CN105047862A - Preparation method for WS2-in situ biological carbon composite anode material - Google Patents

Preparation method for WS2-in situ biological carbon composite anode material Download PDF

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CN105047862A
CN105047862A CN201510312337.0A CN201510312337A CN105047862A CN 105047862 A CN105047862 A CN 105047862A CN 201510312337 A CN201510312337 A CN 201510312337A CN 105047862 A CN105047862 A CN 105047862A
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biology
mixed solution
beta
gossypose
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CN105047862B (en
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黄剑锋
王鑫
曹丽云
李嘉胤
程娅伊
殷立雄
许占位
费杰
郝巍
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Zhuhai Dongjie Technology 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
    • H01M4/362—Composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 WS2-in situ biological carbon composite anode material. The preparation method comprises the following steps of: adding sodium tungstate dihydrate, thiourea, Beta-cyclodextrin and raffinose into deionized water and carrying out ultrasonic oscillation for full dissolving; adjusting pH to be 3-7 by using hydrochloric acid; carrying out ultrasonic oscillation to obtain a suspension liquid; placing the suspension liquid in a high-throughput ultrahigh-pressure microwave digestion device for reaction; and taking out a product, and sequentially washing, freezing and drying the product to obtain the WS2-in situ biological carbon composite anode material. The preparation method is a simple and green method by which the morphology and the constituent of the product can be controlled through controlling the proportion of a precursor solution and the like; compared with the normal hydrothermal method and a solvothermal method, the preparation method has the advantages of high efficiency, rapidness and high nucleation rate; and the prepared WS2-in situ biological carbon composite anode material is high in purity and dispensability, is uniform in size and morphology, and is simultaneously endowed with high rate capability.

Description

A kind of WS 2the preparation method of-biology in situ carbon compound cathode materials
Technical field
The present invention relates to one and prepare high magnification WS 2the method of-biology in situ carbon composite, particularly a kind of ultrasonic auxiliary microwave hydrothermal method legal system is for WS 2the method of-biology in situ carbon compound anode material of lithium-ion battery.
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 [HaoLiu, DaweiSu, GuoxiuWang, ShiZhangQiao.AnorderedmesoporousWS 2anodematerialwithsuperiorelectrochemicalperformanceforli thiumionbatteries [J] .J.Mater.Chem., 2012,22:17437-17440]; Thermal decomposition-reversion legal system is for WS 2-carbon nano tube compound material [RaymondL.D.Whitby, WenKuangHsu, PeterK.Fearonetal, MultiwalledCarbonNanotubesCoatedwithTungstenDisulfide [J] .Chem.Mater., 2002,14:2209-2217]; In addition, hydro thermal method is adopted to prepare WS 2-Graphene compound sodium-ion battery positive material [DaweiSu, ShixueDou, GuoxiuWang.WS 2graphenenanocompositesasanodematerialsforNa-ionbatteries withenhancedelectrochemicalperformances [J] .Chem.Comm., 2014,50:4192-4195.] and surface active agent assisting alcohol-hydrothermal method prepared WS 2-nitrogen-doped graphene laminar composite [DongyunChen, GeJi, BoDing, YueMa, BaihuaQu, WeixiangChen, JimYangLee.Insitunitrogenatedgrapheme-few-layerWS 2compositesforfastandreversibleLi +storage [J] .Nanoscale, 2013,5:7890-7896].But, relevant WS 2with the research of biology in situ carbon composite and the relevant report as anode material of lithium-ion battery less.
