CN104953119A - Preparation method for two-dimensional matrix rod-like WS2 anode material - Google Patents

Preparation method for two-dimensional matrix rod-like WS2 anode material Download PDF

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CN104953119A
CN104953119A CN201510310069.9A CN201510310069A CN104953119A CN 104953119 A CN104953119 A CN 104953119A CN 201510310069 A CN201510310069 A CN 201510310069A CN 104953119 A CN104953119 A CN 104953119A
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dimensional matrix
solution
microwave
preparation
aqueous solution
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CN104953119B (en
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黄剑锋
王鑫
李嘉胤
曹丽云
许占位
费杰
孔新刚
李翠艳
姚春燕
郝巍
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Guangxi Free Trade Zone Jianju Technology Co.,Ltd.
Guangxi Qinbao Real Estate Co., Ltd;
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Shaanxi University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/139—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
    • 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 preparation method for a two-dimensional matrix rod-like WS2 anode material. The preparation method comprises the following steps: adding tungsten powder in hydrogen peroxide to obtain a solution A; diluting the solution A by adopting isopropanol and adding L-cysteine and trisodium citrate to form a precursor solution; pouring the precursor solution into an ultrasonic, microwave and ultraviolet three-in-one synthesis reaction apparatus, and meanwhile, starting an ultrasonic, microwave and ultraviolet synthesis mode for heat preservation, centrifuging for separating a product, and washing and freeze-drying sequentially, so as to obtain the two-dimensional matrix rod-like WS2 anode material. By adopting the method, controllable synthesis of the WS2 anode material can be realized and the prepared WS2 anode material has good capacity and other better electrochemical performance.

Description

The bar-shaped WS of a kind of two-dimensional matrix 2the preparation method of negative material
Technical field
The present invention relates to one and prepare the bar-shaped WS of two-dimensional matrix 2the method of negative material, particularly a kind of trisodium citrate complexing ultrasonic microwave ultraviolet synthetic method prepares the bar-shaped WS of two-dimensional matrix 2the method of negative material.
Background technology
WS 2crystal structure and MoS 2similar, be also the layer structure of close-packed hexagonal.Have strong chemical bond to be connected between tungsten atom with sulphur atom, and interlayer sulphur atom is connected by weak molecular link with between sulphur atom.Adhesion is between layers still Van der Waals force, with MoS 2compare, WS 2interlamellar spacing comparatively large, coefficient of friction is lower, between 0.03 ~ 0.05.
WS 2almost do not dissolve in all media, comprise water, oil, alkali and nearly all acid.But it is more responsive with hydrofluoric acid to free gaseous fluorine, hot sulfuric acid.WS 2thermal stability also better, its decomposition temperature is in an atmosphere 510 DEG C, and 539 DEG C of rapid oxidation, in vacuum, decomposition temperature is 1150 DEG C.WS 2radiation resistance be better than graphite, MoS 2, there is good greasy property, be not only applicable to usual lubricating condition, and may be used for high temperature, high pressure, high vacuum, high load capacity, have radiation and operational environment that the medium that is corrosive etc. is harsh.This also fully shows WS 2can be used as stable battery electrode material.
