CN104103818A - Multi-edge WS2 nanosheet/graphene composite nanomaterial and preparation method - Google Patents

Multi-edge WS2 nanosheet/graphene composite nanomaterial and preparation method Download PDF

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CN104103818A
CN104103818A CN201410339843.4A CN201410339843A CN104103818A CN 104103818 A CN104103818 A CN 104103818A CN 201410339843 A CN201410339843 A CN 201410339843A CN 104103818 A CN104103818 A CN 104103818A
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graphene
nanometer sheet
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CN104103818B (en
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陈涛
陈卫祥
马琳
孙虎
叶剑波
陈倩男
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Zhejiang University ZJU
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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
    • H01M4/366—Composites as layered products
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 discloses a multi-edge WS2 nanosheet/graphene composite nanomaterial and a preparation method thereof. The multi-edge WS2 nanosheet/graphene composite nanomaterial is composited by multi-edge WS2 nanosheets with a few layers and graphene, and a substance ratio of WS2 nanosheets to graphene is (1:1)-(1:4). The preparation method comprises the steps as follows: graphene oxide is ultrasonically dispersed in deionized water firstly, added with an ionic liquid, sufficiently stirred and then sequentially added with L-cysteine and ammonium thiotungstate, and L-cysteine and ammonium thiotungstate are sufficiently stirred and dissolved; and the hybrid dispersion is transferred to a hydrothermal reaction kettle to have a hydrothermal reaction for 24 hours at the temperature of 240 DEG C and is naturally cooled to the room temperature, and solid products are collected centrifugally, sufficiently washed by deionized water, dried and subjected to thermal treatment finally to prepare the multi-edge WS2 nanosheet/graphene composite nanomaterial. The method has the advantages of simplicity and convenience and is prone to enlargement of industrial application.

Description

Multiple edge WS 2nanometer sheet/Graphene composite nano materials and preparation method
Technical field
The present invention relates to composite nano materials and preparation method thereof, relate in particular to multiple edge WS 2nanometer sheet/Graphene composite nano materials and hydrothermal preparing process thereof, belong to inorganic composite nano material technology field.
Background technology
Two-dimensional nano material has the characteristic of numerous excellences with its unique pattern, its research has caused people's very big interest.Graphene is most typical two-dimensional nano material, and its unique two-dimensional nano chip architecture makes the performances such as physics, chemistry and the mechanics of its numerous uniquenesses, has important scientific research meaning and technology application prospect widely.Graphene has high specific area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, these excellent characteristics make Graphene be with a wide range of applications at aspects such as micro-nano electronic device, energy storage material and novel catalyst carriers.
The immense success that the discovery of Graphene and research thereof obtain has excited the very big interest of people to other inorganic two-dimensional nano investigations of materials, as the transition metal dichalcogenide of individual layer or few number of plies etc.As a kind of typical case and important transition metal dichalcogenide, WS 2having and layer structure like graphite-like, is the S-W-S unit of covalent bonds in its layer, and combination is between layers weak Van der Waals force.This typical layered structure and weak Van der Waals force, make WS 2having lower friction factor as kollag, particularly under the condition such as high temperature, high vacuum, still have lower coefficient of friction, is a kind of good kollag.In addition, layer structure WS 2can allow the embedding of external atom or ion, therefore WS 2lamellar compound is also a kind of rising electrochemical lithium storage and storage Development of Magnesium Electrode Materials.
Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for the inorganic material of layer structure, in the time that its number of plies reduces (below approximately 6 layers), especially while reducing to individual layer, its electronic property or band structure can produce obvious variation, thereby cause it to show the physics and chemistry characteristic different from corresponding body phase material.Except Graphene, research recently shows as body phase WS 2reduce to few number of plies when individual layer (below 6 layers, especially), shown and the visibly different physics of body phase material, chemistry and electronics property.Studies have reported that the WS of individual layer or few number of plies 2there is better electrochemistry storage lithium performance and good electrocatalytic hydrogen evolution reactivity.But as storage lithium electrode material and the electrocatalysis material of electrochemical reaction, WS 2low electric conductivity between layers affected the performance of its application.