The preparation WS reported at present 2the method of material mainly contains 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-HuiLi, YiMinZhao, RenZhiMa, YanQiuZhu, NilesFisher, YiZhengJin, XinPingZhang.NovelRoutetoWOxNanorodsandWS 2nanotubesfromWS 2inorganicFullerenes [J] .J.Phys.Chem.B.2006,110:18191-18195.], original position evaporation synthetic method [AMargolin, FLDeepak, RPopovitz-Biro, MBar-Sadan1, YFeldman, RTenne.Fullerene-likeWS 2nanoparticlesandnanotubesbythevapor-phasesynthesisofWCl nandH 2s [J] .Nanotechnology.2008,19:95601-95611.], spray pyrolysis [SeungHoChoi, YunChanKang.SodiumionstoragepropertiesofWS 2-decoratedthree-dimensionalreducedgrapheneoxidemicrospher es [J] .Nanoscale.2015,7:3965 – 3970]; Precipitate in addition reducing process [Zheng loses all, 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.]; Chemical vapour deposition technique (CVD) [ArunvinayPrabakaran, FrankDillon, JodieMelbourne, etal.WS 22Dnanosheetsin3Dnanoflowers [J] .Chem.Commun.2014,50:12360-12362].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, in addition, and prepared WS 2easily introduce impurity in nano material, and powder is easily reunited.
Summary of the invention
The object of the present invention is to provide a kind of WS 2the preparation method of-biology in situ carbon compound cathode materials.
For achieving the above object, present invention employs following technical scheme:
Step one: Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are added in deionized water, and be constantly stirred to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving, then sonic oscillation 20 ~ 60min, obtains mixed solution A; In mixed solution A, tungsten is (1 ~ 4) with the ratio of the amount of substance of sulphur: (1 ~ 4), and the concentration controlling Disodium tungstate (Na2WO4) dihydrate and thiocarbamide in mixed solution A total is 0.005 ~ 0.2molL -1;
Step 2: add beta-schardinger dextrin-and gossypose in mixed solution A, then 30 ~ 70 DEG C of stirrings, beta-schardinger dextrin-and gossypose are dissolved, then sonic oscillation 20 ~ 60min, obtains mixed solution B; The mass fraction sum controlling beta-schardinger dextrin-and gossypose in mixed solution B is 5 ~ 50%, and the mass ratio of beta-schardinger dextrin-and gossypose is (1 ~ 5): (2 ~ 7);
Step 3: adopt 1 ~ 4molL -1hydrochloric acid regulates pH to 3 ~ 7 of mixed solution B, and then sonic oscillation 30 ~ 90min, obtains suspension-turbid liquid;
Step 4: suspension-turbid liquid is poured in microwave hydrothermal still, the compactedness of microwave hydrothermal still controls 45 ~ 65%, then microwave hydrothermal still is sealed, microwave hydrothermal still after sealing is put into high flux superhigh pressure microwave dissolver react, controlling reaction temperature is 120 ~ 260 DEG C, reaction pressure is 2 ~ 10MPa, and the reaction time is 0.5 ~ 5h, naturally cools to room temperature after reaction terminates;
Step 5: after step 4, opens described microwave hydrothermal still, and take out product, product is black precipitate, namely obtains WS after adopting deionized water and absolute ethyl alcohol repeated washing product 4 ~ 6 times successively in-30 ~-70 DEG C of freeze dryings 2-biology in situ carbon compound cathode materials.
In described step one and step 2, stirring the model adopting Mettler-Toledo Instrument (Shanghai) Co., Ltd. to produce is the magnetic stirring apparatus of RCTBS25.
Described step one is in step 3, and sonic oscillation adopts high power numerical control ultrasonic cleaner (model that Kunshan Ultrasonic Instruments Co., Ltd. produces: KQ-1000KDB), and the power of sonic oscillation is 300 ~ 1000W.
The model that described high flux superhigh pressure microwave dissolver adopts Xinyi Microwave Chemistry Tech Co., Ltd. to manufacture: MDS-10.
In described step 5, the LGJ-10 freeze drier that freeze drying adopts Beijing development in science and technology Co., Ltd of Song Yuan Huaxing to manufacture, controlling cryodesiccated vacuum degree is 0.0 ~ 10.0Pa, and sublimation drying is 4 ~ 8h.
