CN105923652B - A kind of multilevel hierarchy VS4Nano-powder and its preparation method and application - Google Patents
A kind of multilevel hierarchy VS4Nano-powder and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 title description 3
- 239000011858 nanopowder Substances 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 25
- 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
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005864 Sulphur Substances 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 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 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 241000186216 Corynebacterium Species 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000012856 packing Methods 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
- 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
- 238000004804 winding 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
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000010405 anode material Substances 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
- 150000001875 compounds Chemical class 0.000 description 2
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 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
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 238000002156 mixing Methods 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
- 239000011368 organic material Substances 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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 kind of multilevel hierarchy VS4Nano-powder and its preparation method and application, first vanadium source solution and sulphur source solution are mixed under agitation, it is 1 to control the mol ratio of vanadium and sulphur:1~1:2, obtain mixed liquor；Then mixed liquor is subjected to hydro-thermal reaction, after reaction terminates, cooling, washing, collected, drying, you can obtain multilevel hierarchy VS4Nano-powder.This method technique is simple and easy to control, obtained VS4Nano-powder chemical composition is homogeneous, and purity is higher, and excellent chemical property is shown when it is as lithium/sodium ion battery electrode material.In addition, the method overcome the shortcomings that conventional calcination method temperature is high, and large scale equipment and harsh reaction condition are not needed, raw material is cheap and easy to get, and cost is low, and yield is high, environmentally friendly without post-processing, can be adapted to mass produce.
Description
【Technical field】
The present invention relates to a kind of preparation method of four vanadic sulfides nano material, and in particular to a kind of multilevel hierarchy VS4Nanometer
Powder and its preparation method and application.
【Background technology】
Lithium ion battery is extensive due to having the advantages that operating voltage is high, capacity is high, self discharge is small and has extended cycle life
Applied to portable electronic market.But global lithium resource will be unable to the great demand for effectively meeting 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 is due to aboundresources, cost
The features such as cheap, environment-friendly, it is considered to be replacement lithium ion battery is as electric powered motor power supply of future generation and on a large scale
The ideal chose of the supporting power supply of energy-accumulating power station, therefore the storage sodium electrode material for seeking high power capacity and excellent cycling performance turns into mesh
Study hotspot [Slater M D, Kim D, Lee E, et the al. Sodium-Ion Batteries [J] of preceding field of batteries
.Advanced Functional Materials,2013,23(8):947-958]。。
At present, the research of anode material of lithium-ion battery be concentrated mainly on hard carbon/soft carbon, alloy material, compound and
Organic material etc..The transient metal sulfides such as molybdenum, tungsten and vanadium are a kind of more satisfactory lithium ions and sodium-ion battery negative pole
Material, because this kind of sulfide typically has layer structure, their interlamellar spacing is all bigger, with lithium and sodium electrochemical reaction
During, lithium ion and sodium ion can be embedded into layer structure.And another important feature of this kind of sulfide is between layer gap
Van der Waals force be present, it can provide the embedded space of lithium ion or sodium ion.Insertion reaction occurs in lithium ion or sodium ion
When, in a complete charging reaction generating process, existing lithium ion or sodium ion store up lithium (sodium) by being diffused into lamellar spacing,
Same also generation metal ion is reduced to lower valency storage lithium (sodium).It is particularly nearest grind to make internal disorder or usurp show, transition metal curing
Thing is by compound with highly conductive carbon material, formation MoS2、WS2And VS2The composite such as carbon fiber and graphene shows fabulous
Storage lithium or storage sodium performance [synthesis of the magnificent sulfide composite of uncle Zhai and its storage lithium (sodium) performance study [D] Hunan are big
Learn, 2014].
Molybdenum sulfide and sulphur are but concentrated mainly on report of the transient metal sulfide as anode material of lithium-ion battery
Change the research of tungsten.Vanadium disulfide is also concentrated mainly on reporting for work for vanadic sulfide, many researchers are reported by hydro-thermal legal system
It is standby go out the vanadium disulfide with nanometer sheet, nanometer flower structure.Because the synthesis condition of four vanadic sulfides is harsh, reaction is unmanageable,
It result in relatively slower always to its progress.It is even more few as the report of lithium/sodium ion battery electrode material on it
See.
