CN104953119B - A kind of bar-shaped WS of two-dimensional matrix2The preparation method of negative material - Google Patents

A kind of bar-shaped WS of two-dimensional matrix2The preparation method of negative material Download PDF

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CN104953119B
CN104953119B CN201510310069.9A CN201510310069A CN104953119B CN 104953119 B CN104953119 B CN 104953119B CN 201510310069 A CN201510310069 A CN 201510310069A CN 104953119 B CN104953119 B CN 104953119B
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negative material
bar
shaped
aqueous solution
dimensional matrix
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CN104953119A (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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of two-dimensional matrix bar-shaped WS2The preparation method of negative material：Tungsten powder addition hydrogen peroxide is obtained into solution A；Dilute and add L cysteine and trisodium citrate to form precursor aqueous solution solution A using isopropanol, pour precursor aqueous solution into ultrasonic microwave ultraviolet Trinity synthetic reaction instrument, the insulation of ultrasound wave, microwave and ultraviolet synthesis model is opened simultaneously, centrifugation product, washing, lyophilization successively, that is, obtain the bar-shaped WS of two-dimensional matrix2Negative material, the present invention realize WS2The controlledly synthesis of negative material, and prepared WS2Negative material has the preferably chemical property such as high power capacity.

Description

A kind of bar-shaped WS of two-dimensional matrix2The preparation method of negative material
Technical field
The present invention relates to one kind prepares the bar-shaped WS of two-dimensional matrix2The method of negative material, more particularly to a kind of citric acid three The ultraviolet synthetic method of sodium complexation ultrasonic microwave prepares the bar-shaped WS of two-dimensional matrix2The method of negative material.
Background technology
WS2Crystal structure and MoS2It is similar, and the layer structure of close-packed hexagonal.Have between tungsten atom and sulphur atom strong Chemical bond is connected, and is connected by weak molecular link between interlayer sulphur atom and sulphur atom.Adhesion between layers is still For Van der Waals force, with MoS2Compare, WS2Interlamellar spacing it is larger, coefficient of friction is lower, between 0.03～0.05.
WS2Almost all do not dissolve in all of medium, including water, oil, alkali and almost all of acid.But it to dissociate Gaseous fluorine, hot sulphuric acid compare sensitive with Fluohydric acid..WS2Heat stability also preferably, its decomposition temperature in an atmosphere is 510 DEG C, 539 DEG C of rapid oxidations, in vacuum, decomposition temperature is 1150 DEG C.WS2Radiation resistance be better than graphite, MoS2, with good Greasy property, is applicable not only to usual lubricating condition, and can be used for high temperature, high pressure, fine vacuum, high load capacity, have radiation and Be corrosive the harsh working environment such as medium.This also fully shows WS2Can be used as stable battery electrode material.
Nanometer WS2The focus of the area researches such as domestic outer chemical, physics, material science is become, except being widely used in It is outer in terms of solid lubrication, there is huge application potential at aspects such as catalyst, electrode material, electron probes.Especially WS2Make Cause the extensive concern of people for lithium ion battery and sodium ion battery electrode material.Report that vacuum impregnation technology is prepared in order Mesoporous WS2Anode material for lithium-ion batteries [Hao Liu, Dawei Su, Guoxiu Wang, Shi Zhang Qiao.An ordered mesoporous WS2anode material with superior electrochemical performance for lithium ion batteries[J].J.Mater.Chem.,2012,22:17437-17440.]； Gas-phase presulfiding reaction method is prepared for WS2Nano-particle and WS2Nanotube [A Margolin, F L Deepak, R Popovitz- Biro,et al,Fullerene-like WS2nanoparticles and nanotubes by the vapor-phase synthesis of WCln and H2S[J].Nanotechnology,200,19:95601-95611.]；Chemical vapor deposition Method is prepared for the WS of lamellar self assembly2Bouquet (CVD) [Arunvinay Prabakaran, Frank Dillon, Jodie Melbourne,et al.WS2 2D nanosheets in 3D nanoflowers[J].Chem.Commun.2014,50: 12360-12362.]；Surface active agent assisting alcohol-hydrothermal method is prepared for WS2Nanometer rods [Guogang Tang, Hua Tang, Changsheng Li,Wenjing Li,Xiaorui Ji.Surfactant-assisted hydrothermal synthesis and characterization of WS2nanorods[J]. Materials Letters.2011,65: 3457-3460.].In addition, being prepared for WS using hydro-thermal method2- Graphene be combined sodium-ion battery positive material [Dawei Su, Shixue Dou, Guoxiu Wang.WS2@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 be prepared for WS2- 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 WS2composites for fast and reversible Li+ storage[J].Nanoscale,2013,5:7890-7896.].But, it is relevant to prepare the bar-shaped WS of single nanometer two-dimensional matrix2 Research and less as the relevant report of anode material of lithium-ion battery.