Beneficial effect of the present invention is embodied in:
Because the present invention once completes preparation WS in the liquid phase 2-biology in situ carbon composite and process equipment are simple, do not need the crystallization and thermal treatment in later stage, thus avoid nanometer WS 2the defects such as impurity are introduced in the reunion that may cause in heat treatment process, grain coarsening and atmosphere reaction.Meanwhile, more cheap raw material can be used to obtain uniform crystal particles, the comparatively light and WS that pattern is single of reunion degree 2-biology in situ carbon composite.The more important thing is, the equipment that microwave-hydrothermal method requires and instrument more simple and more efficiently can prepare crystallinity rapidly better, particle diameter is less and be evenly distributed, the WS of morphology controllable 2-biology in situ carbon composite.Adopt beta-schardinger dextrin-and gossypose as biological carbon source, green, clean, harmless and be more conducive to nanometer WS 2structure regulating and composite modified, so more efficient, economical, feasible.In addition, microwave heating efficiency is higher, is conducive to rapid diffusion mass transfer under thermal and hydric environment, can nucleation-growth at short notice, finally realizes nanometer WS 2synthesis is carried out with beta-schardinger dextrin-and gossypose carbonization, cracking reaction in-situ simultaneously, and prepared WS 2-biology in situ carbon composite has good chemical property, namely has excellent high rate during charging-discharging.
The present invention proposes a kind of economical, efficiently, and the mentality of designing of feasible anode material of lithium-ion battery: by nanometer WS 2with biology in situ material with carbon element compound as anode material of lithium-ion battery, effectively WS can be realized on the one hand 2the regulation and control of-biological carbon composite material microstructure, prepare the electrode material that specific area is large; On the other hand, effectively WS is improved 2the conductivity of material, the chemical properties such as charge/discharge capacity.The more important thing is, compared with Graphene, carbon nano-tube and SuperP etc., biological carbon material is economical and practical, and adjustable control is standby, thus reduces the application cost of battery electrode material.
Accompanying drawing explanation
The WS of Fig. 1 prepared by the embodiment of the present invention 1 2the SEM figure of-biology in situ carbon compound cathode materials;
The WS of Fig. 2 prepared by the embodiment of the present invention 1 2the XRD figure of-biology in situ carbon compound cathode materials;
The WS of Fig. 3 prepared by the embodiment of the present invention 1 2the high rate performance figure of-biology in situ carbon compound cathode materials under different current density (voltage range 0 ~ 3V); Capacity: charge/discharge capacity, Cyclenumber: cycle-index.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
Step one: by analytically pure Disodium tungstate (Na2WO4) dihydrate (Na 2wO 42H 2and thiocarbamide (CH O) 4n 2s) add in deionized water, the ratio of the amount of control tungsten, sulfur material is n w: n s=1: 3, the ultrasonic cleaner sonic oscillation 60min that power is 300W is put into after being constantly stirred to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving, Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are fully dissolved, and the concentration controlling Disodium tungstate (Na2WO4) dihydrate and thiocarbamide in mixed solution total is 0.005molL -1, this mixed solution is designated as solution A;
Step 2: the mixture adding analytically pure beta-schardinger dextrin-and commercially available gossypose (Tian Run bio tech ltd, Henan produces, and purity is 99.3%) again in solution A, the mass ratio of beta-schardinger dextrin-and gossypose is m beta-schardinger dextrin-: m gossypose=1: 2, control beta-schardinger dextrin-and the total addition of gossypose is wt%=5%, and add thermal agitation at 40 DEG C beta-schardinger dextrin-and gossypose are fully dissolved, then put into the ultrasonic cleaner sonic oscillation 20min of 300W, gained solution is designated as solution B;
Step 3: adopt 3molL -1hCl regulates the pH to 4 of solution B, then puts into the ultrasonic cleaner sonic oscillation 30min of 500W, obtains suspension-turbid liquid;
Step 4: above-mentioned suspension-turbid liquid (precursor aqueous solution) is poured in microwave hydrothermal still, compactedness controls 45%, then microwave hydrothermal still is sealed, microwave hydrothermal still after sealing is put into high flux superhigh pressure microwave dissolver, controlling microwave hydrothermal temperature is 140 DEG C, pressure is 2MPa, and reaction 1.5h, naturally cools to room temperature after reaction terminates;
Step 5: open microwave hydrothermal still, takes out product, adopts deionized water and absolute ethyl alcohol repeated washing to be placed on the freeze drier inner drying 8h that temperature is-40 DEG C, vacuum degree is 1.0Pa for 4 times successively and namely obtains WS 2-biology in situ carbon composite.