Nanometer WS 2become the focus of the area researches such as domestic and international chemistry, physics, material science, except being widely used in solid lubrication aspect, in catalyst, electrode material, electron microprobe etc., have huge application potential.Especially WS 2the extensive concern of people is caused as lithium ion battery and sodium ion battery electrode material.Report that vacuum impregnation technology has prepared order mesoporous WS 2anode material for lithium-ion batteries [Hao Liu, Dawei Su, Guoxiu Wang, Shi Zhang Qiao.An ordered mesoporous WS 2anode material with superior electrochemical performance for lithium ion batteries [J] .J.Mater.Chem., 2012,22:17437-17440.]; Gas-phase presulfiding reaction method has prepared WS 2nano particle and WS 2nanotube [A Margolin, F L Deepak, R Popovitz-Biro, et al, Fullerene-like WS 2nanoparticles and nanotubes by the vapor-phase synthesis of WCl nand H 2s [J] .Nanotechnology, 200,19:95601-95611.]; Chemical vapour deposition technique has prepared the WS of sheet self assembly 2bouquet (CVD) [Arunvinay Prabakaran, Frank Dillon, Jodie Melbourne, et al.WS 22D nanosheets in 3D nanoflowers [J] .Chem.Commun.2014,50:12360-12362.]; Surface active agent assisting alcohol-hydrothermal method has prepared WS 2nanometer rods [Guogang Tang, Hua Tang, Changsheng Li, Wenjing Li, Xiaorui Ji.Surfactant-assisted hydrothermal synthesis and characterization of WS 2nanorods [J] .Materials Letters.2011,65:3457-3460.].In addition, hydro thermal method is adopted to prepare WS 2-Graphene compound sodium-ion battery positive material [Dawei Su, Shixue Dou, Guoxiu Wang.WS 2@graphene nanocomposites as anode materials for Na-ion batteries with enhanced electrochemical performances [J] .Chem.Comm., 2014,50:4192-4195.] and surface active agent assisting alcohol-hydrothermal method prepared WS 2-nitrogen-doped graphene laminar composite [Dongyun Chen, Ge Ji, Bo Ding, Yue Ma, Baihua Qu, Weixiang Chen, Jim Yang Lee.In situ nitrogenated grapheme-few-layer WS 2composites for fast and reversible Li +storage [J] .Nanoscale, 2013,5:7890-7896.].But, the bar-shaped WS of the single nanometer two-dimensional matrix of relevant preparation 2research and relevant report as anode material of lithium-ion battery less.
The preparation WS reported at present 2the method of material mainly contain thermal decomposition method [Zhu Yajun, Zhang Xuebin, Ji Yi etc. the preparation method of nano tungsten disulfide and molybdenum bisuphide and application [J]. Chemical Industry in Guangzhou, 2012,3 (40): 4-6.]; Gu-gas sulfuration method [Yan-Hui Li, Yi Min Zhao, Ren Zhi Ma, Yan Qiu Zhu, Niles Fisher, Yi Zheng Jin, Xin Ping Zhang.Novel Route to WOx Nanorods and WS 2nanotubes from WS 2inorganic Fullerenes [J] .J.Phys.Chem.B.2006,110:18191-18195.]; Original position evaporation synthetic method [A Margolin, F L Deepak, R Popovitz-Biro, M Bar-Sadan1, Y Feldman, R Tenne.Fullerene-like WS 2nanoparticles and nanotubes by the vapor-phase synthesis of WCl nand H 2s [J] .Nanotechnology.2008,19:95601-95611.]; Spray pyrolysis [Seung Ho Choi, Yun Chan Kang.Sodium ion storage properties of WS 2-decorated three-dimensional reduced graphene oxide microspheres [J] .Nanoscale.2015,7:3965-3970]; Mechanical activation method [Zhuangzhi Wu, Dezhi Wang, Xiuqi Zan, Aokui Sun.Synthesis of WS 2nanosheets by a novel mechanical activation method [J] .Materials Letters, 2010,64:856-858.] [Zheng loses all to precipitate reducing process in addition, Song Xuchun, Liu Bo, Han Gui, Xu Zhude. the synthesis of nested spherical stratiform enclosed construction nano tungsten disulfide and Exploration of Mechanism [J]. Journal of Inorganic Materials, 2004,3 (19): 653-656.]; Precipitation reducing process, thermal decomposition method and solid phase vulcanizing method all synthesize WS under high-temperature atmosphere condition 2, powder is easily reunited and process conditions are difficult to control, to preparation WS 2the utilance of needed raw material is very little; And solid phase method sinters or vulcanization reaction occurs under reducing atmosphere condition, also can cause nanocrystalline reunion, abnormal grain growth, the microstructure of material is difficult to regulation and control.Meanwhile, the high and proportioning of reactant is difficult to control to equipment requirement for original position evaporation and chemical vapour deposition technique, and prepared WS 2easily introduce impurity in nano material, and powder is easily reunited.In addition, hydro thermal method and solvent-thermal method need to prepare nano material under high temperature and high pressure environment, and high to equipment requirement, poor stability.
