CN105322147B - A kind of tungsten disulfide/carbon nano-fiber/graphene composite material and preparation method thereof - Google Patents
A kind of tungsten disulfide/carbon nano-fiber/graphene composite material and preparation method thereof Download PDFInfo
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- CN105322147B CN105322147B CN201510622958.9A CN201510622958A CN105322147B CN 105322147 B CN105322147 B CN 105322147B CN 201510622958 A CN201510622958 A CN 201510622958A CN 105322147 B CN105322147 B CN 105322147B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 81
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 78
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 33
- 239000002121 nanofiber Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000001802 infusion Methods 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- -1 thio ammonium tungstate Chemical compound 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 230000005686 electrostatic field Effects 0.000 claims description 3
- 230000002045 lasting effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- 229910002804 graphite Inorganic materials 0.000 claims 2
- 239000010439 graphite Substances 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 230000036571 hydration Effects 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 230000001052 transient effect Effects 0.000 abstract description 2
- 229910052976 metal sulfide Inorganic materials 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- 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 belongs to transient metal sulfide carbon material technical field, specially a kind of tungsten disulfide/carbon nano-fiber/graphene composite material and preparation method thereof.The preparation method of the present invention includes：Polyacrylonitrile nanofiber film is prepared by electrostatic spinning, graphene oxide is wrapped up on polyacrylonitrile nanofiber by solution infusion method, carbon nano-fiber/graphene composite film is prepared by high temperature cabonization again, finally by a step solvent-thermal method on carbon nano-fiber/graphene growth in situ tungsten disulfide nano slices.Graphene/carbon nanofiber prepared by the present invention has the advantages that chemical property stabilization, good conductivity, good mechanical performance, can as a kind of preferable high-performance electric catalysis material, and the new energy devices such as lithium ion battery and solar cell electrode material.
Description
Technical field
The invention belongs to transient metal sulfide-carbon material technical field, and in particular to a kind of tungsten disulfide/carbon Nanowire
Dimension/graphene composite material and preparation method thereof.
Technical background
Carbon nano-fiber has adhered to the excellent physical and chemical performance of carbon nanomaterial, such as excellent mechanical property, high ratio
Surface area and good chemical stability etc., it is multiple that these special natures make it be widely used in catalyst carrier, high molecular nanometer
The fields such as the flexible base material of condensation material, energy conversion and memory device.Electrostatic spinning is that one kind simply and effectively prepares carbon
The technology of nanofiber, carries out spinning by polymer solution by high-pressure electrostatic, then carries out pre-oxidation and high temperature cabonization to prepare
Obtain the Static Spinning carbon nanofiber membrane with three-dimensional porous structure and high-specific surface area.This patent uses electrostatic spinning process,
Polyacrylonitrile solution is subjected to spinning and polyacrylonitrile nanofiber film is prepared by pre-oxidation, is existed by solution infusion method
Graphene oxide is wrapped up on polyacrylonitrile nanofiber, then carbon nano-fiber/graphene is prepared by high temperature cabonization and is combined
Film, and further prepare high-performance composite materials as base material.
Tungsten disulfide is the Transition-metal dichalcogenide of a quasi-representative, and it is very strong S- that it, which belongs in hexagonal crystal system, layer,
W-S covalent bonds, interlayer is weaker Van der Waals force, and thickness in monolayer is about 0.65 nm.The tungsten disulfide nano slices layer of individual layer can be with
Peeled off with adhesive tape or the method for lithium ion intercalation is obtained.Research shows that there is liberation of hydrogen to urge at the active edge of tungsten disulfide exposure
Change activity, therefore there is extensive use in electrochemical catalysis field.But, pure tungsten disulfide is easy to reunite, and it is preferential raw
Long inert endothecium structure, rather than active lamella edge, substantial amounts of aggregate also further suppress the exposure at active edge, then
Plus its poor electric conductivity, the excellent properties of pure tungsten disulfide can not often be fully used.Therefore, by tungsten disulfide with
It is significant that the base material of other high conductivity carries out high efficiency composition.
The present invention prepares a kind of new tungsten disulfide/carbon nano-fiber/graphene by simple technological design
Composite.The composite has following advantage：Static Spinning carbon nano-fiber has unique three-dimensional porous structure, higher
Specific surface area and excellent mechanical property；It is whole that graphene parcel carbon nano-fiber can improve carbon nano-fiber/graphene composite film
The electric conductivity of body, promotes the quick transmission of electronics；Tungsten disulfide nano slices are equably grown on carbon nano-fiber/graphene,
The reunion of tungsten disulfide itself can effectively be suppressed, make the active edge of tungsten disulfide nano slices obtain more fully exposing；Carbon is received
The excellent mechanical property of rice fiber makes composite to be applied to catalysis and energy storage device as flexible electrode material；Two sulphur
Change tungsten nanometer sheet and possess higher catalytic activity and theoretical stored energy capacitance value in itself, the overall catalytic performance of composite can be improved
With energy stores performance.Therefore, carbon nano-fiber/graphene and tungsten disulfide nano slices are carried out effectively being combined, it is possible to achieve
Good synergy between three, to prepare the composite of excellent performance.