WS as seen from Figure 1 prepared by embodiment 1 2-biology in situ carbon composite structures is even, even size distribution, and without obviously reuniting, present the composite construction of fine particle and sheet, grain diameter is 80nm, and the thickness of nanometer sheet is 50nm.
WS as seen from Figure 2 prepared by embodiment 1 2there are two kinds of crystalline phases in-biology in situ carbon composite, is respectively the WS of six side's phases 2with six side phase C, and diffraction peak intensity is comparatively strong, respectively with the card PDF84-1399HexagonalWS of standard 2match with PDF74-2328HexagonalC.
The WS prepared by embodiment 1 can be drawn by Fig. 3 2-biology in situ carbon composite, be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is respectively 100mAg -1, 200mAg -1, 500mAg -1, 1000mAg -1, 2000mAg -1under condition, the reversible storage sodium capacity of prepared material is respectively 504mAhg -1, 430mAhg -1, 384mAhg -1, 350mAhg -1, 301mAhg -1, there is excellent high rate during charging-discharging.
Embodiment 2:
Step one: by analytically pure Disodium tungstate (Na2WO4) dihydrate (Na 2wO 42H 2and thiocarbamide (CH O) 4n 2s) add respectively in deionized water, the ratio of the amount of control tungsten, sulfur material is n w: n s=2: 1, the ultrasonic cleaner sonic oscillation 20min that power is 1000W is put into after being constantly stirred to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving, Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are fully dissolved, and the concentration controlling Disodium tungstate (Na2WO4) dihydrate and thiocarbamide in mixed solution total is 0.015molL -1, this mixed solution is designated as solution A;
Step 2: the mixture adding analytically pure beta-schardinger dextrin-and commercially available gossypose (Tian Run bio tech ltd, Henan produces, and purity is 99.3%) again in solution A, the mass ratio of beta-schardinger dextrin-and gossypose is m beta-schardinger dextrin-: m gossypose=5: 3, the total addition controlling beta-schardinger dextrin-and gossypose is wt%=40%, and adds thermal agitation at 65 DEG C beta-schardinger dextrin-and gossypose are fully dissolved, and then put into the ultrasonic cleaner sonic oscillation 20min of 1000W, gained solution is designated as solution B;
Step 3: adopt 1molL -1hCl regulates the pH to 6.5 of solution B, then puts into the ultrasonic cleaner sonic oscillation 20min of 1000W, obtains suspension-turbid liquid;
Step 4: above-mentioned suspension-turbid liquid (precursor aqueous solution) is poured in microwave hydrothermal still, compactedness controls 60%, then microwave hydrothermal still is sealed, microwave hydrothermal still after sealing is put into high flux superhigh pressure microwave dissolver, controlling microwave hydrothermal temperature is 200 DEG C, pressure is 8MPa, and reaction 4.5h, naturally cools to room temperature after reaction terminates;
Step 5: open microwave hydrothermal still, takes out product, adopts deionized water and absolute ethyl alcohol repeated washing to be placed on the freeze drier inner drying 4h that temperature is-55 DEG C, vacuum degree is 4.0Pa for 5 times successively and namely obtains WS 2-biology in situ carbon composite.
Institute obtains WS 2there are two kinds of crystalline phases in-biology in situ carbon composite, is respectively the WS of six side's phases 2with six side phase C, present the composite construction of fine particle and sheet, grain diameter is 30nm, and the thickness of nanometer sheet is 20nm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is respectively 100mAg -1, 200mAg -1, 500mAg -1, 1000mAg -1, 2000mAg -1under condition, the reversible storage sodium capacity of prepared material is respectively 520mAhg -1, 450mAhg -1, 398mAhg -1, 360mAhg -1, 310mAhg -1.