The preparation WS for being reported at present2The method of material mainly have thermal decomposition method [Zhu Yajun, Zhang Xuebin, Ji Yi etc. nanometer The preparation method and application [J] of tungsten disulfide and molybdenum bisuphide. Chemical Industry in Guangzhou, 2012,3 (40):4-6.]；Solid-gas vulcanize 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 WS2Nanotubes from WS2 Inorganic 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 WS2 nanoparticles and nanotubes by the vapor-phase synthesis of WCln and H2S[J] .Nanotechnology.2008,19:95601-95611.]；Spray pyrolysis [Seung Ho Choi, Yun Chan Kang.Sodium ion storage properties of WS2-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 WS2 nanosheets by a novel mechanical activation method[J].Materials Letters,2010,64:856-858.] also have Precipitation reducing process [Zheng loses all, Song Xuchun, Liu Bo, Han Gui, Xu Zhude. nested spherical stratiform enclosed construction nano tungsten disulfide Synthesis and Exploration of Mechanism [J]. Journal of Inorganic Materials, 2004,3 (19):653-656.]；Precipitation reducing process, thermal decomposition method and solid phase Sulfuration method synthesizes WS under the conditions of high-temperature atmosphere2, powder body is easily reunited and process conditions are difficult to control to, to preparing WS2Required original The utilization rate very little of material；And solid phase method sinters under the conditions of reducing atmosphere or vulcanization reaction occurs, can also cause nanometer Brilliant reunion, abnormal grain growth, the microstructure of material are difficult to.Meanwhile, evaporation in situ and chemical vapour deposition technique To equipment requirements, the proportioning of high and reactant is difficult to control to, and prepared WS2Impurity is readily incorporated in nano material, and Powder body is easily reunited.In addition, hydro-thermal method and solvent-thermal method need nano material is prepared under high temperature and high pressure environment, and to equipment Have high demands, poor stability.
The content of the invention
It is an object of the invention to provide a kind of bar-shaped WS of two-dimensional matrix2The preparation method of negative material.
To reach above-mentioned purpose, technical scheme below is present invention employs：
Step one：After 1.0～6.0g tungsten powders are added in the aqueous hydrogen peroxide solution that 10～80mL mass fractions are 30% 0.5～4h of stirring, filters after stirring, filters gained filtrate and is designated as solution A；
Step 2：Solution A is diluted into 0.5～3 times using isopropanol, L-Cysteine is added in the solution A after dilution And trisodium citrate, and precursor aqueous solution after continuing 0.5～3h of stirring, is formed, in precursor aqueous solution, the concentration of L-Cysteine is 0.04～4.0mol/L, in precursor aqueous solution, the concentration of trisodium citrate is 4.0～10.0g/L；
Step 3：Pour precursor aqueous solution the reaction vessel of the ultraviolet Trinity synthetic reaction instrument of ultrasonic microwave into In, the compactedness of reaction vessel is controlled 30～60%, then reaction vessel is put in the Trinity synthetic reaction instrument；So Afterwards, while opening ultrasound wave, microwave and ultraviolet synthesis model, will be the forerunner in reaction vessel molten using 5～40min of microwave Jing Liquid is heated to 50～120 DEG C from room temperature, is then incubated 0.5～4h, and insulation naturally cools to room temperature after terminating；
Step 4：After step 3, the Trinity synthetic reaction instrument, and centrifugation product are opened, product is Grey black is precipitated, and is done after -20～-70 DEG C of freezings for 4～6 times using deionized water and dehydrated alcohol repeated washing product successively It is dry, that is, obtain the bar-shaped WS of two-dimensional matrix2Negative material.