Summary of the invention
The object of the present invention is to provide the bar-shaped WS of a kind of two-dimensional matrix 2the preparation method of negative material.
For achieving the above object, present invention employs following technical scheme:
Step one: 1.0 ~ 6.0g tungsten powder being added 10 ~ 80mL mass fraction is rear stirring 0.5 ~ 4h in the aqueous hydrogen peroxide solution of 30%, filters after stirring, and filtration gained filtrate is designated as solution A;
Step 2: adopt isopropyl alcohol by solution A dilution 0.5 ~ 3 times, Cys and trisodium citrate is added in the solution A after dilution, and form precursor aqueous solution after continuing stirring 0.5 ~ 3h, in precursor aqueous solution, the concentration of Cys is 0.04 ~ 4.0mol/L, and in precursor aqueous solution, the concentration of trisodium citrate is 4.0 ~ 10.0g/L;
Step 3: poured into by precursor aqueous solution in the reaction vessel of ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, the compactedness of reaction vessel controls 30 ~ 60%, then reaction vessel is put into described Trinity synthetic reaction instrument; Then, open ultrasonic wave, microwave and ultraviolet synthesis model simultaneously, utilize microwave, through 5 ~ 40min, the precursor aqueous solution in reaction vessel is heated to 50 ~ 120 DEG C from room temperature, be then incubated 0.5 ~ 4h, after insulation terminates, naturally cool to room temperature;
Step 4: after step 3, open described Trinity synthetic reaction instrument, and centrifugation product, product is grey black precipitation, to adopt after deionized water and absolute ethyl alcohol repeated washing product 4 ~ 6 times in-20 ~-70 DEG C of freeze dryings successively, namely obtain the bar-shaped WS of two-dimensional matrix 2negative material.
In described step one and step 2, stir the magnetic stirring apparatus that the model adopting Mettler-Toledo Instrument (Shanghai) Co., Ltd. to produce is RCT B S25.
In described step 3, the model that microwave ultraviolet ultrasonic wave Trinity synthetic reaction instrument adopts Xinyi Microwave Chemistry Tech Co., Ltd. to manufacture: UWave-1000.
The ultrasonic power of described Trinity synthetic reaction instrument controls at 100 ~ 800W, and microwave power controls at 200 ~ 1000W, and UV power controls at 300W.
In described step 4, cryodesiccated vacuum degree is 0.0 ~ 10.0Pa, and sublimation drying is 3 ~ 8h, the model that freeze drier adopts Beijing development in science and technology Co., Ltd of Song Yuan Huaxing to manufacture: LGJ-10.
Beneficial effect of the present invention is embodied in:
Because the present invention prepares the bar-shaped WS of two-dimensional matrix 2the reaction of negative material once completes in low-temperature atmosphere-pressure liquid phase and process equipment is simple, does not need the crystallization and thermal treatment in later stage, thus avoids WS 2the defects such as impurity are introduced in the reunion that negative material may cause in heat treatment process, grain coarsening and atmosphere reaction.Meanwhile, reunion degree is comparatively light, more cheap raw material can be used to obtain uniform crystal particles and the single bar-shaped WS of two-dimensional matrix of pattern 2negative material.The more important thing is, the equipment that microwave ultraviolet ultrasonic synthesis requires and instrument more simple and more effectively can prepare crystallinity better, oriented growth pattern is single, and particle diameter is less and be evenly distributed, the WS that purity is higher 2.Adopt isopropyl alcohol as solvent, under trisodium citrate Complexation conditions, green, clean, harmless and be more conducive to WS 2oriented growth, thin rod is self-assembled into two-dimensional matrix bar structure, so more efficient, economy, safety.In addition, microwave heating efficiency is higher, under ultrasonic wave and ultraviolet effect, be conducive to rapid diffusion mass transfer, can nucleation-oriented growth at short notice, finally realizes WS 2the controlledly synthesis of negative material, and prepared WS 2negative material has the better chemical properties such as high power capacity.
