CN105047862B - A kind of WS2The preparation method of biology in situ carbon compound cathode materials - Google Patents
A kind of WS2The preparation method of biology in situ carbon compound cathode materials Download PDFInfo
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- H01M4/362—Composites
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
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- 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
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- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The present invention provides a kind of WS2The preparation method of biology in situ carbon compound cathode materials：Disodium tungstate (Na2WO4) dihydrate and thiocarbamide and beta cyclodextrin and gossypose are added in deionized water and sonic oscillation fully dissolves, using salt acid for adjusting pH to 3~7, then sonic oscillation, obtains suspension；Suspension is put into high flux super-pressure microwave dissolver and reacted, product is taken out, washs successively, be freeze-dried i.e. acquisition WS2Biology in situ carbon compound cathode materials.The present invention is a kind of simple green, and can be by the method for the pattern and component for the regulation and control product such as control precursor aqueous solution to match, and efficiently quicker than common hydro-thermal method and solvent-thermal method, nucleation rate is very fast, the WS being made2Biology in situ carbon compound cathode materials purity is high, and good dispersion, size uniform, pattern is homogeneous, while having high rate capability.
Description
Technical field
High magnification WS is prepared the present invention relates to one kind2The method of-biology in situ carbon composite, more particularly to a kind of ultrasound
Auxiliary microwave hydrothermal method method prepares WS2The method that-biology in situ carbon is combined anode material of lithium-ion battery.
Background technology
WS2Crystal structure and MoS2It is similar, it is also the layer structure of close-packed hexagonal.Have between tungsten atom and sulphur atom strong
Chemical bond is connected, and is connected between interlayer sulphur atom and sulphur atom by weak molecular link.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 dissolved in all media, including water, oil, alkali and almost all of acid.But it is to free
Gaseous fluorine, hot sulfuric acid are compared sensitive with hydrofluoric acid.WS2Heat endurance it is also preferable, its decomposition temperature in an atmosphere is 510
DEG C, 539 DEG C of rapid oxidations, decomposition temperature is 1150 DEG C in vacuum.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, high vacuum, high load capacity, have radiation and
Be corrosive the harsh working environment such as medium.This also fully shows WS2Stable battery electrode material can be used as.
Nanometer WS2The focus of the area researches such as domestic outer chemical, physics, material science is turned into, except being widely used in
It is outer in terms of solid lubrication, there is huge application potential in terms of catalyst, electrode material, electron probe.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]；
Thermal decomposition-reversion method is prepared for WS2- carbon nano tube compound material [Raymond L.D.Whitby, Wen Kuang Hsu,
Peter K.Fearon et al,Multiwalled Carbon Nanotubes Coated with Tungsten
Disulfide[J].Chem.Mater.,2002,14:2209-2217]；In addition, being prepared for WS using hydro-thermal method2- graphene is multiple
Close 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 surfactant it is auxiliary
Hydro-thermal method is helped to 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, relevant WS2Research to biology in situ carbon composite and it is used as the related of anode material of lithium-ion battery
Report is less.
The preparation WS reported at present2The method of material mainly has thermal decomposition method [Zhu Yajun, Zhang Xuebin, nanometers of Ji Yi etc.
Preparation method and application [J] Chemical Industry in Guangzhou of tungsten disulfide and molybdenum disulfide, 2012,3 (40):4-6.], solid-gas vulcanization 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 WS2Inorganic
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
WS2nanoparticles 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]；Also precipitate reducing process [Zheng
Lose all, Song Xuchun, Liu Bo, Han Gui, the synthesis of the nested spherical stratiform enclosed construction nano tungsten disulfides of Xu Zhu morals and Exploration of Mechanism
[J] Journal of Inorganic Materials, 2004,3 (19):653-656.]；Chemical vapour deposition technique (CVD) [Arunvinay
Prabakaran,Frank Dillon,Jodie Melbourne,et al.WS22D nanosheets in 3D
nanoflowers[J].Chem.Commun.2014,50:12360-12362].Precipitate reducing process, thermal decomposition method and solid phase vulcanizing
Method synthesizes WS under the conditions of high-temperature atmosphere2, powder is easily reunited and process conditions are difficult to control to, to preparing WS2Required raw material
Utilization rate very little；And solid phase method sinters under the conditions of reducing atmosphere or occurs vulcanization reaction, it can also cause nanocrystalline
Reunite, abnormal grain growth, the microstructure of material is difficult to regulate and control.Meanwhile, evaporation in situ and chemical vapour deposition technique pair are set
It is standby to require that high and reactant proportioning is difficult to control to, in addition, prepared WS2Impurity, and powder are readily incorporated in nano material
Body is easily reunited.