【The content 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 operated
Simply, and reaction temperature i.e. available by a step hydro-thermal is low, reaction time is short, obtained VS4Chemical constituent is homogeneous, purity
It 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 vanadium source solution and sulphur source solution are mixed under agitation,
It is 1 to control the mol ratio of vanadium and sulphur:1~1:2, mixed liquor is obtained, the concentration in vanadium source is 0.06~0.6mol/L；Then will mixing
Liquid carries out hydro-thermal reaction, after reaction terminates, cooling, washing, collects, drying, you can obtain multilevel hierarchy VS4Nano-powder；Institute
The temperature for stating hydro-thermal reaction is 160~200 DEG C, and the time is 12~36h.
Further, the packing ratio of the hydro-thermal reaction is 40~80%.
Further, the mode of washing is filtering and washing or centrifuge washing, and collection mode is that collected by suction or centrifugation are received
Collection.
Further, after the completion of hydro-thermal reaction, reacted solution is filtered, successively with deionized water and anhydrous second
Alcohol is washed, to remove caused impurity in hydrothermal reaction process.
Further, the temperature of the drying is 60~120 DEG C, and the time is 6~24h.
Further, described agitating mode is magnetic agitation or ultrasonic disperse.
Further, the vanadium source is in sodium metavanadate, sodium vanadate, ammonium metavanadate, vanadic anhydride and potassium metavanadate
One or more.
Further, the sulphur source is one kind in thioacetamide, sodium oiethyl dithiocarbamate and sulphur simple substance
It is or several.
A kind of multilevel hierarchy VS4Nano-powder, multilevel hierarchy VS4Nano-powder is with hollow corynebacterium VS4And load
In stub be wound in it is spherical on, wherein, a diameter of 50nm of hollow stub, length 200nm.One kind passes through above method system
Standby multilevel hierarchy VS4The application of nano-powder, multilevel hierarchy VS4Application of nanopowder in sodium/lithium/Magnesium ion battery and
Photocatalysis field.
Relative to prior art, the present invention at least has the advantages that：
The present invention is prepared for VS using low-temperature hydrothermal synthetic method4Nano-powder, it the method overcome conventional calcination method temperature
The shortcomings that high, and large scale equipment and harsh reaction condition are not needed, without pattern controlling agent, raw material is cheap and easy to get, and cost is low,
Yield is high, environmentally friendly without post-processing, can be adapted to mass produce.Meanwhile this method technique is simple and easy to control, system
Standby VS4Nano-powder chemical composition is homogeneous, and purity and crystallinity are higher.
In addition, the VS prepared by this method4Nano-powder shows hollow corynebacterium VS4It is carried on stub winding ball
Shape VS4On multilevel hierarchy.Multilevel hierarchy VS4Application of nanopowder in sodium/lithium/Magnesium ion battery and photocatalysis field, its
Excellent chemical property is shown during as lithium/sodium ion battery electrode material.
【Brief description of the drawings】
Fig. 1 is VS prepared by the embodiment of the present invention 14X-ray diffraction (XRD) collection of illustrative plates of nano-powder；
Fig. 2 and Fig. 3 is VS prepared by the embodiment of the present invention 14ESEM (SEM) photo of nano-powder.
【Embodiment】
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
A kind of multilevel hierarchy VS4The preparation method of nano-powder, comprises the following steps：
Step 1：Vanadium source and sulphur source material are weighed, vanadium source and sulphur source material are dissolved in 40~80mL deionized waters, is controlled
The mol ratio of vanadium and sulphur processed is 1:1~1:Solution A, the concentration in vanadium source are obtained after 2,10~60min of magnetic agitation or ultrasonic disperse
For 0.06~0.6mol/L.Vanadium source is one in sodium metavanadate, sodium vanadate, ammonium metavanadate, vanadic anhydride and potassium metavanadate
Kind is several.Sulphur source is the one or more in thioacetamide, sodium oiethyl dithiocarbamate and sulphur simple substance.
Step 2：Solution A 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 40~80%, and 12~36h is reacted under the conditions of 160~200 DEG C of synthesis temperature.
Step 3：Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing 2~5 times, alcohol washes 2~5 times
After collect, and under conditions of 60~120 DEG C dry 6~24h, you can obtain multilevel hierarchy VS4Nano-powder.Mode of washing is
Filtering and washing or centrifuge washing, collection mode are collected by suction or are collected by centrifugation.