Accompanying drawing explanation
Fig. 1 is WS prepared by the embodiment of the present invention 1 2the XRD figure of nanocrystalline negative material;
Fig. 2 is WS prepared by the embodiment of the present invention 1 2the SEM figure of nanocrystalline negative material;
Fig. 3 is WS prepared by the embodiment of the present invention 1 2cycle performance figure (the current density: 200mA g of nanocrystalline negative material -1; Voltage: 0 ~ 3V).Discharge: electric discharge, Charge: charging.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated.
Embodiment 1:
Step one: it is in the aqueous hydrogen peroxide solution of 30% that analytically pure for 1.5g tungsten powder is slowly added 20mL mass fraction, and constantly fully stir, avoid reacting and release a large amount of heat, filter after reaction 1h, remove sediment, the filtrate obtained is designated as solution A;
Step 2: adopt isopropyl alcohol that solution A is diluted 1 times again, and add Cys, controlling Cys concentration is 0.04mol/L, adds analytically pure trisodium citrate simultaneously, controlling trisodium citrate addition is 4.0g/L, and forms uniform precursor aqueous solution after continuing to stir 1h;
Step 3: poured into by precursor aqueous solution in four neck round-bottomed flasks of UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, compactedness controls 60%, then four neck round-bottomed flasks are put into described Trinity synthetic reaction instrument, and fixes; Open ultrasonic microwave ultraviolet synthesis model simultaneously and (adopt ultrasonic microwave ultraviolet synthesis model, make it act on pre-reaction material simultaneously, wherein ultrasonic power controls at 200W, microwave power controls at 300W, UV power controls at 300W), utilize microwave, through 10min, precursor aqueous solution is heated to 60 DEG C from room temperature, be then incubated 4h, after insulation terminates, naturally cool to room temperature;
Step 4: open UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, centrifugation product, adopt deionized water and absolute ethyl alcohol repeated washing to be placed on temperature 4 times successively and be-20 DEG C, vacuum degree is that namely the freeze drier inner drying 8h of 2.0Pa obtains WS 2nanocrystalline.
WS as seen from Figure 1 prepared by embodiment 1 2nanocrystalline purity is high, and diffraction maximum is comparatively sharp-pointed, and is single six side phase WS 2, with the PDF 84-1399WS of standard 2card matches.
WS as seen from Figure 2 prepared by embodiment 1 2nanocrystalline pattern is homogeneous, even size distribution, without obviously reuniting, presents self assembly two-dimensional matrix bar structure, and the length of rod is 2 μm.
The WS prepared by embodiment 1 can be drawn by Fig. 3 2nanocrystalline, be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is 200mA g -1charge-discharge performance under condition, initial discharge capacity is 385mAh g -1, after cycle-index (Cycle Number) reaches 50 times, prepared material still maintains 295mAh g -1capacity (Capacity), capability retention is higher.
Embodiment 2:
Step one: it is in the aqueous hydrogen peroxide solution of 30% that analytically pure for 6.0g tungsten powder is slowly added 80mL mass fraction, and constantly fully stir, avoid reacting and release a large amount of heat, filter after reaction 3h, remove sediment, the filtrate obtained is designated as solution A;
Step 2: adopt isopropyl alcohol that solution A is diluted 2.5 times again, and add Cys, controlling Cys concentration is 2mol/L, adds analytically pure trisodium citrate simultaneously, controlling trisodium citrate addition is 8.0g/L, and forms uniform precursor aqueous solution after continuing to stir 3h;
Step 3: poured into by precursor aqueous solution in four neck round-bottomed flasks of UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, compactedness controls 45%, then four neck round-bottomed flasks are put into described Trinity synthetic reaction instrument, and fixes; Open ultrasonic microwave ultraviolet synthesis model simultaneously and (adopt ultrasonic microwave ultraviolet synthesis model, make it act on pre-reaction material simultaneously, wherein ultrasonic power controls at 700W, microwave power controls at 800W, UV power controls at 300W), utilize microwave, through 30min, precursor aqueous solution is heated to 120 DEG C from room temperature, be then incubated 3.5h, after insulation terminates, naturally cool to room temperature;
Step 4: open UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, centrifugation product, adopt deionized water and absolute ethyl alcohol repeated washing to be placed on temperature 5 times successively and be-70 DEG C, vacuum degree is that namely the freeze drier inner drying 7h of 10.0Pa obtains WS 2nanocrystalline.