The content of the invention
It is an object of the invention to provide a kind of WS2The preparation method of-biology in situ carbon compound cathode materials.
To reach above-mentioned purpose, present invention employs following technical scheme：
Step one：Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are added in deionized water, and be stirred continuously to Disodium tungstate (Na2WO4) dihydrate and
Thiocarbamide dissolves, and then 20~60min of sonic oscillation, obtains mixed solution A；The ratio between amount of material of tungsten and sulphur in mixed solution A
For (1~4): (1~4), it is 0.005~0.2molL to control Disodium tungstate (Na2WO4) dihydrate and the total concentration of thiocarbamide in mixed solution A-1；
Step 2：Beta-schardinger dextrin and gossypose are added into mixed solution A, then makes beta-schardinger dextrin in 30~70 DEG C of stirrings
With gossypose dissolving, then 20~60min of sonic oscillation, obtains mixed solution B；Control beta-schardinger dextrin and cotton in mixed solution B
The mass fraction sum of sub- sugar is 5~50%, and the mass ratio of beta-schardinger dextrin and gossypose is (1~5): (2~7)；
Step 3：Using 1~4molL-1Hydrochloric acid regulation mixed solution B pH to 3~7, then sonic oscillation 30~
90min, obtains suspension；
Step 4：Suspension is poured into microwave hydrothermal kettle, the control of the compactedness of microwave hydrothermal kettle is 45~65%, then
Microwave hydrothermal kettle is sealed, the microwave hydrothermal kettle after sealing is put into high flux super-pressure microwave dissolver and reacted, is controlled
Reaction temperature is 120~260 DEG C, and reaction pressure is 2~10MPa, and the reaction time is 0.5~5h, and reaction terminates rear natural cooling
To room temperature；
Step 5：After step 4, the microwave hydrothermal kettle is opened, product is taken out, product is black precipitate, is adopted successively
With deionized water and absolute ethyl alcohol repeated washing product 4~6 times WS is obtained after -30~-70 DEG C of freeze-dryings2- in situ raw
Thing carbon compound cathode materials.
In the step one and step 2, stirring is produced using Mettler-Toledo Instrument (Shanghai) Co., Ltd.
Model RCT B S25 magnetic stirring apparatus.
The step one is into step 3, and sonic oscillation uses high power numerical control ultrasonic cleaner (city of Kunshan's Ultrasound Instrument
The model of device Co., Ltd production：KQ-1000KDB), the power of sonic oscillation is 300~1000W.
The high flux super-pressure microwave dissolver uses the model that Xinyi Microwave Chemistry Tech Co., Ltd. manufactures：
MDS-10。
In the step 5, the LGJ-10 freezings that freeze-drying is manufactured using Beijing development in science and technology Co., Ltd of Song Yuan Huaxing
Drying machine, the vacuum for controlling freeze-drying is 0.0~10.0Pa, and sublimation drying is 4~8h.
Beneficial effects of the present invention are embodied in：
Because the present invention once completes to prepare WS in the liquid phase2- biology in situ carbon composite and process equipment are simple, no
The crystallization and thermal treatment in later stage is needed, so as to avoid a nanometer WS2In heat treatment process may caused by reunite, grain coarsening and
Atmosphere reaction introduces the defects such as impurity.Meanwhile, relatively inexpensive raw material can be used to obtain crystal grain uniformly, reunion lesser extent and shape
The single WS of looks2- biology in situ carbon composite.Importantly, the equipment and instrument of microwave-hydrothermal method requirement are more simple
And it more efficient can rapidly prepare crystallinity preferably, particle diameter is smaller and is evenly distributed, the WS of morphology controllable2- biology in situ
Carbon composite.Biological carbon source, green, cleaning, harmless and more conducively nanometer WS are used as using beta-schardinger dextrin and gossypose2Knot
Structure regulates and controls and composite modified, so highly efficient, economical, feasible.In addition, the microwave efficiency of heating surface is higher, have under thermal and hydric environment
Beneficial to quick diffusion mass transfer, can nucleation-growth in a short time, finally realize nanometer WS2Synthesis and beta-schardinger dextrin and cotton seed
Sugar charcoal, cracking reaction in-situ are carried out simultaneously, and prepared WS2- biology in situ carbon composite has preferable electrochemistry
Performance, i.e., with excellent high rate during charging-discharging.