The content of the invention
It is an object of the invention to provide a kind of tungsten disulfide/carbon nano-fiber/graphene of electrochemical performance is multiple
Condensation material and preparation method thereof.
Tungsten disulfide/carbon nano-fiber/graphene composite material provided by the present invention, its preparing raw material composition includes：
Polyacrylonitrile,N,N-Dimethylformamide, graphene oxide, thio ammonium tungstate and hydrazine hydrate.
Tungsten disulfide/carbon nano-fiber/graphene composite material provided by the present invention, its preparation process includes：Pass through
Electrostatic spinning prepares polyacrylonitrile nanofiber film, and oxidation is wrapped up on polyacrylonitrile nanofiber by solution infusion method
Graphene, then carbon nano-fiber/graphene composite film is prepared by high temperature cabonization, finally by a step solvent-thermal method in stone
Growth in situ tungsten disulfide nano slices on black alkene/carbon nano-fiber, are comprised the following steps that：
（1）Polyacrylonitrile powder is added toN,N-In solvent dimethylformamide, lasting stirring obtains homogeneous sticky
Dispersion liquid；
（2）Obtained polyacrylonitrile dispersion liquid is subjected to electrostatic spinning, polyacrylonitrile nanofiber film is obtained；
（3）Polyacrylonitrile spinning film is pre-oxidized in air atmosphere, the polyacrylonitrile nano after being pre-oxidized
Tunica fibrosa；
（4）Polyacrylonitrile nanofiber film after gained is pre-oxidized soaks in graphene oxide solution, obtains poly- third
Alkene nitrile nanofibre/graphene oxide composite membrane；
（5）Gained polyacrylonitrile nanofiber/graphene composite film is subjected to high temperature cabonization under inert gas shielding, obtained
To carbon nano-fiber/graphene composite film；
（6）Thio ammonium tungstate and hydrazine hydrate are dissolved in organic solvent, homogeneous salting liquid is obtained；
（7）By obtained above-mentioned salting liquid and carbon nano-fiber/graphene composite film by solvent thermal reaction, two sulphur are obtained
Change tungsten/carbon nano-fiber/graphene composite material；
（8）Obtained above-mentioned tungsten disulfide/carbon nano-fiber/graphene composite material is carried out under inert gas shielding
Heat treatment, to improve the crystal structure of tungsten disulfide.
In the present invention, step（2）Described electrostatic spinning process, its adjust technological parameter be：Electrostatic field voltage 15 ~ 25
KV, the mm min of spinning speed 0.2 ~ 0.4-1, receive the cm of distance 15 ~ 25.
In the present invention, step（3）Described preoxidation process, the temperature of pre-oxidation is 250 ~ 300 DEG C, and heating rate is 1
~2℃ min-1, preoxidation time is 1 ~ 2 h, preferably 1.5 h.
In the present invention, step（4）The solution immersion process, the concentration of graphene oxide is 0.5 ~ 2mg mL-1, during immersion
Between be 12 ~ 36 h.
In the present invention, step（5）During described high temperature cabonization, inert gas used is high-purity argon gas or High Purity Nitrogen
Gas, high temperature cabonization temperature is 1000 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3 h, preferably 2h.
In the present invention, step（6）In described salting liquid preparation process, the organic solvent isN,N-Dimethyl formyl
Amine,N,N-Dimethyl acetamide orN-The thio ammonium tungstate of methyl pyrrolidone；The concentration of the thio ammonium tungstate of configuration is 1 ~ 3 mg
mL-1, preferably 2 mg mL-1；Described concentration of hydrazine hydrate is 30% ~ 80%, and consumption is 0.1 ~ 0.3 mL.
In the present invention, step（7）Described solvent thermal reaction, reaction temperature be 160 ~ 220 DEG C, preferably 180 ~ 200 DEG C, instead
It is 10 ~ 24 h, preferably 12 ~ 15 h between seasonable.
In the present invention, step（8）In described heat treatment process, inert gas used is high-purity argon gas or High Purity Nitrogen
Gas, heat treatment temperature is 250 ~ 400 DEG C, and preferably 300 ~ 350 DEG C, heat treatment time is 1 ~ 4 h, preferably 2 ~ 3 h.