The VS prepared by the above method4Nano material has hollow corynebacterium VS4It is carried on stub winding glomeration VS4
On multilevel hierarchy, wherein the diameter of hollow stub is about 50nm, length is about 200nm.Multilevel hierarchy VS4Nano-powder should
For sodium/lithium/Magnesium ion battery and photocatalysis field.Especially when it is applied to sodium-ion battery, show excellent
Chemical property.
Embodiment 1
Step 1：Sodium metavanadate and thioacetamide are weighed, is dissolved in 60mL deionized waters, controls mole of vanadium and sulphur
Than for 1:Solution A is obtained after 1, magnetic agitation 60min, the concentration in vanadium source is 0.06mol/L.
Step 2：Solution A 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 3：Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing 3 times, alcohol receives after washing 3 times
Collection, and dry 12h under conditions of 60 DEG C, you can obtain multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is washed for suction filtration
Wash, 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.
It is about 50nm that diameter is can be clearly seen that from Fig. 2-3, and length is about 200nm corynebacteriums VS4It is carried on stub
Wind glomeration VS4On multilevel hierarchy.
Embodiment 2
Step 1：Sodium metavanadate and thioacetamide are weighed, is dissolved in 40mL deionized waters, controls mole of vanadium and sulphur
Than for 1:Solution A is obtained after 1.5, ultrasonic disperse 10min, the concentration in vanadium source is 0.1mol/L.
Step 2：Solution A 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 80%, reacts 12h under the conditions of 160 DEG C of synthesis temperature.
Step 3：Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing 2 times, alcohol receives after washing 2 times
Collection, and dry 6h under conditions of 80 DEG C, you can obtain multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is washed for suction filtration
Wash, collection mode is collected by suction.
Embodiment 3
Step 1：Sodium metavanadate and thioacetamide are weighed, is dissolved in 50mL deionized waters, controls mole of vanadium and sulphur
Than for 1:Solution A is obtained after 2, ultrasonic disperse 30min, the concentration in vanadium source is 0.6mol/L.
Step 2：Solution A 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 40%, reacts 18h under the conditions of 170 DEG C of synthesis temperature.
Step 3：Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing 4 times, alcohol receives after washing 4 times
Collection, and dry 18h under conditions of 100 DEG C, you can obtain multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is washed for centrifugation
Wash, collection mode is to be collected by centrifugation.
Embodiment 4
Step 1：Sodium metavanadate and thioacetamide are weighed, is dissolved in 80mL deionized waters, controls mole of vanadium and sulphur
Than for 1:Solution A is obtained after 1.8, magnetic agitation 50min, the concentration in vanadium source is 0.4mol/L.
Step 2：Solution A 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 50%, reacts 36h under the conditions of 200 DEG C of synthesis temperature.
Step 3：Terminate after hydro-thermal reaction and take out reaction product after natural cooling, washing 5 times, alcohol receives after washing 5 times
Collection, and dry 24h under conditions of 120 DEG C, you can obtain multilevel hierarchy VS4Nano-powder.Wherein, mode of washing is washed for centrifugation
Wash, collection mode is to be collected by centrifugation.
Relative to prior art, the present invention at least has the advantages that：
The present invention is prepared for VS using low-temperature hydrothermal synthetic method4Nano-powder, it the method overcome conventional calcination method temperature
The shortcomings that high, and large scale equipment and harsh reaction condition are not needed, without pattern controlling agent, raw material is cheap and easy to get, and cost is low,
Yield is high, environmentally friendly without post-processing, can be adapted to mass produce.Meanwhile this method technique is simple and easy to control, system
Standby VS4Nano-powder chemical composition is homogeneous, and purity and crystallinity are higher.
In addition, the VS prepared by this method4Nano-powder shows hollow corynebacterium VS4It is carried on stub winding ball
Shape VS4On multilevel hierarchy.Multilevel hierarchy VS4Application of nanopowder in sodium/lithium/Magnesium ion battery and photocatalysis field, its
Excellent chemical property is shown during as lithium/sodium ion battery electrode material.