The present invention propose it is a kind of economical, efficiently, the mentality of designing of feasible anode material of lithium-ion battery：By nanometer WS2
It is compound as anode material of lithium-ion battery with biology in situ carbon material, it on the one hand can effectively realize WS2- biological carbon composite wood
Expect the regulation and control of microstructure, prepare the big electrode material of specific surface area；On the other hand, WS is effectively improved2The electric conductivity of material,
The chemical properties such as charge/discharge capacity.Importantly, compared with graphene, CNT and Super P etc., biological carbon materials
Material is economical and practical, and adjustable control is standby, so as to reduce the application cost of battery electrode material.
Brief description of the drawings
Fig. 1 is the WS prepared by the embodiment of the present invention 12The SEM figures of-biology in situ carbon compound cathode materials；
Fig. 2 is the WS prepared by the embodiment of the present invention 12The XRD of-biology in situ carbon compound cathode materials；
Fig. 3 is the WS prepared by the embodiment of the present invention 12- biology in situ carbon compound cathode materials are under different current densities
High rate performance figure (0~3V of voltage range)；Capacity:Charge/discharge capacity, Cycle number:Cycle-index.
Embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1：
Step one：By analytically pure Disodium tungstate (Na2WO4) dihydrate (Na2WO4·2H2) and thiocarbamide (CH O4N2S deionized water) is added
In, the ratio between control tungsten, amount of sulfur material are nW∶nS=1: 3, it is stirred continuously and is put into work(to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving
Rate is sonic oscillation 60min in 300W ultrasonic cleaner so that Disodium tungstate (Na2WO4) dihydrate and thiocarbamide fully dissolve, control mixing
Disodium tungstate (Na2WO4) dihydrate and the total concentration of thiocarbamide are 0.005molL in solution-1, this mixed solution is designated as solution A；
Step 2：Analytically pure beta-schardinger dextrin is added into solution A again and commercially available gossypose (Henan Tian Run biotechnologies
Co., Ltd produces, and purity is mixture 99.3%), and the mass ratio of beta-schardinger dextrin and gossypose is mBeta-schardinger dextrin∶mGossypose=1: 2,
It is wt%=5% to control beta-schardinger dextrin and the total addition of gossypose, and makes beta-schardinger dextrin and gossypose in 40 DEG C of heating stirrings
Fully dissolving, is then placed in sonic oscillation 20min in 300W ultrasonic cleaner, resulting solution is designated as solution B；
Step 3：Using 3molL-1HCl adjusts the pH to 4 of solution B, is then placed in 500W ultrasonic cleaner and surpasses
Sound oscillation 30min, obtains suspension；
Step 4：Above-mentioned suspension (precursor aqueous solution) is poured into microwave hydrothermal kettle, compactedness is controlled in 45%, Ran Houmi
Microwave hydrothermal kettle is sealed, the microwave hydrothermal kettle after sealing is put into high flux super-pressure microwave dissolver, microwave hydrothermal temperature is controlled
Spend for 140 DEG C, pressure is 2MPa, react 1.5h, reaction naturally cools to room temperature after terminating；
Step 5：Microwave hydrothermal kettle is opened, product is taken out, successively using deionized water and absolute ethyl alcohol repeated washing 4 times
It is placed in afterwards in the freeze drier that temperature is -40 DEG C, vacuum is 1.0Pa and dries 8h and obtain WS2- biology in situ carbon composite wood
Material.
WS prepared by embodiment 1 as seen from Figure 12- biology in situ carbon composite structures are uniform, and Size Distribution is equal
It is even, without substantially reunion, fine particle and the composite construction of sheet is presented, grain diameter is 80nm, and the thickness of nanometer sheet is 50nm.
WS prepared by embodiment 1 as seen from Figure 22There are two kinds of crystalline phases, respectively six in-biology in situ carbon composite
The WS of square phase2With hexagonal phase C, and diffraction peak intensity is stronger, respectively with the card PDF 84-1399 Hexagonal of standard
WS2Matched with PDF 74-2328 Hexagonal C.