Due to WS 2nanometer sheet and Graphene have similar two-dimensional nano sheet pattern, and both have good similitude on microscopic appearance and crystal structure.If by WS 2the composite material of nanometer sheet and the compound preparation of Graphene, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite material, strengthen the electronics transmission in electrochemistry storage lithium and electrocatalytic reaction process, can further improve electrochemistry storage lithium performance and the electrocatalysis characteristic of composite material.Research shows WS 2the catalytic activity of the electrocatalytic hydrogen evolution reaction of nanometer sheet is mainly derived from its active sites edge, increases WS 2the active sites edge of nanometer sheet is an approach of the electrocatalysis characteristic of enhancing.In addition, as electrochemistry storage lithium electrode material, the more WS of multiple edge 2nanometer sheet can provide more and relatively short lithium ion diffusion admittance, contributes to booster electrochemistry storage lithium performance.With common WS 2nanometer sheet comparison, multiple edge WS 2nanometer sheet not only has more edge, and has more contact area with electrolyte.Therefore, this multiple edge WS 2the chemical property that the composite nano materials of nanometer sheet/Graphene has a wide range of applications and strengthens as electrochemistry storage lithium electrode material and evolving hydrogen reaction eelctro-catalyst.
But, up to the present, multiple edge WS 2nanometer sheet and Graphene composite nano materials and preparation thereof have not been reported.The present invention is taking graphene oxide and sulfo-ammonium tungstate as raw material, and the hydro-thermal reaction approach of assisting by ionic liquid has been prepared the multiple edge WS of few number of plies 2the composite nano materials of nanometer sheet and Graphene.This multiple edge WS for preparing 2the method of the composite nano materials of nanometer sheet/Graphene has simply, facilitates and be easy to expand industrial applications a little.
Summary of the invention
The object of the present invention is to provide a kind of multiple edge WS 2nanometer sheet/Graphene composite nano materials and preparation method thereof, this composite nano materials is the multiple edge WS by few number of plies 2the compound formation of nanometer sheet and Graphene, multiple edge WS 2the ratio of the amount of substance between nanometer sheet and Graphene is 1:1-1:4.
In technique scheme, few number of plies refers to below 6 layers or 6 layers.
As preferably, multiple edge WS 2the number of plies of nanometer sheet is 2-5 layer.
Multiple edge WS of the present invention 2the preparation method of nanometer sheet/Graphene composite nano materials carries out in the steps below:
(1) be dispersed in deionized water ultrasonic graphene oxide, then add appropriate ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF 4), its structure is shown in the schematic diagram of Fig. 1, and fully stirs;
(2) then Cys and sulfo-ammonium tungstate are joined successively in the mixed system that step (1) obtains; and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely; the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, sulfo-ammonium tungstate with the ratio of the amount of substance of graphene oxide at 1:1 ~ 1:4;
(3) mixed dispersion step (2) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, the content of hydro-thermal reaction system intermediate ion liquid is 6.25 ~ 25 mL/L, this reactor sealing is placed in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal solid product, and fully wash with deionized water, vacuumize at 100 DEG C, by the hydro-thermal solid product obtaining in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2 h, in mist, the volume fraction of hydrogen is 10%, prepare multiple edge WS 2the composite nano materials of nanometer sheet/Graphene.
Above-mentioned graphene oxide adopts improved Hummers method preparation.
