change field.
Relative to prior art, the present invention at least has the advantages that
The present invention uses low-temperature hydrothermal synthetic method to be prepared for VS4Nano-powder, the method overcomes high the lacking of conventional calcination method temperature
Point, and need not main equipment and harsh reaction condition, it is not necessary to morphology control agent, cheaper starting materials is easy to get, low cost, and productivity is high,
Process without the later stage, environmentally friendly, large-scale production can be suitable for.Meanwhile, the method technique is simple and easy to control, the VS of preparation4
Nano-powder chemical composition is homogeneous, and purity and crystallinity are the highest.
Additionally, the VS prepared by the method4Nano-powder shows hollow corynebacterium VS4It is carried on stub and is wound around spherical VS4
On multilevel hierarchy.This multilevel hierarchy VS4Application of nanopowder in sodium/lithium/Magnesium ion battery and photocatalysis field, its as lithium/
The chemical property of excellence is shown during sodium ion battery electrode material.
[accompanying drawing explanation]
Fig. 1 is the VS of the embodiment of the present invention 1 preparation4X-ray diffraction (XRD) collection of illustrative plates of nano-powder；
Fig. 2 and Fig. 3 is the VS of the embodiment of the present invention 1 preparation4Scanning electron microscope (SEM) photo of nano-powder.
[detailed description of the invention]
Below in conjunction with the accompanying drawings and the present invention is described in further detail by embodiment.
A kind of multilevel hierarchy VS4The preparation method of nano-powder, comprises the following steps:
Step one: weigh vanadium source and sulfur source material, be dissolved in 40～80mL deionized waters in vanadium source and sulfur source material, controls vanadium
Being 1:1～1:2 with the mol ratio of sulfur, obtain solution A after magnetic agitation or ultrasonic disperse 10～60min, the concentration in vanadium source is
0.06～0.6mol/L.Vanadium source is the one in sodium metavanadate, vanadic acid sodium, ammonium metavanadate, vanadic anhydride and potassium metavanadate or several
Kind.Sulfur source is one or more in thioacetamide, sodium oiethyl dithiocarbamate and sulfur simple substance.
Step 2: solution A transferred in hydro-thermal reaction liner, installs outer still additional and is placed in homogeneous reaction instrument, controls hydro-thermal anti-
The packing ratio answered is 40～80%, reacts 12～36h under the conditions of the synthesis temperature of 160～200 DEG C.
Step 3: until hydro-thermal reaction terminate and natural cooling after by product take out, wash 2～5 times, alcohol wash 2～5 times after collection,
And under conditions of 60～120 DEG C, dry 6～24h, i.e. can get multilevel hierarchy VS4Nano-powder.Mode of washing is filtering and washing
Or centrifuge washing, collection mode is collected by suction or centrifugal collection.
The VS prepared by said method4Nano material has hollow corynebacterium VS4It is carried on stub and is wound in spherical VS4On many
Level structure, wherein the diameter of hollow stub is about 50nm, and length is about 200nm.This multilevel hierarchy VS4Application of nanopowder in
Sodium/lithium/Magnesium ion battery and photocatalysis field.Especially when it is applied to sodium-ion battery, show the electrochemistry of excellence
Performance.
Embodiment 1
Step one: weigh sodium metavanadate and thioacetamide, be dissolved in 60mL deionized water, the mol ratio controlling vanadium and sulfur is
1:1, obtains solution A after magnetic agitation 60min, the concentration in vanadium source is 0.06mol/L.
Step 2: solution A transferred in hydro-thermal reaction liner, installs outer still additional and is placed in homogeneous reaction instrument, controls hydro-thermal anti-
The packing ratio answered is 60%, reacts 24h under the conditions of the synthesis temperature of 180 DEG C.
Step 3: until hydro-thermal reaction terminate and natural cooling after by product take out, wash 3 times, alcohol wash 3 times after collection, and
Under conditions of 60 DEG C, dry 12h, i.e. can get multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is filtering and washing, receives
Mode set is collected by suction.
From figure 1 it appears that all of X-ray powder diffraction peak can index be all VS4Nano-powder, and almost without other
Impurity peaks occurs, therefore embodiment 1 is high-purity VS of synthesis4Nano-powder.
Can be clearly seen that from Fig. 2-3 diameter is about 50nm, length is about 200nm corynebacterium VS4It is carried on stub to be wound around
Glomeration VS4On multilevel hierarchy.
Embodiment 2
Step one: weigh sodium metavanadate and thioacetamide, be dissolved in 40mL deionized water, the mol ratio controlling vanadium and sulfur is
1:1.5, obtains solution A after ultrasonic disperse 10min, the concentration in vanadium source is 0.1mol/L.
Step 2: solution A transferred in hydro-thermal reaction liner, installs outer still additional and is placed in homogeneous reaction instrument, controls hydro-thermal anti-
The packing ratio answered is 80%, reacts 12h under the conditions of the synthesis temperature of 160 DEG C.
Step 3: until hydro-thermal reaction terminate and natural cooling after by product take out, wash 2 times, alcohol wash 2 times after collection, and
Under conditions of 80 DEG C, dry 6h, i.e. can get multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is filtering and washing, receives
Mode set is collected by suction.