In the step one and step 2, stirring is using Mettler-Toledo Instrument's production The magnetic stirring apparatuss of model RCT B S25.
In the step 3, microwave ultraviolet ultrasound wave Trinity synthetic reaction instrument adopts the new instrument microwave chemical in Shanghai The model of Science and Technology Ltd.'s manufacture：UWave-1000.
The ultrasonic power control of the Trinity synthetic reaction instrument in 100～800W, microwave power control 200～ 1000W, UV power are controlled in 300W.
In the step 4, cryodesiccated vacuum is 0.0～10.0Pa, and sublimation drying is 3～8h, is freezed dry Model of the dry machine using the manufacture of Beijing development in science and technology company limited of Song Yuan Huaxing：LGJ-10.
Beneficial effects of the present invention are embodied in：
As the present invention prepares the bar-shaped WS of two-dimensional matrix2The reaction of negative material once complete in low-temperature atmosphere-pressure liquid phase and Process equipment is simple, it is not necessary to the crystallization and thermal treatment in later stage, so as to avoid WS2Negative material may cause in heat treatment process Reunion, grain coarsening and atmosphere reaction introduce the defect such as impurity.Meanwhile, reunion lesser extent, it is possible to use relatively inexpensive Raw material obtains the bar-shaped WS of two-dimensional matrix that crystal grain is uniform and pattern is single2Negative material.Importantly, microwave ultraviolet is super Equipment and instrument that sound wave synthetic method is required is more simple and preferable, the oriented growth pattern that can produce more efficiently at out crystallinity Single, particle diameter is less and is evenly distributed, the higher WS of purity2.Using isopropanol as solvent, trisodium citrate Complexation conditions Under, green, cleaning, harmless and more conducively WS2Oriented growth, thin rod is self-assembled into two-dimensional matrix rod structure, so more high Effect, economic, safety.Additionally, microwave heating efficiency is higher, be conducive to quick diffusion mass transfer under ultrasound wave and ultraviolet effect, can With nucleation-oriented growth at short notice, WS is finally realized2The controlledly synthesis of negative material, and prepared WS2Negative material With the preferably chemical property such as high power capacity.
Description of the drawings
Fig. 1 is WS prepared by the embodiment of the present invention 12The XRD figure of nanocrystalline negative material；
Fig. 2 is WS prepared by the embodiment of the present invention 12The SEM figures of nanocrystalline negative material；
Fig. 3 is WS prepared by the embodiment of the present invention 12Cycle performance figure (the electric current density of nanocrystalline negative material：200mA g-1；Voltage：0～3V).Discharge:Electric discharge, Charge:Charge.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is elaborated.
Embodiment 1：
Step one：1.5g analytically pure tungsten powder is slowly added to into the aqueous hydrogen peroxide solution that 20mL mass fractions are 30% In, and be constantly sufficiently stirred for, it is to avoid substantial amounts of heat is released in reaction, filters, remove precipitate after reaction 1h, the filtrate note for obtaining For solution A；
Step 2：Solution A is diluted into 1 times using isopropanol again, and adds L-Cysteine, control L-Cysteine concentration For 0.04mol/L, while adding analytically pure trisodium citrate, it is 4.0g/L to control trisodium citrate addition, and continues to stir Uniform precursor aqueous solution is formed after mixing 1h；
Step 3：Pour precursor aqueous solution into UWave-1000 type ultrasonic microwaves ultraviolet Trinity synthetic reaction instrument Four neck round-bottom flasks in, compactedness is controlled 60%, then four neck round-bottom flasks is put into the Trinity synthetic reaction instrument In, and fix；The ultraviolet synthesis model of ultrasonic microwave is opened simultaneously (adopts the ultraviolet synthesis mould of ultrasonic microwave Formula so as to which, while acting on pre-reaction material, wherein in 200W, microwave power is controlled in 300W, ultraviolet for ultrasonic power control Power Control is in 300W), precursor aqueous solution is heated to into 60 DEG C from room temperature using microwave Jing 10min, 4h is then incubated, insulation terminates After naturally cool to room temperature；
Step 4：Open the ultraviolet Trinity synthetic reaction instrument of UWave-1000 type ultrasonic microwaves, centrifugation Product, is placed in temperature for -20 DEG C after adopting deionized water and dehydrated alcohol repeated washing 4 times successively, and vacuum is cold for 2.0Pa's 8h is dried in lyophilizer and obtains WS2It is nanocrystalline.