The WS of gained 2nanocrystalline is single six side phase WS 2, with the PDF 84-1399WS of standard 2card matches; Present self assembly two-dimensional matrix bar structure, the length of rod is 3.5 μm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is 200mA g -1under condition, initial discharge capacity is 405mAh g -1, after cycle-index (Cycle Number) reaches 50 times, prepared material still maintains 310mAh g -1capacity (Capacity).
Embodiment 3:
Step one: it is in the aqueous hydrogen peroxide solution of 30% that analytically pure for 4.0g tungsten powder is slowly added 60mL mass fraction, and constantly fully stir, avoid reacting and release a large amount of heat, filter after reaction 2.5h, remove sediment, the filtrate obtained is designated as solution A;
Step 2: adopt isopropyl alcohol that solution A is diluted 2 times again, and add Cys, controlling Cys concentration is 1.0mol/L, adds analytically pure trisodium citrate simultaneously, controlling trisodium citrate addition is 6.0g/L, and forms uniform precursor aqueous solution after continuing to stir 2h;
Step 3: poured into by precursor aqueous solution in four neck round-bottomed flasks of UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, compactedness controls 45%, then four neck round-bottomed flasks are put into described Trinity synthetic reaction instrument, and fixes; Open ultrasonic microwave ultraviolet synthesis model simultaneously and (adopt ultrasonic microwave ultraviolet synthesis model, make it act on pre-reaction material simultaneously, wherein ultrasonic power controls at 500W, microwave power controls at 600W, UV power controls at 300W), utilize microwave, through 25min, precursor aqueous solution is heated to 100 DEG C from room temperature, be then incubated 3.5h, after insulation terminates, naturally cool to room temperature;
Step 4: open UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, centrifugation product, adopt deionized water and absolute ethyl alcohol repeated washing to be placed on temperature 6 times successively and be-50 DEG C, vacuum degree is that namely the freeze drier inner drying 5h of 9.0Pa obtains WS 2nanocrystalline.
The WS of gained 2nanocrystalline is single six side phase WS 2, with the PDF 84-1399WS of standard 2card matches; Present self assembly two-dimensional matrix bar structure, the length of rod is 3 μm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is 200mA g -1under condition, initial discharge capacity is 395mAh g -1, after cycle-index (Cycle Number) reaches 50 times, prepared material still maintains 305mAh g -1capacity (Capacity).
Embodiment 4:
Step one: it is in the aqueous hydrogen peroxide solution of 30% that analytically pure for 2.0g tungsten powder is slowly added 30mL mass fraction, and constantly fully stir, avoid reacting and release a large amount of heat, filter after reaction 1.5h, remove sediment, the filtrate obtained is designated as solution A;
Step 2: adopt isopropyl alcohol that solution A is diluted 1.5 times again, and add Cys, controlling Cys concentration is 0.08mol/L, adds analytically pure trisodium citrate simultaneously, controlling trisodium citrate addition is 5.0g/L, and forms uniform precursor aqueous solution after continuing to stir 1.5h;
Step 3: poured into by precursor aqueous solution in four neck round-bottomed flasks of UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, compactedness controls 50%, then four neck round-bottomed flasks are put into described Trinity synthetic reaction instrument, and fixes; Open ultrasonic microwave ultraviolet synthesis model simultaneously and (adopt ultrasonic microwave ultraviolet synthesis model, make it act on pre-reaction material simultaneously, wherein ultrasonic power controls at 300W, microwave power controls at 400W, UV power controls at 300W), utilize microwave, through 15min, precursor aqueous solution is heated to 80 DEG C from room temperature, be then incubated 3h, after insulation terminates, naturally cool to room temperature;
Step 4: open UWave-1000 type ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, centrifugation product, adopt deionized water and absolute ethyl alcohol repeated washing to be placed on temperature 5 times successively and be-40 DEG C, vacuum degree is that namely the freeze drier inner drying 6h of 4.0Pa obtains WS 2nanocrystalline.