As the WS prepared by Fig. 3 can draw embodiment 12- biology in situ carbon composite, is used as sodium-ion battery negative pole
Material is 0~3V in voltage, and current density is respectively 100mA g-1, 200mA g-1, 500mA g-1, 1000mA g-1, 2000mA
g-1Under the conditions of, the reversible storage sodium capacity of prepared material is respectively 504mAh g-1, 430mAh g-1, 384mAh g-1, 350mAh
g-1, 301mAh g-1, with excellent high rate during charging-discharging.
Embodiment 2：
Step one：By analytically pure Disodium tungstate (Na2WO4) dihydrate (Na2WO4·2H2) and thiocarbamide (CH O4N2S) it is separately added into deionization
In water, the ratio between control tungsten, amount of sulfur material are nW∶nS=2: 1, it is stirred continuously to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving and is put into
Power is sonic oscillation 20min in 1000W ultrasonic cleaner so that Disodium tungstate (Na2WO4) dihydrate and thiocarbamide fully dissolve, control
Disodium tungstate (Na2WO4) dihydrate and the total concentration of thiocarbamide are 0.015molL in mixed solution-1, this mixed solution is designated as solution A；
Step 2：Analytically pure beta-schardinger dextrin is added into solution A again and commercially available gossypose (Henan Tian Run biotechnologies
Co., Ltd produces, and purity is mixture 99.3%), and the mass ratio of beta-schardinger dextrin and gossypose is mBeta-schardinger dextrin∶mGossypose=5: 3,
The total addition for controlling beta-schardinger dextrin and gossypose is wt%=40%, and makes beta-schardinger dextrin and cotton seed in 65 DEG C of heating stirrings
Sugared fully dissolving, is then placed in sonic oscillation 20min in 1000W ultrasonic cleaner, resulting solution is designated as solution B；
Step 3：Using 1molL-1HCl adjusts the pH to 6.5 of solution B, is then placed in 1000W ultrasonic cleaner
Middle sonic oscillation 20min, obtains suspension；
Step 4：Above-mentioned suspension (precursor aqueous solution) is poured into microwave hydrothermal kettle, compactedness is controlled in 60%, Ran Houmi
Microwave hydrothermal kettle is sealed, the microwave hydrothermal kettle after sealing is put into high flux super-pressure microwave dissolver, microwave hydrothermal temperature is controlled
Spend for 200 DEG C, pressure is 8MPa, react 4.5h, reaction naturally cools to room temperature after terminating；
Step 5：Microwave hydrothermal kettle is opened, product is taken out, successively using deionized water and absolute ethyl alcohol repeated washing 5 times
It is placed in afterwards in the freeze drier that temperature is -55 DEG C, vacuum is 4.0Pa and dries 4h and obtain WS2- biology in situ carbon composite wood
Material.
Resulting WS2There are two kinds of crystalline phases, the respectively WS of hexagonal phase in-biology in situ carbon composite2With hexagonal phase C, it is in
The composite construction of existing fine particle and sheet, grain diameter is 30nm, and the thickness of nanometer sheet is 20nm；It is negative as sodium-ion battery
Pole material is 0~3V in voltage, and current density is respectively 100mA g-1, 200mA g-1, 500mA g-1, 1000mA g-1,
2000mA g-1Under the conditions of, the reversible storage sodium capacity of prepared material is respectively 520mAh g-1, 450mAh g-1, 398mAh g-1,
360mAh g-1, 310mAh g-1。
Embodiment 3：
Step one：By analytically pure Disodium tungstate (Na2WO4) dihydrate (Na2WO4·2H2) and thiocarbamide (CH O4N2S deionized water) is added
In, the ratio between control tungsten, amount of sulfur material are nW∶nS=1: 1, it is stirred continuously and is put into work(to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving
Rate is sonic oscillation 30min in 800W ultrasonic cleaner so that Disodium tungstate (Na2WO4) dihydrate and thiocarbamide fully dissolve, control mixing
Disodium tungstate (Na2WO4) dihydrate and the total concentration of thiocarbamide are 0.02molL in solution-1, this mixed solution is designated as solution A；
Step 2：Analytically pure beta-schardinger dextrin is added into solution A again and commercially available gossypose (Henan Tian Run biotechnologies
Co., Ltd produces, and purity is mixture 99.3%), and the mass ratio of beta-schardinger dextrin and gossypose is mBeta-schardinger dextrin∶mGossypose=3: 7,
The total addition for controlling beta-schardinger dextrin and gossypose is wt%=20%, and makes beta-schardinger dextrin and cotton seed in 55 DEG C of heating stirrings
Sugared fully dissolving, is then placed in sonic oscillation 30min in 800W ultrasonic cleaner, resulting solution is designated as solution B；
Step 3：Using 2molL-1HCl adjusts the pH to 6 of solution B, is then placed in 800W ultrasonic cleaner and surpasses
Sound oscillation 40min, obtains suspension；
Step 4：Above-mentioned suspension (precursor aqueous solution) is poured into microwave hydrothermal kettle, compactedness is controlled in 55%, Ran Houmi
Microwave hydrothermal kettle is sealed, the microwave hydrothermal kettle after sealing is put into high flux super-pressure microwave dissolver, microwave hydrothermal temperature is controlled
Spend for 180 DEG C, pressure is 6MPa, react 3h, reaction naturally cools to room temperature after terminating；
Step 5：Microwave hydrothermal kettle is opened, product is taken out, successively using deionized water and absolute ethyl alcohol repeated washing 6 times
It is placed in afterwards in the freeze drier that temperature is -50 DEG C, vacuum is 3.0Pa and dries 5h and obtain WS2- biology in situ carbon composite wood
Material.