WS prepared by embodiment 1 as seen from Figure 12Nanocrystalline purity is high, and diffraction maximum is more sharp, and is single six side Phase WS2, the PDF 84-1399WS with standard2Card matches.
WS prepared by embodiment 1 as seen from Figure 22Nanocrystalline pattern is homogeneous, even size distribution, without substantially reunion, Self assembly two-dimensional matrix rod structure is presented, the length of rod is 2 μm.
WS by prepared by Fig. 3 can draw embodiment 12It is nanocrystalline, as anode material of lithium-ion battery voltage be 0 ～3V, electric current density are 200mA g-1Under the conditions of charge-discharge performance, initial discharge capacity be 385mAh g-1, circulation time After number (Cycle Number) reaches 50 times, prepared material still maintains 295mAh g-1Capacity (Capacity), capacity Conservation rate is higher.
Embodiment 2：
Step one：6.0g analytically pure tungsten powder is slowly added to into the aqueous hydrogen peroxide solution that 80mL mass fractions are 30% In, and be constantly sufficiently stirred for, it is to avoid substantial amounts of heat is released in reaction, filters, remove precipitate after reaction 3h, the filtrate note for obtaining For solution A；
Step 2：Solution A is diluted into 2.5 times using isopropanol again, and adds L-Cysteine, control L-Cysteine is dense Spend for 2mol/L, while add analytically pure trisodium citrate, control trisodium citrate addition for 8.0g/L, and continue to stir Uniform precursor aqueous solution is formed after 3h；
Step 3：Pour precursor aqueous solution into UWave-1000 type ultrasonic microwaves ultraviolet Trinity synthetic reaction instrument Four neck round-bottom flasks in, compactedness is controlled 45%, then four neck round-bottom flasks is put into the Trinity synthetic reaction instrument In, and fix；The ultraviolet synthesis model of ultrasonic microwave is opened simultaneously (adopts the ultraviolet synthesis mould of ultrasonic microwave Formula so as to which, while acting on pre-reaction material, wherein in 700W, microwave power is controlled in 800W, ultraviolet for ultrasonic power control Power Control is in 300W), precursor aqueous solution is heated to into 120 DEG C from room temperature using microwave Jing 30min, 3.5h is then incubated, is incubated Room temperature is naturally cooled to after end；
Step 4：Open the ultraviolet Trinity synthetic reaction instrument of UWave-1000 type ultrasonic microwaves, centrifugation Product, is placed in temperature for -70 DEG C after adopting deionized water and dehydrated alcohol repeated washing 5 times successively, and vacuum is 10.0Pa's 7h is dried in freezer dryer and obtains WS2It is nanocrystalline.
The WS of gained2It is nanocrystalline for single hexagonal phase WS2, the PDF 84-1399WS with standard2Card matches；Present certainly Assembling two-dimensional matrix rod structure, the length of rod is 3.5 μm；It is 0～3V in voltage as anode material of lithium-ion battery, electric current is close Spend for 200mA g-1Under the conditions of, initial discharge capacity is 405mAh g-1, cycle-index (Cycle Number) reaches 50 times Afterwards, prepared material still maintains 310mAh g-1Capacity (Capacity).