Multiple edge WS of the present invention 2nanometer sheet/Graphene composite nano materials and preparation method thereof has the following advantages:
Graphene oxide surface and edge with a lot of oxygen-containing functional groups (as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups are more easily dispersed in water or organic liquid graphene oxide, but these oxygen-containing functional groups make graphene oxide surface with negative electrical charge, make graphene oxide and the WS with negative electrical charge 4 2-ion is incompatible, and the present invention is first adsorbed onto graphene oxide surface, WS by positively charged ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (its structure is shown in the schematic diagram of Fig. 1) by electrostatic interaction 4 2-ion is just easier to interact and combine with the graphene oxide that has adsorbed ionic liquid.Research shows WS 2the surface energy of its basic side can be much higher than in the surface at nanometer sheet edge, therefore, and WS prepared by general hydro-thermal reaction 2nanometer sheet edge is less.Prepare the more WS of multiple edge 2nanometer sheet will manage to reduce WS 2the surface energy at nanometer sheet edge.In hydro-thermal reaction, add ionic liquid, can reduce WS 2the surface energy at nanometer sheet edge, the hydro-thermal reaction approach of therefore assisting by ionic liquid can prepare the more WS of multiple edge 2the composite nano materials of nanometer sheet/Graphene.Compared with common quaternary cationics, the cationic positive charge of ionic liquid is the (as: imidazole ring being distributed in nitrogen heterocyclic ring, see Fig. 1), this nitrogen heterocyclic ring containing positive charge can interact with electronegative graphene oxide better than general quaternary cationics.This is because positively charged quaternary ammonium N is sp in general quaternary cationics 3hydridization, in succession 3 methyl and a long alkyl chain, hindered the quaternary ammonium N of positively charged and the mutual electrostatic interaction of graphene oxide; And 2 sp that N is planar structure in heterocycle in ionic liquid 2hydridization, can interact with graphene oxide better by Π-Π accumulation and electrostatic force.Multiple edge WS 2nanometer sheet/graphene composite material can also increase the contact area of itself and electrolyte.Therefore this multiple edge WS that, prepared by the present invention 2nanometer sheet/graphene composite material has electrocatalysis characteristic and the electrochemistry storage lithium performance of remarkable enhancing to evolving hydrogen reaction.Preparation method of the present invention has simply, facilitates and be easy to expand the feature of industrial applications.
Brief description of the drawings
Fig. 1 ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF 4) structural representation.
The multiple edge WS that Fig. 2 embodiment 1 prepares 2the XRD figure of nanometer sheet/Graphene composite nano materials.
The multiple edge WS that Fig. 3 embodiment 1 prepares 2sEM shape appearance figure and the transmission electron microscope photo of nanometer sheet/Graphene composite nano materials.
WS prepared by Fig. 4 comparative example 2the TEM of nanometer sheet and Graphene composite nano materials, HRTEM photo.
Embodiment
Further illustrate the present invention below in conjunction with embodiment.
Graphene oxide in following example adopts improved Hummers method preparation: 0 ounder C ice bath, by 10.0 mMol (0.12 g) graphite powder dispersed with stirring in the 50 mL concentrated sulfuric acids, under constantly stirring, slowly add KMnO 4, institute adds KMnO 4quality be 4 times of graphite powder, stir 50 minutes, in the time of temperature rise to 35 DEG C, slowly add 50 mL deionized waters, then stir 30 minutes, add the H of 15 mL mass fractions 30% 2o 2, stir 30 minutes, through centrifugation, successively with obtaining graphene oxide after mass fraction 5%HCl solution, deionized water and acetone cyclic washing.
Embodiment 1.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add 0.5 mL ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (its structure is shown in the schematic diagram of Fig. 1), and fully stir;
2) then add successively 0.76g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume;
3) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares multiple edge WS 2the composite nano materials of nanometer sheet/Graphene, WS in composite nano materials 2with the ratio of Graphene amount of substance be 1:2.
With XRD, SEM and TEM/HRTEM are to the prepared multiple edge WS that obtains 2the composite nano materials of nanometer sheet/Graphene characterizes, and characterization result shows WS in composite nano materials 2be the multiple edge nanometer sheet of few number of plies, its number of plies is at 2-5 layer, and the average number of plies is 3 layers (seeing Fig. 2 and Fig. 3).
Comparative example
Do not add ionic liquid, prepare WS by above-mentioned similar approach 2the composite nano materials of nanometer sheet/Graphene, concrete preparation process is as follows:
Be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add successively 0.76g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepare WS 2the composite nano materials of nanometer sheet/Graphene, WS 2with the ratio of Graphene amount of substance be 1:2.