Embodiment 3:
Step one: by analytically pure Disodium tungstate (Na2WO4) dihydrate (Na 2wO 42H 2and thiocarbamide (CH O) 4n 2s) add in deionized water, the ratio of the amount of control tungsten, sulfur material is n w: n s=1: 1, the ultrasonic cleaner sonic oscillation 30min that power is 800W is put into after being constantly stirred to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving, Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are fully dissolved, and the concentration controlling Disodium tungstate (Na2WO4) dihydrate and thiocarbamide in mixed solution total is 0.02molL -1, this mixed solution is designated as solution A;
Step 2: the mixture adding analytically pure beta-schardinger dextrin-and commercially available gossypose (Tian Run bio tech ltd, Henan produces, and purity is 99.3%) again in solution A, the mass ratio of beta-schardinger dextrin-and gossypose is m beta-schardinger dextrin-: m gossypose=3: 7, the total addition controlling beta-schardinger dextrin-and gossypose is wt%=20%, and adds thermal agitation at 55 DEG C beta-schardinger dextrin-and gossypose are fully dissolved, and then put into the ultrasonic cleaner sonic oscillation 30min of 800W, gained solution is designated as solution B;
Step 3: adopt 2molL -1hCl regulates the pH to 6 of solution B, then puts into the ultrasonic cleaner sonic oscillation 40min of 800W, obtains suspension-turbid liquid;
Step 4: above-mentioned suspension-turbid liquid (precursor aqueous solution) is poured in microwave hydrothermal still, compactedness controls 55%, then microwave hydrothermal still is sealed, microwave hydrothermal still after sealing is put into high flux superhigh pressure microwave dissolver, controlling microwave hydrothermal temperature is 180 DEG C, pressure is 6MPa, and reaction 3h, naturally cools to room temperature after reaction terminates;
Step 5: open microwave hydrothermal still, takes out product, adopts deionized water and absolute ethyl alcohol repeated washing to be placed on the freeze drier inner drying 5h that temperature is-50 DEG C, vacuum degree is 3.0Pa for 6 times successively and namely obtains WS 2-biology in situ carbon composite.
Institute obtains WS 2there are two kinds of crystalline phases in-biology in situ carbon composite, is respectively the WS of six side's phases 2with six side phase C, present the composite construction of fine particle and sheet, grain diameter is 40nm, and the thickness of nanometer sheet is 30nm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is respectively 100mAg -1, 200mAg -1, 500mAg -1, 1000mAg -1, 2000mAg -1under condition, the reversible storage sodium capacity of prepared material is respectively 515mAhg -1, 440mAhg -1, 395mAhg -1, 355mAhg -1, 308mAhg -1.
Embodiment 4:
Step one: by analytically pure Disodium tungstate (Na2WO4) dihydrate (Na 2wO 42H 2and thiocarbamide (CH O) 4n 2s) add in deionized water, the ratio of the amount of control tungsten, sulfur material is n w: n s=1: 2, the ultrasonic cleaner sonic oscillation 40min that power is 500W is put into after being constantly stirred to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving, Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are fully dissolved, and the concentration controlling Disodium tungstate (Na2WO4) dihydrate and thiocarbamide in mixed solution total is 0.01molL -1, this mixed solution is designated as solution A;
Step 2: the mixture adding analytically pure beta-schardinger dextrin-and commercially available gossypose (Tian Run bio tech ltd, Henan produces, and purity is 99.3%) again in solution A, the mass ratio of beta-schardinger dextrin-and gossypose is m beta-schardinger dextrin-: m gossypose=2: 3, the total addition controlling beta-schardinger dextrin-and gossypose is wt%=10%, and adds thermal agitation at 50 DEG C beta-schardinger dextrin-and gossypose are fully dissolved, and then put into the ultrasonic cleaner sonic oscillation 40min of 500W, gained solution is designated as solution B;
Step 3: adopt 2.5molL -1hCl regulates the pH to 5 of solution B, then puts into the ultrasonic cleaner sonic oscillation 80min of 500W, obtains suspension-turbid liquid;
Step 4: above-mentioned suspension-turbid liquid (precursor aqueous solution) is poured in microwave hydrothermal still, compactedness controls 50%, then microwave hydrothermal still is sealed, microwave hydrothermal still after sealing is put into high flux superhigh pressure microwave dissolver, controlling microwave hydrothermal temperature is 160 DEG C, pressure is 4MPa, and reaction 2h, naturally cools to room temperature after reaction terminates;
Step 5: open microwave hydrothermal still, takes out product, adopts deionized water and absolute ethyl alcohol repeated washing to be placed on the freeze drier inner drying 6h that temperature is-45 DEG C, vacuum degree is 2.0Pa for 5 times successively and namely obtains WS 2-biology in situ carbon composite.