Embodiment 3：
Step one：4.0g analytically pure tungsten powder is slowly added to into the aqueous hydrogen peroxide solution that 60mL mass fractions are 30% In, and be constantly sufficiently stirred for, it is to avoid substantial amounts of heat is released in reaction, filters, remove precipitate, the filtrate for obtaining after reaction 2.5h It is designated as solution A；
Step 2：Solution A is diluted into 2 times using isopropanol again, and adds L-Cysteine, control L-Cysteine concentration For 1.0mol/L, while adding analytically pure trisodium citrate, it is 6.0g/L to control trisodium citrate addition, and continues stirring Uniform precursor aqueous solution is formed after 2h；
Step 3：Pour precursor aqueous solution into UWave-1000 type ultrasonic microwaves ultraviolet Trinity synthetic reaction instrument Four neck round-bottom flasks in, compactedness is controlled 45%, then four neck round-bottom flasks is put into the Trinity synthetic reaction instrument In, and fix；The ultraviolet synthesis model of ultrasonic microwave is opened simultaneously (adopts the ultraviolet synthesis mould of ultrasonic microwave Formula so as to which, while acting on pre-reaction material, wherein in 500W, microwave power is controlled in 600W, ultraviolet for ultrasonic power control Power Control is in 300W), precursor aqueous solution is heated to into 100 DEG C from room temperature using microwave Jing 25min, 3.5h is then incubated, is incubated Room temperature is naturally cooled to after end；
Step 4：Open the ultraviolet Trinity synthetic reaction instrument of UWave-1000 type ultrasonic microwaves, centrifugation Product, is placed in temperature for -50 DEG C after adopting deionized water and dehydrated alcohol repeated washing 6 times successively, and vacuum is cold for 9.0Pa's 5h is dried in lyophilizer and obtains WS2It is nanocrystalline.
The WS of gained2It is nanocrystalline for single hexagonal phase WS2, the PDF 84-1399WS with standard2Card matches；Present certainly Assembling two-dimensional matrix rod structure, the length of rod is 3 μm；As anode material of lithium-ion battery voltage be 0～3V, electric current density For 200mA g-1Under the conditions of, initial discharge capacity is 395mAh g-1, after cycle-index (Cycle Number) reaches 50 times, institute The material of preparation still maintains 305mAh g-1Capacity (Capacity).
Embodiment 4：
Step one：2.0g analytically pure tungsten powder is slowly added to into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% In, and be constantly sufficiently stirred for, it is to avoid substantial amounts of heat is released in reaction, filters, remove precipitate, the filtrate for obtaining after reaction 1.5h It is designated as solution A；
Step 2：Solution A is diluted into 1.5 times using isopropanol again, and adds L-Cysteine, control L-Cysteine is dense Spend for 0.08mol/L, while adding analytically pure trisodium citrate, it is 5.0g/L control trisodium citrate addition, and is continued Uniform precursor aqueous solution is formed after stirring 1.5h；
Step 3：Pour precursor aqueous solution into UWave-1000 type ultrasonic microwaves ultraviolet Trinity synthetic reaction instrument Four neck round-bottom flasks in, compactedness is controlled 50%, then four neck round-bottom flasks is put into the Trinity synthetic reaction instrument In, and fix；The ultraviolet synthesis model of ultrasonic microwave is opened simultaneously (adopts the ultraviolet synthesis mould of ultrasonic microwave Formula so as to which, while acting on pre-reaction material, wherein in 300W, microwave power is controlled in 400W, ultraviolet for ultrasonic power control Power Control is in 300W), precursor aqueous solution is heated to into 80 DEG C from room temperature using microwave Jing 15min, 3h is then incubated, insulation terminates After naturally cool to room temperature；
Step 4：Open the ultraviolet Trinity synthetic reaction instrument of UWave-1000 type ultrasonic microwaves, centrifugation Product, is placed in temperature for -40 DEG C after adopting deionized water and dehydrated alcohol repeated washing 5 times successively, and vacuum is cold for 4.0Pa's 6h is dried in lyophilizer and obtains WS2It is nanocrystalline.