The WS of gained 2nanocrystalline is single six side phase WS 2, with the PDF 84-1399WS of standard 2card matches; Present self assembly two-dimensional matrix bar structure, the length of rod is 2.5 μm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is 200mA g -1under condition, initial discharge capacity is 390mAh g -1, after cycle-index (Cycle Number) reaches 50 times, prepared material still maintains 300mAh g -1capacity (Capacity).
The present invention prepares the WS of gained 2nanocrystalline is single six side phase WS 2, with the PDF 84-1399WS of standard 2card matches; Present self assembly two-dimensional matrix bar structure, the length of rod is 1 ~ 5 μm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is 200mA g -1under condition, initial discharge capacity is 380 ~ 405mAh g -1, after cycle-index (Cycle Number) reaches 50 times, prepared material still maintains 290 ~ 320mAh g -1capacity (Capacity).
In a word, the present invention proposes a kind of simple, and economical, the technology of preparing of efficient anode material of lithium-ion battery, this technical regulation prepares the bar-shaped WS of single two-dimensional matrix 2nanocrystalline, simple green, efficiently controlled and can by controlling the regulation and control pattern of product such as complexing agent addition and precursor aqueous solution proportioning and component, and it is efficiently quicker than hydro thermal method, microwave-hydrothermal method and solvent-thermal method, simple and safe, nucleation rate is very fast, and ultrasonic vibration impels component homogeneous reaction and nucleation and morphology controllable.The bar-shaped WS of two-dimensional matrix that under low-temperature atmosphere-pressure condition of the present invention, trisodium citrate complexing ultrasonic microwave ultraviolet synthetic method is made 2nanocrystalline purity is high, good dispersion, size uniform, and pattern is homogeneous, and has higher capacity, effectively improves WS 2nanocrystalline specific area and chemical property.

Claims (4)

1. the bar-shaped WS of two-dimensional matrix 2the preparation method of negative material, is characterized in that: comprise the following steps:
Step one: 1.0 ~ 6.0g tungsten powder being added 10 ~ 80mL mass fraction is rear stirring 0.5 ~ 4h in the aqueous hydrogen peroxide solution of 30%, filters after stirring, and filtration gained filtrate is designated as solution A;
Step 2: adopt isopropyl alcohol by solution A dilution 0.5 ~ 3 times, Cys and trisodium citrate is added in the solution A after dilution, and form precursor aqueous solution after continuing stirring 0.5 ~ 3h, in precursor aqueous solution, the concentration of Cys is 0.04 ~ 4.0mol/L, and in precursor aqueous solution, the concentration of trisodium citrate is 4.0 ~ 10.0g/L;
Step 3: poured into by precursor aqueous solution in the reaction vessel of ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, the compactedness of reaction vessel controls 30 ~ 60%, then reaction vessel is put into described Trinity synthetic reaction instrument; Then, open ultrasonic wave, microwave and ultraviolet synthesis model simultaneously, utilize microwave, through 5 ~ 40min, the precursor aqueous solution in reaction vessel is heated to 50 ~ 120 DEG C from room temperature, be then incubated 0.5 ~ 4h, after insulation terminates, naturally cool to room temperature;
Step 4: after step 3, opens described Trinity synthetic reaction instrument, and centrifugation product, to adopt after deionized water and absolute ethanol washing product in-20 ~-70 DEG C of freeze dryings successively, namely obtains the bar-shaped WS of two-dimensional matrix 2negative material.
2. the bar-shaped WS of a kind of two-dimensional matrix according to claim 1 2the preparation method of negative material, is characterized in that: in described step one and step 2, stirs and adopts magnetic stirring apparatus.
3. the bar-shaped WS of a kind of two-dimensional matrix according to claim 1 2the preparation method of negative material, is characterized in that: the ultrasonic power of described Trinity synthetic reaction instrument controls at 100 ~ 800W, and microwave power controls at 200 ~ 1000W, and UV power controls at 300W.
4. the bar-shaped WS of a kind of two-dimensional matrix according to claim 1 2the preparation method of negative material, is characterized in that: in described step 4, and cryodesiccated vacuum degree is 0.0 ~ 10.0Pa, and sublimation drying is 3 ~ 8h.
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