Embodiment 3
Step one: weigh sodium metavanadate and thioacetamide, be dissolved in 50mL deionized water, the mol ratio controlling vanadium and sulfur is
1:2, obtains solution A after ultrasonic disperse 30min, the concentration in vanadium source is 0.6mol/L.
Step 2: solution A transferred in hydro-thermal reaction liner, installs outer still additional and is placed in homogeneous reaction instrument, controls hydro-thermal anti-
The packing ratio answered is 40%, reacts 18h under the conditions of the synthesis temperature of 170 DEG C.
Step 3: until hydro-thermal reaction terminate and natural cooling after by product take out, wash 4 times, alcohol wash 4 times after collection, and
Under conditions of 100 DEG C, dry 18h, i.e. can get multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is centrifuge washing,
Collection mode is collected for centrifugal.
Embodiment 4
Step one: weigh sodium metavanadate and thioacetamide, be dissolved in 80mL deionized water, the mol ratio controlling vanadium and sulfur is
1:1.8, obtains solution A after magnetic agitation 50min, the concentration in vanadium source is 0.4mol/L.
Step 2: solution A transferred in hydro-thermal reaction liner, installs outer still additional and is placed in homogeneous reaction instrument, controls hydro-thermal anti-
The packing ratio answered is 50%, reacts 36h under the conditions of the synthesis temperature of 200 DEG C.
Step 3: until hydro-thermal reaction terminate and natural cooling after by product take out, wash 5 times, alcohol wash 5 times after collection, and
Under conditions of 120 DEG C, dry 24h, i.e. can get multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is centrifuge washing,
Collection mode is collected for centrifugal.
Relative to prior art, the present invention at least has the advantages that
The present invention uses low-temperature hydrothermal synthetic method to be prepared for VS4Nano-powder, the method overcomes high the lacking of conventional calcination method temperature
Point, and need not main equipment and harsh reaction condition, it is not necessary to morphology control agent, cheaper starting materials is easy to get, low cost, and productivity is high,
Process without the later stage, environmentally friendly, large-scale production can be suitable for.Meanwhile, the method technique is simple and easy to control, the VS of preparation4
Nano-powder chemical composition is homogeneous, and purity and crystallinity are the highest.
Additionally, the VS prepared by the method4Nano-powder shows hollow corynebacterium VS4It is carried on stub and is wound around spherical VS4
On multilevel hierarchy.This multilevel hierarchy VS4Application of nanopowder in sodium/lithium/Magnesium ion battery and photocatalysis field, its as lithium/
The chemical property of excellence is shown during sodium ion battery electrode material.
Claims (10)
1. a multilevel hierarchy VS4The preparation method of nano-powder, it is characterised in that first vanadium source solution and sulfur source solution are being stirred
Mixing lower mixing, the mol ratio controlling vanadium and sulfur is 1:1～1:2, obtains mixed liquor, and the concentration in vanadium source is 0.06～0.6mol/L；Then
Mixed liquor is carried out hydro-thermal reaction, after reaction terminates, cooling, wash, collect, dry, i.e. can get multilevel hierarchy VS4Nanometer
Powder body；The temperature of described hydro-thermal reaction is 160～200 DEG C, and the time is 12～36h.
A kind of multilevel hierarchy VS the most according to claim 14The preparation method of nano-powder, it is characterised in that: described water
The packing ratio of thermal response is 40～80%.
A kind of multilevel hierarchy VS the most according to claim 14The preparation method of nano-powder, it is characterised in that wash described in:
The mode of washing is filtering and washing or centrifuge washing, and collection mode is collected by suction or centrifugal collection.
4. according to a kind of multilevel hierarchy VS described in claim 1 or 34The preparation method of nano-powder, it is characterised in that: water
After thermal response completes, reacted solution is carried out sucking filtration, successively washs with deionized water and dehydrated alcohol, to remove hydro-thermal
The impurity produced in course of reaction.
A kind of multilevel hierarchy VS the most according to claim 14The preparation method of nano-powder, it is characterised in that: described baking
Dry temperature is 60～120 DEG C, and the time is 6～24h.
A kind of multilevel hierarchy VS the most according to claim 14The preparation method of nano-powder, it is characterised in that: described
Alr mode is magnetic agitation or ultrasonic disperse.
A kind of multilevel hierarchy VS the most according to claim 14The preparation method of nano-powder, it is characterised in that: described vanadium
Source is one or more in sodium metavanadate, vanadic acid sodium, ammonium metavanadate, vanadic anhydride and potassium metavanadate.
A kind of multilevel hierarchy VS the most according to claim 14The preparation method of nano-powder, it is characterised in that: described sulfur
Source is one or more in thioacetamide, sodium oiethyl dithiocarbamate and sulfur simple substance.
9. the multilevel hierarchy VS prepared based on the method described in claim 14Nano-powder, it is characterised in that: this is multistage
Structure VS4Nano-powder has hollow corynebacterium VS4It is carried on stub and is wound around spherical VS4On multilevel hierarchy, wherein, hollow is short
A diameter of 50nm, a length of 200nm of rod.
10. the multilevel hierarchy VS that prepared by a method according to claim 14The application of nano-powder, it is characterised in that
This multilevel hierarchy VS4Application of nanopowder is in sodium/lithium/Magnesium ion battery, ultracapacitor and photocatalysis field.
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