Institute obtains WS 2there are two kinds of crystalline phases in-biology in situ carbon composite, is respectively the WS of six side's phases 2with six side phase C, present the composite construction of fine particle and sheet, grain diameter is 60nm, and the thickness of nanometer sheet is 40nm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is respectively 100mAg -1, 200mAg -1, 500mAg -1, 1000mAg -1, 2000mAg -1under condition, the reversible storage sodium capacity of prepared material is respectively 510mAhg -1, 435mAhg -1, 390mAhg -1, 353mAhg -1, 305mAhg -1.
The preparation-obtained WS of the present invention 2there are two kinds of crystalline phases in-biology in situ carbon composite, is respectively the WS of six side's phases 2with six side phase C, present the composite construction of fine particle and sheet, grain diameter is 20 ~ 100nm, and the thickness of nanometer sheet is 10 ~ 60nm; Be 0 ~ 3V as anode material of lithium-ion battery at voltage, current density is respectively 100mAg -1, 200mAg -1, 500mAg -1, 1000mAg -1, 2000mAg -1under condition, the reversible storage sodium capacity of prepared material is respectively 460 ~ 520mAhg -1, 420 ~ 450mAhg -1, 370 ~ 400mAhg -1, 330 ~ 365mAhg -1, 290 ~ 315mAhg -1.
In a word, the present invention proposes a kind of ultrasonic technique being combined with microwave hydrothermal technology and prepares WS 2the technology of-biology in situ carbon composite---ultrasonic auxiliary microwave hydrothermal method technology of preparing, a kind of simple green, and can by controlling the regulation and control pattern of product and the methods of component such as precursor aqueous solution proportioning, and than common hydro thermal method and solvent-thermal method efficiently quick, nucleation rate is very fast, and ultrasonic vibration impels component homogeneous reaction and nucleation.The WS that low temperature ultrasonic auxiliary microwave hydrothermal method preparation method of the present invention makes 2-biology in situ carbon compound anode material of lithium-ion battery purity is high, good dispersion, and size uniform, pattern is homogeneous, has high rate capability simultaneously.

Claims (4)

1. a WS 2the preparation method of-biology in situ carbon compound cathode materials, is characterized in that: comprise the following steps:
Step one: Disodium tungstate (Na2WO4) dihydrate and thiocarbamide are added in deionized water, and be constantly stirred to Disodium tungstate (Na2WO4) dihydrate and thiocarbamide dissolving, then sonic oscillation 20 ~ 60min, obtains mixed solution A; In mixed solution A, tungsten is (1 ~ 4) with the ratio of the amount of substance of sulphur: (1 ~ 4), and the concentration controlling Disodium tungstate (Na2WO4) dihydrate and thiocarbamide in mixed solution A total is 0.005 ~ 0.2molL -1;
Step 2: add beta-schardinger dextrin-and gossypose in mixed solution A, then 30 ~ 70 DEG C of stirrings, beta-schardinger dextrin-and gossypose are dissolved, then sonic oscillation 20 ~ 60min, obtains mixed solution B; The mass fraction sum controlling beta-schardinger dextrin-and gossypose in mixed solution B is 5 ~ 50%, and the mass ratio of beta-schardinger dextrin-and gossypose is (1 ~ 5): (2 ~ 7);
Step 3: adopt the hydrochloric acid of 1 ~ 4mol/L to regulate pH to 3 ~ 7 of mixed solution B, then sonic oscillation 30 ~ 90min, obtains suspension-turbid liquid;
Step 4: described suspension-turbid liquid is poured in microwave hydrothermal still, the compactedness of microwave hydrothermal still controls 45 ~ 65%, then microwave hydrothermal still is sealed, microwave hydrothermal still after sealing is put into high flux superhigh pressure microwave dissolver react, controlling reaction temperature is 120 ~ 260 DEG C, reaction pressure is 2 ~ 10MPa, and the reaction time is 0.5 ~ 5h, naturally cools to room temperature after reaction terminates;
Step 5: after step 4, opens described microwave hydrothermal still, takes out product, namely obtains WS after adopting deionized water and absolute ethanol washing successively in-30 ~-70 DEG C of freeze dryings 2-biology in situ carbon compound cathode materials.