Claims (8)
- A kind of 1. multilevel hierarchy VS4The preparation method of nano-powder, it is characterised in that first removing vanadium source solution and sulphur source solution It is uniformly mixed in ionized water, it is 1 to control the mol ratio of vanadium and sulphur:1~1:2, mixed liquor is obtained, the concentration in vanadium source is 0.06 ~0.6mol/L；Then mixed liquor is subjected to hydro-thermal reaction, the packing ratio of the hydro-thermal reaction is 40~80%, and reaction terminates Afterwards, cool down, washing, collect, drying, you can obtain multilevel hierarchy VS4Nano-powder；The temperature of the hydro-thermal reaction be 160~ 200 DEG C, the time is 12~36h, the VS prepared by this method4Nano material has hollow corynebacterium VS4It is carried on stub winding Glomeration VS4On multilevel hierarchy；The mode of washing is filtering and washing or centrifuge washing, collection mode be collected by suction or from The heart is collected.
- A kind of 2. multilevel hierarchy VS according to claim 14The preparation method of nano-powder, it is characterised in that：Hydro-thermal reaction After the completion of, reacted solution is filtered, successively washed with deionized water and absolute ethyl alcohol, to remove hydro-thermal reaction During caused impurity.
- A kind of 3. multilevel hierarchy VS according to claim 14The preparation method of nano-powder, it is characterised in that：The drying Temperature be 60~120 DEG C, the time is 6~24h.
- A kind of 4. multilevel hierarchy VS according to claim 14The preparation method of nano-powder, it is characterised in that：Described stirs It is magnetic agitation or ultrasonic disperse to mix mode.
- A kind of 5. multilevel hierarchy VS according to claim 14The preparation method of nano-powder, it is characterised in that：The vanadium source For the one or more in sodium metavanadate, sodium vanadate, ammonium metavanadate, vanadic anhydride and potassium metavanadate.
- A kind of 6. multilevel hierarchy VS according to claim 14The preparation method of nano-powder, it is characterised in that：The sulphur source For the one or more in thioacetamide, sodium oiethyl dithiocarbamate and sulphur simple substance.
- A kind of 7. multilevel hierarchy VS prepared by method based on described in claim 14Nano-powder, it is characterised in that：The multistage is tied Structure VS4Nano-powder has hollow corynebacterium VS4It is carried on stub and winds spherical VS4On multilevel hierarchy, wherein, hollow stub A diameter of 50nm, length 200nm.
- A kind of 8. multilevel hierarchy VS prepared by method according to claim 114The application of nano-powder, it is characterised in that should Multilevel hierarchy VS4Application of nanopowder is in sodium/lithium/Magnesium ion battery, ultracapacitor field.
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| 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 |
| CN108126712B (en) * | 2017-12-22 | 2020-11-13 | 陕西科技大学 | VOOH/VS4Micron composite powder and its prepn and application |
| CN108862381B (en) * | 2018-06-26 | 2021-01-22 | 中国科学院宁波材料技术与工程研究所 | Vanadium tetrasulfide electrode material and preparation method and application thereof |
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| 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 |
| CN110180556B (en) * | 2019-05-28 | 2022-03-11 | 广州大学 | Modified vanadium tetrasulfide Fenton catalyst and preparation method and application thereof |
| CN110302804B (en) * | 2019-06-21 | 2022-01-04 | 江苏理工学院 | VS (virtual switch)4-TiO2AC photocatalyst and preparation method thereof |
| CN110299527B (en) * | 2019-07-02 | 2020-03-31 | 张蓓 | Lithium ion battery cathode material and preparation method thereof |
| 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 |
| CN111584829A (en) * | 2020-05-26 | 2020-08-25 | 青岛科技大学 | Flexible VS2Thin film electrode and preparation method thereof |
| CN112054160B (en) * | 2020-09-30 | 2023-06-16 | 河北华普化工设备科技有限公司 | Vanadium pentoxide positive electrode material and preparation method and application thereof |
| CN112490438B (en) * | 2020-11-27 | 2022-03-11 | 青岛科技大学 | Mo-VS4Positive electrode material of/N-GNTs magnesium ion battery |
| CN113413905B (en) * | 2021-07-30 | 2022-06-21 | 陕西科技大学 | Vanadium tetrasulfide-nickel sulfide/graphite phase carbon nitride photocatalyst and preparation method thereof |
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