With XRD, SEM and TEM are to prepared WS 2the nano composite material of nanometer sheet/Graphene characterizes, and characterization result shows WS in composite nano materials 2for the nanometer sheet (see figure 4) of layer structure.
Electrocatalytic reaction Hydrogen Evolution Performance is tested and is compared: by the multiple edge WS of the above-mentioned preparation of 4 .0 mg 2nanometer sheet/Graphene composite nano materials (or WS of preparing of comparative example 2nanometer sheet/Graphene composite nano materials) add in deionized water-alcohol mixeding liquid body of 1.0 mL (volume ratio 1:1), add again the Nafion solution (5 wt%) of 30 uL, ultrasonic processing 2 h, make it fully mix and be uniformly dispersed, obtain uniform slurry, the mixed slurry of getting 5 uL with liquid-transfering gun drips on the glassy carbon electrode of diameter 5 mm, after drying at 80 DEG C, obtains test job electrode.Electrolyte is the aqueous sulfuric acid of 0.5 M, and reference electrode is saturated calomel electrode, and platinized platinum, as to electrode, is used the electrocatalysis characteristic of linear potential sweep test material to evolving hydrogen reaction on CHI660B electrochemical workstation, and sweep speed is 5 mV/s.Test result is presented under identical cathodic polarization overpotential, multiple edge WS 2electrode prepared by nanometer sheet/Graphene composite nano materials compares WS 2electrode prepared by nanometer sheet/Graphene composite nano materials has higher evolving hydrogen reaction electric current.As: under 0.20 V vs. RHE current potential, at multiple edge WS 2on nanometer sheet/Graphene composite nano materials electrode, electrochemical catalysis evolving hydrogen reaction electric current is 18.2 mA, at WS 2on nanometer sheet/Graphene composite nano materials electrode, evolving hydrogen reaction electric current is 7.3 mA.Due to multiple edge WS to the enhancing of evolving hydrogen reaction electrocatalysis characteristic 2multiple edge WS in nanometer sheet/Graphene composite nano materials 2nanometer sheet compares WS 2wS in nanometer sheet/Graphene composite nano materials 2nanometer sheet has more active sites edge (comparison diagram 3 and Fig. 4 can find this point).In addition, multiple edge WS 2nanometer sheet/Graphene composite nano materials compares WS 2nanometer sheet/Graphene composite nano materials has more and electrolyte contact area.
Embodiment 2.
1) be dispersed in 60 mL deionized waters ultrasonic 3.75 mmol graphene oxides, then add 1.0 mL ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborates, and fully stir;
2) then add successively 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume;
3) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares multiple edge WS 2the composite nano materials of nanometer sheet/Graphene, WS in composite nano materials 2with the ratio of Graphene amount of substance be 1:3.With XRD, SEM and TEM/HRTEM are to the prepared multiple edge WS that obtains 2the composite nano materials of nanometer sheet/Graphene characterizes, and characterization result shows WS in composite nano materials 2be the multiple edge nanometer sheet of few number of plies, its number of plies is at 2-5 layer, and the average number of plies is 3 layers.
Embodiment 3.
1) be dispersed in 60 mL deionized waters ultrasonic 2.5 mmol graphene oxides, then add 1.5 mL ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborates, and fully stir;
2) then add successively 12.5 mmol Cys and 2.5 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume;
3) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares multiple edge WS 2the composite nano materials of nanometer sheet/Graphene, WS in composite nano materials 2with the ratio of Graphene amount of substance be 1:1.With XRD, SEM and TEM/HRTEM are to the prepared multiple edge WS that obtains 2the composite nano materials of nanometer sheet/Graphene characterizes, and characterization result shows WS in composite nano materials 2be the multiple edge nanometer sheet of few number of plies, its number of plies is at 2-5 layer, and the average number of plies is 3 layers.
Embodiment 4.