2. a kind of WS according to claim 1 2the preparation method of-biology in situ carbon compound cathode materials, is characterized in that: in described step one and step 2, stirs and adopts magnetic stirring apparatus.
3. a kind of WS according to claim 1 2the preparation method of-biology in situ carbon compound cathode materials, is characterized in that: described step one is in step 3, and sonic oscillation adopts ultrasonic cleaner, and the power of sonic oscillation is 300 ~ 1000W.
4. a kind of WS according to claim 1 2the preparation method of-biology in situ carbon compound cathode materials, is characterized in that: in described step 5, and controlling cryodesiccated vacuum degree is 0.0 ~ 10.0Pa, and sublimation drying is 4 ~ 8h.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109449411A (en) * 2018-10-30 2019-03-08 陕西科技大学 A kind of method of confinement synthesis tungsten disulfide@C combination electrode material
CN110683581A (en) * 2018-07-04 2020-01-14 湖北大学 Self-assembly thousand-layer-shaped WS2Method for preparing nano structure
CN111001397A (en) * 2019-12-31 2020-04-14 东北农业大学 Method for synthesizing β cyclodextrin conjugated biochar by microwave-assisted one-pot method and application thereof
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CN113351164A (en) * 2021-07-12 2021-09-07 中南大学 Hydrothermal carbon/calcium silicate hydrate coupling material, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110104551A1 (en) * 2009-11-05 2011-05-05 Uchicago Argonne, Llc Nanotube composite anode materials suitable for lithium ion battery applications
CN102942210A (en) * 2012-11-14 2013-02-27 陕西科技大学 Preparation method of red-shift cadmium sulfide ball cluster microcrystalline
CN102980928A (en) * 2012-11-27 2013-03-20 信阳师范学院 Tungsten sulfide-graphene electrochemical sensor as well as preparation method and application of sensor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110104551A1 (en) * 2009-11-05 2011-05-05 Uchicago Argonne, Llc Nanotube composite anode materials suitable for lithium ion battery applications
CN102942210A (en) * 2012-11-14 2013-02-27 陕西科技大学 Preparation method of red-shift cadmium sulfide ball cluster microcrystalline
CN102980928A (en) * 2012-11-27 2013-03-20 信阳师范学院 Tungsten sulfide-graphene electrochemical sensor as well as preparation method and application of sensor

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CN110683581A (en) * 2018-07-04 2020-01-14 湖北大学 Self-assembly thousand-layer-shaped WS2Method for preparing nano structure
CN109449411A (en) * 2018-10-30 2019-03-08 陕西科技大学 A kind of method of confinement synthesis tungsten disulfide@C combination electrode material
CN109449411B (en) * 2018-10-30 2020-12-01 陕西科技大学 Method for synthesizing tungsten disulfide @ C composite electrode material in limited domain
CN111001397A (en) * 2019-12-31 2020-04-14 东北农业大学 Method for synthesizing β cyclodextrin conjugated biochar by microwave-assisted one-pot method and application thereof
CN111554935A (en) * 2020-05-15 2020-08-18 陕西科技大学 Preparation method of wheat straw/carbon nano tube for sulfur-doped lithium battery negative electrode material
CN112397699A (en) * 2020-11-16 2021-02-23 西北大学 Transition metal chalcogenide/carbon composite material rich in anion vacancies and preparation method and application thereof
CN113351164A (en) * 2021-07-12 2021-09-07 中南大学 Hydrothermal carbon/calcium silicate hydrate coupling material, and preparation method and application thereof
CN113351164B (en) * 2021-07-12 2023-02-28 中南大学 Hydrothermal carbon/calcium silicate hydrate coupling material, and preparation method and application thereof

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