Resulting WS2There are two kinds of crystalline phases, the respectively WS of hexagonal phase in-biology in situ carbon composite2With hexagonal phase C, it is in
The composite construction of existing fine particle and sheet, grain diameter is 40nm, and the thickness of nanometer sheet is 30nm；It is negative as sodium-ion battery
Pole material is 0~3V in voltage, and current density is respectively 100mA g-1, 200mA g-1, 500mA g-1, 1000mA g-1,
2000mA g-1Under the conditions of, the reversible storage sodium capacity of prepared material is respectively 515mAh g-1, 440mAh g-1, 395mAh g-1,
355mAh g-1, 308mAh g-1。
Embodiment 4：
Step one：By analytically pure Disodium tungstate (Na2WO4) dihydrate (Na2WO4·2H2) and thiocarbamide (CH O4N2S deionized water) is added
In, the ratio between control tungsten, amount of sulfur material are nW∶nS=1: 2, it is stirred continuously and is put into work(to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving
Rate is sonic oscillation 40min in 500W ultrasonic cleaner so that Disodium tungstate (Na2WO4) dihydrate and thiocarbamide fully dissolve, control mixing
Disodium tungstate (Na2WO4) dihydrate and the total concentration of thiocarbamide are 0.01molL in solution-1, this mixed solution is designated as solution A；
Step 2：Analytically pure beta-schardinger dextrin is added into solution A again and commercially available gossypose (Henan Tian Run biotechnologies
Co., Ltd produces, and purity is mixture 99.3%), and the mass ratio of beta-schardinger dextrin and gossypose is mBeta-schardinger dextrin∶mGossypose=2: 3,
The total addition for controlling beta-schardinger dextrin and gossypose is wt%=10%, and makes beta-schardinger dextrin and cotton seed in 50 DEG C of heating stirrings
Sugared fully dissolving, is then placed in sonic oscillation 40min in 500W ultrasonic cleaner, resulting solution is designated as solution B；
Step 3：Using 2.5molL-1HCl adjusts the pH to 5 of solution B, is then placed in 500W ultrasonic cleaner
Sonic oscillation 80min, obtains suspension；
Step 4：Above-mentioned suspension (precursor aqueous solution) is poured into microwave hydrothermal kettle, compactedness is controlled in 50%, Ran Houmi
Microwave hydrothermal kettle is sealed, the microwave hydrothermal kettle after sealing is put into high flux super-pressure microwave dissolver, microwave hydrothermal temperature is controlled
Spend for 160 DEG C, pressure is 4MPa, react 2h, reaction naturally cools to room temperature after terminating；
Step 5：Microwave hydrothermal kettle is opened, product is taken out, successively using deionized water and absolute ethyl alcohol repeated washing 5 times
It is placed in afterwards in the freeze drier that temperature is -45 DEG C, vacuum is 2.0Pa and dries 6h and obtain WS2- biology in situ carbon composite wood
Material.