1) be dispersed in 60 mL deionized waters ultrasonic 5.0 mmol graphene oxides, then add 2.0 mL ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborates, and fully stir;
2) then add successively 0.76 g (6.25 mmol) Cys and 1.25 mmol sulfo-ammonium tungstates, and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely, with extremely approximately 80 mL of deionized water adjustment volume;
3) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100 mL, this reactor is put in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2h, in mist, the volume fraction of hydrogen is 10%, prepares multiple edge WS 2the composite nano materials of nanometer sheet/Graphene, WS in composite nano materials 2with the ratio of Graphene amount of substance be 1:4.With XRD, SEM and TEM/HRTEM are to the prepared multiple edge WS that obtains 2the composite nano materials of nanometer sheet/Graphene characterizes, and characterization result shows WS in composite nano materials 2be the multiple edge nanometer sheet of few number of plies, its number of plies is at layer 2-4, and the average number of plies is 3 layers.

Claims (3)

1. a multiple edge WS 2the composite nano materials of nanometer sheet/Graphene, is characterized in that, this composite nano materials is the multiple edge WS by few number of plies 2the compound formation of nanometer sheet and Graphene, multiple edge WS 2the ratio of the amount of substance between nanometer sheet and Graphene is 1:1-1:4.
2. multiple edge WS according to claim 1 2the composite nano materials of nanometer sheet/Graphene, is characterized in that, described multiple edge WS 2the number of plies of nanometer sheet is 2 ~ 5 layers.
3. multiple edge WS described in a claim 1 2the preparation method of the composite nano materials of nanometer sheet/Graphene, is characterized in that, described preparation method carries out in the steps below:
(1) be dispersed in deionized water ultrasonic graphene oxide, then add appropriate ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIM] BF 4), and fully stir;
(2) then Cys and sulfo-ammonium tungstate are joined successively in the mixed system that step (1) obtains; and constantly stir Cys and sulfo-ammonium tungstate are dissolved completely; the ratio of the amount of substance of Cys and sulfo-ammonium tungstate consumption is 5:1, sulfo-ammonium tungstate with the ratio of the amount of substance of graphene oxide at 1:1-1:4;
(3) mixed dispersion step (2) being obtained is transferred in hydrothermal reaction kettle, and add deionized water to adjust volume to 80% of hydrothermal reaction kettle nominal volume, the content of hydro-thermal reaction system intermediate ion liquid is 6.25 ~ 25 mL/L, reactor sealing is placed in constant temperature oven, at 240 DEG C after hydro-thermal reaction 24 h, allow it naturally cool to room temperature, with centrifugation collection hydro-thermal solid product, and fully wash with deionized water, vacuumize at 100 DEG C, by obtained hydro-thermal solid product in nitrogen/hydrogen mixed gas atmosphere at 500 DEG C heat treatment 2 h, in mist, the volume fraction of hydrogen is 10%, prepare multiple edge WS 2the composite nano materials of nanometer sheet/Graphene.
CN201410339843.4A 2014-07-17 2014-07-17 Multi-edge WS2 nanosheet/graphene composite nanomaterial and preparation method Expired - Fee Related CN104103818B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102142550A (en) * 2011-02-25 2011-08-03 浙江大学 Compound nano material of graphene nano slice and WS2 and preparation method thereof
CN102694171A (en) * 2012-06-08 2012-09-26 浙江大学 Hydrothermal preparation method for composite material of single-layer WS2 and graphene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102142550A (en) * 2011-02-25 2011-08-03 浙江大学 Compound nano material of graphene nano slice and WS2 and preparation method thereof
CN102694171A (en) * 2012-06-08 2012-09-26 浙江大学 Hydrothermal preparation method for composite material of single-layer WS2 and graphene

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HUI LI等: "Electrochemical lithiation/delithiation performances of 3D flowerlike MoS2 powders prepared by ionic liquid assisted hydrothermal route", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 471, 18 June 2008 (2008-06-18), pages 442 - 447, XP 025994443, DOI: doi:10.1016/j.jallcom.2008.03.133 *
马　琳等: "轻度剥离二硫化钼／石墨烯复合材料的制备及其电化学储锂性能", 《中国科技论文》, vol. 8, no. 12, 31 December 2013 (2013-12-31), pages 1247 - 1252 *

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