Use SEM（SEM）, X-ray diffractometer（XRD）Come characterize the present invention obtained tungsten disulfide/
The structure and morphology of carbon nano-fiber/graphene composite material, its result is as follows：
（1）SEM test results show：In carbon nano-fiber/graphene composite film, graphene sheet layer is closely wrapped in
On carbon nano-fiber surface, the diameter of carbon nano-fiber is about 200 ~ 300 nm.In tungsten disulfide/carbon nano-fiber/graphene
In composite, tungsten disulfide nano slices are equably grown on carbon nano-fiber/graphene, effectively inhibit tungsten disulfide certainly
The reunion of body, makes the active edge of tungsten disulfide nano slices layer fully be exposed.This has benefited from carbon nano-fiber/graphene three
Dimension space structure and higher specific surface area, more sites are provided for the growth of tungsten disulfide.Referring to accompanying drawing 1 and accompanying drawing 2；
（2）XRD test results show, prepared carbon nano-fiber/graphene composite film have at 2 θ=26 ° one compared with
Wide diffraction maximum, corresponding to carbon nano-fiber and graphene（002）Crystal face.Prepared tungsten disulfide/carbon nano-fiber/stone
Black alkene composite shows the characteristic peak of tungsten disulfide, diffraction occurs at 2 θ=13.3 °, 33.8 °, 39.6 ° and 59.9 °
Peak, corresponds respectively to tungsten disulfide（002）,（101）,（103）With（100）Crystal face.Meanwhile, prepared tungsten disulfide/carbon
Nanofiber/graphene composite material occurs in that the characteristic peak of carbon nano-fiber/graphene at 2 θ=26 °, it was confirmed that carbon is received
The effective of rice fiber/both graphene and tungsten disulfide is combined.Referring to accompanying drawing 3.
The advantage of the invention is that：
（1）Preparation process is simple, it is easy to operate, and is a kind of convenient effective preparation method；
（2）Experimental design is ingenious.By electrostatic spinning, solution immersion and high temperature cabonization technology, simply and effectively it is prepared into
Carbon nano-fiber/graphene composite film with three-dimensional porous structure and high-specific surface area has been arrived, and as base material, has been led to
Step solvent-thermal method growth in situ tungsten disulfide nano slices on carbon nano-fiber/graphene are crossed, tungsten disulfide is effectively inhibited
The reunion of itself, realizes one-dimensional material and the high efficiency composition of two-dimensional material, so as to construct the composite wood with multilevel hierarchy
Material；
（3）Prepared tungsten disulfide/carbon nano-fiber/graphene composite material has preferable pliability, higher
Electric conductivity and higher catalytic performance and energy stores performance.Carbon nano-fiber/graphene and tungsten disulfide nano slices are carried out
It is effectively compound, both advantages can be enable to give full play to, so as to construct novel high-performance composite.
Tungsten disulfide/carbon nano-fiber/graphene composite material prepared by the present invention, can be used as high performance catalyst material
And the ideal electrode material of the new energy devices such as lithium ion battery, solar cell.
Brief description of the drawings
Fig. 1 is the SEM figures of carbon nano-fiber/graphene composite material in the present invention.
Fig. 2 is the SEM figures of tungsten disulfide/carbon nano-fiber/graphene composite material in the present invention.
Fig. 3 is the XRD of tungsten disulfide/carbon nano-fiber/graphene composite material of the present invention.
Embodiment
With reference to instantiation, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention and
It is not used in limitation the scope of the present invention.In addition, after the content of the invention lectured has been read, those skilled in the art can be right
The present invention makes various changes or modification, and these equivalent form of values equally fall within the application appended claims limited range.
Embodiment 1, the present embodiment comprise the following steps：
（1）1 g polyacrylonitrile powders are added to 5 mLN,N-In solvent dimethylformamide, lasting stirring is prepared into
To homogeneous sticky dispersion liquid；
（2）Obtained polyacrylonitrile dispersion liquid is subjected to electrostatic spinning, its regulation technological parameter is：Electrostatic field voltage 20
KV, the mm min of spinning speed 0.3-1, the cm of distance 20 is received, polyacrylonitrile nanofiber film is prepared；
（3）Obtained polyacrylonitrile spinning film is pre-oxidized in air atmosphere, the temperature of pre-oxidation is 250 DEG C,
Heating rate is 1 DEG C of min-1, preoxidation time is 1.5 h, prepares the polyacrylonitrile nanofiber film after pre-oxidation；
（4）Polyacrylonitrile nanofiber film after gained is pre-oxidized is in 1 mg mL-124 are soaked in graphene oxide solution
H, prepares polyacrylonitrile nanofiber/graphene oxide composite membrane；
（5）Gained polyacrylonitrile nanofiber/graphene oxide composite membrane is subjected to high temperature cabonization in high pure nitrogen, it is high
Warm carburizing temperature is 1200 DEG C, and the high temperature cabonization time is 2 h, prepares carbon nano-fiber/graphene composite film；
（6）The thio ammonium tungstates of 20 mg and the hydrazine hydrates of 0.1 mL 50% are dissolved in 10 mLN,N-Solvent dimethylformamide
In, prepare homogeneous salting liquid；
（7）The salting liquid prepared and carbon nano-fiber/graphene composite film are put into water heating kettle, in 200 DEG C
15h is reacted, after after Temperature fall, taking out tunica fibrosa and cleaning multiple and dry repeatedly with deionized water and ethanol, is prepared
Tungsten disulfide/carbon nano-fiber/graphene composite material, is designated as WS2/CNF/G-1；
（8）Tungsten disulfide/carbon nano-fiber/the graphene composite material prepared is carried out under inert gas shielding
Heat treatment, to improve the crystal structure of tungsten disulfide.Heat treatment temperature is 350 DEG C, and heat treatment time is 3 h.