Resulting WS2There are two kinds of crystalline phases, the respectively WS of hexagonal phase in-biology in situ carbon composite2With hexagonal phase C, it is in
The composite construction of existing fine particle and sheet, grain diameter is 60nm, and the thickness of nanometer sheet is 40nm；It is negative as sodium-ion battery
Pole material is 0~3V in voltage, and current density is respectively 100mA g-1, 200mA g-1, 500mA g-1, 1000mA g-1,
2000mA g-1Under the conditions of, the reversible storage sodium capacity of prepared material is respectively 510mAh g-1, 435mAh g-1, 390mAh g-1,
353mAh g-1, 305mAh g-1。
The preparation-obtained WS of the present invention2There are two kinds of crystalline phases, the respectively WS of hexagonal phase in-biology in situ carbon composite2
With hexagonal phase C, be presented the composite construction of fine particle and sheet, grain diameter is 20~100nm, the thickness of nanometer sheet for 10~
60nm；As anode material of lithium-ion battery voltage be 0~3V, current density is respectively 100mA g-1, 200mA g-1,
500mA g-1, 1000mA g-1, 2000mA g-1Under the conditions of, the reversible storage sodium capacity of prepared material is respectively 460~520mAh
g-1, 420~450mAh g-1, 370~400mAh g-1, 330~365mAh g-1, 290~315mAh g-1。
In a word, the present invention proposes that a kind of be combined ultrasonic technique with microwave hydrothermal technology prepares WS2- biology in situ carbon is answered
The technology of condensation material --- ultrasonic auxiliary microwave hydrothermal method technology of preparing, is a kind of simple green, and can be by controlling forerunner
The method of the pattern and component of the regulation and control product such as solution ratio, and, nucleation efficiently quicker than common hydro-thermal method and solvent-thermal method
Speed is very fast, and ultrasonic vibration promotes component homogeneous reaction and nucleation.The low temperature ultrasonic auxiliary microwave hydrothermal method preparation method of the present invention
The WS being made2- biology in situ carbon is combined anode material of lithium-ion battery purity height, and good dispersion, size uniform, pattern is homogeneous,
There is high rate capability simultaneously.
Claims (4)
1. a kind of WS2The preparation method of-biology in situ carbon compound cathode materials, it is characterised in that：Comprise the following steps：
Step one：Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are added in deionized water, and are stirred continuously to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide
Dissolving, then 20~60min of sonic oscillation, obtains mixed solution A；The ratio between amount of material of tungsten and sulphur is (1 in mixed solution A
~4): (1~4), it is 0.005~0.2molL to control Disodium tungstate (Na2WO4) dihydrate and the total concentration of thiocarbamide in mixed solution A-1；
Step 2：Beta-schardinger dextrin and gossypose are added into mixed solution A, then makes beta-schardinger dextrin and cotton in 30~70 DEG C of stirrings
Sub- sugar dissolving, then 20~60min of sonic oscillation, obtains mixed solution B；Control beta-schardinger dextrin and gossypose in mixed solution B
Mass fraction sum be 5~50%, the mass ratio of beta-schardinger dextrin and gossypose is (1~5): (2~7)；
Step 3：Mixed solution B pH to 3~7 is adjusted using 1~4mol/L hydrochloric acid, then 30~90min of sonic oscillation,
Obtain suspension；
Step 4：The suspension is poured into microwave hydrothermal kettle, the control of the compactedness of microwave hydrothermal kettle is 45~65%, then
Microwave hydrothermal kettle is sealed, the microwave hydrothermal kettle after sealing is put into high flux super-pressure microwave dissolver and reacted, is controlled
Reaction temperature is 120~260 DEG C, and reaction pressure is 2~10MPa, and the reaction time is 0.5~5h, and reaction terminates rear natural cooling
To room temperature；
Step 5：After step 4, the microwave hydrothermal kettle is opened, product is taken out, successively using deionized water and anhydrous second
Alcohol washing obtains WS after -30~-70 DEG C of freeze-dryings2- biology in situ carbon compound cathode materials.
2. a kind of WS according to claim 12The preparation method of-biology in situ carbon compound cathode materials, it is characterised in that：Institute
State in step one and step 2, stir the instrument used for magnetic stirring apparatus.
3. a kind of WS according to claim 12The preparation method of-biology in situ carbon compound cathode materials, it is characterised in that：Institute
Step one is stated into step 3, the instrument that sonic oscillation is used for ultrasonic cleaner, the power of sonic oscillation for 300~
1000W。
4. a kind of WS according to claim 12The preparation method of-biology in situ carbon compound cathode materials, it is characterised in that：Institute
State in step 5, the vacuum for controlling freeze-drying is 0.0~10.0Pa, sublimation drying is 4~8h.
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