The WS of gained2It is nanocrystalline for single hexagonal phase WS2, the PDF 84-1399WS with standard2Card matches；Present certainly Assembling two-dimensional matrix rod structure, the length of rod is 2.5 μm；It is 0～3V in voltage as anode material of lithium-ion battery, electric current is close Spend for 200mA g-1Under the conditions of, 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 gained2It is nanocrystalline for single hexagonal phase WS2, the PDF 84-1399WS with standard2Card phase It coincide；Self assembly two-dimensional matrix rod structure is presented, the length of rod is 1～5 μm；As anode material of lithium-ion battery in voltage it is 0～3V, electric current density are 200mA g-1Under the conditions of, initial discharge capacity is 380～405mAh g-1, cycle-index (Cycle Number, after) reaching 50 times, prepared material still maintains 290～320mAh g-1Capacity (Capacity).
In a word, the present invention proposes a kind of simple, economic, the technology of preparing of efficient anode material of lithium-ion battery, the skill Art regulation and control prepare the bar-shaped WS of single two-dimensional matrix2Nanocrystalline, simple green is efficiently controllable and can be added by control chelating agent Enter the pattern and component of the regulation and control product such as amount and precursor aqueous solution proportioning, and it is higher than hydro-thermal method, microwave-hydrothermal method and solvent-thermal method Effect is quick, simple and safe, and nucleation rate is very fast, and supersonic vibration promotes component homogeneous reaction and nucleation and morphology controllable.The present invention Low-temperature atmosphere-pressure under the conditions of the bar-shaped WS of two-dimensional matrix made by the ultraviolet synthetic method of trisodium citrate complexation ultrasonic microwave2Receive The brilliant purity of rice is high, and good dispersion, size uniform, pattern are homogeneous, and with higher capacity, effectively improve WS2Nanocrystalline ratio Surface area and chemical property.

Claims (4)

1. the bar-shaped WS of a kind of two-dimensional matrix2The preparation method of negative material, it is characterised in that：Comprise the following steps：
Step one：By 1.0 ~ 6.0g tungsten powders add 10 ~ 80mL mass fractions be 30% aqueous hydrogen peroxide solution in after stirring 0.5 ~ 4h, filters after stirring, filters gained filtrate and is designated as solution A；
Step 2：Solution A is diluted into 0.5 ~ 3 times using isopropanol, L-Cysteine and lemon are added in the solution A after dilution Lemon acid trisodium, and forms precursor aqueous solution after continuing 0.5 ~ 3h of stirring, in precursor aqueous solution the concentration of L-Cysteine be 0.04 ~ 4.0mol/L, in precursor aqueous solution, the concentration of trisodium citrate is 4.0 ~ 10.0g/L；
Step 3：Precursor aqueous solution is poured in the reaction vessel of the ultraviolet Trinity synthetic reaction instrument of ultrasonic microwave, is reacted The compactedness of container is controlled 30 ~ 60%, then reaction vessel is put in the Trinity synthetic reaction instrument；Then, while beating Open ultrasound wave, microwave and ultraviolet synthesis model, the precursor aqueous solution in reaction vessel is heated to 50 from room temperature by 5 ~ 40min of Jing ~ 120 DEG C, 0.5 ~ 4h is then incubated, insulation naturally cools to room temperature after terminating；
Step 4：After step 3, the Trinity synthetic reaction instrument, and centrifugation product are opened, adopt successively and go Ionized water and absolute ethanol washing product obtain the bar-shaped WS of two-dimensional matrix after -20 ~ -70 DEG C of lyophilizations2Negative material.
2. the bar-shaped WS of a kind of two-dimensional matrix according to claim 12The preparation method of negative material, it is characterised in that：The step Rapid one and step 2 in, stirring adopt magnetic stirring apparatuss.
3. the bar-shaped WS of a kind of two-dimensional matrix according to claim 12The preparation method of negative material, it is characterised in that：Described three In 100 ~ 800W, microwave power is controlled in 200 ~ 1000W, UV power control for the ultrasonic power control of position one synthetic reaction instrument System is in 300W.
4. the bar-shaped WS of a kind of two-dimensional matrix according to claim 12The preparation method of negative material, it is characterised in that：The step In rapid four, cryodesiccated vacuum is 0.0 ~ 10.0Pa, and sublimation drying is 3 ~ 8h.
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