Embodiment 2, the quality of the thio ammonium tungstate in embodiment 1 is changed into 10 mg, remaining equal be the same as Example 1, final institute
The composite of acquisition is designated as WS2/CNF/G-2.Result of implementation：Tungsten disulfide nano slices be equably grown in carbon nano-fiber/
On graphene；With WS2/ CNF/G-1 is compared, WS2The lamella of tungsten disulfide nano slices in/CNF/G-2 is smaller, and content is also less.
Embodiment 3, the quality of the thio ammonium tungstate in embodiment 1 is changed into 30 mg, remaining equal be the same as Example 1, final institute
The composite of acquisition is designated as WS2/CNF/G-3.Result of implementation：Tungsten disulfide nano slices be equably grown in carbon nano-fiber/
On graphene；With WS2/ CNF/G-1 is compared, WS2The lamella of tungsten disulfide nano slices in/CNF/G-3 is larger, and content is also more,
And there is a small amount of tungsten disulfide aggregate.
Embodiment 4, the solvent thermal reaction temperature in embodiment 1 is changed into 220 DEG C, the reaction time is changed into 24 h, and remaining is equal
Be the same as Example 1, the composite finally obtained is designated as WS2/CNF/G-4.Result of implementation：Tungsten disulfide nano slices are equably given birth to
Length is on carbon nano-fiber/graphene；With WS2/ CNF/G-1 is compared, WS2The lamella of tungsten disulfide nano slices in/CNF/G-4
Larger, crystallization degree is higher.
Embodiment 5, the organic solvent in embodiment 1 is changed toN,N-Dimethyl acetamide, the concentration of hydrazine hydrate is selected
80%, its consumption is changed into 0.3 mL, and remaining equal be the same as Example 1, the composite finally obtained is designated as WS2/CNF/G-5.Implement
As a result：Tungsten disulfide nano slices are equably grown on carbon nano-fiber/graphene；With WS2/ CNF/G-1 is compared, WS2/CNF/
Tungsten disulfide nano slices in G-5 do not change.
Claims (10)
1. a kind of preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material, it is characterised in that：Pass through Static Spinning
Silk prepares polyacrylonitrile nanofiber film, and graphite oxide is wrapped up on polyacrylonitrile nanofiber by solution infusion method
Alkene, then carbon nano-fiber/graphene composite film is prepared by high temperature cabonization, finally by a step solvent-thermal method in graphite
Growth in situ tungsten disulfide nano slices, are comprised the following steps that on alkene/carbon nano-fiber：
（1）Polyacrylonitrile powder is added toN,N-In solvent dimethylformamide, lasting stirring obtains homogeneous sticky scattered
Liquid；
（2）Obtained polyacrylonitrile dispersion liquid is subjected to electrostatic spinning, polyacrylonitrile nanofiber film is obtained；
（3）Polyacrylonitrile nanofiber film is pre-oxidized in air atmosphere, the polyacrylonitrile nano after being pre-oxidized
Tunica fibrosa；
（4）Polyacrylonitrile nanofiber film after gained is pre-oxidized soaks in graphene oxide solution, obtains polyacrylonitrile
Nanofiber/graphene oxide composite membrane；
（5）Gained polyacrylonitrile nanofiber/graphene oxide composite membrane is subjected to high temperature cabonization under inert gas shielding, obtained
To carbon nano-fiber/graphene composite film；
（6）Thio ammonium tungstate and hydrazine hydrate are dissolved in organic solvent, homogeneous salting liquid is obtained；
（7）By obtained above-mentioned salting liquid and carbon nano-fiber/graphene composite film by solvent thermal reaction, curing is obtained
Tungsten/carbon nano-fiber/graphene composite material；
（8）Obtained above-mentioned tungsten disulfide/carbon nano-fiber/graphene composite material is subjected to hot place under inert gas shielding
Reason, to improve the crystal structure of tungsten disulfide.
2. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（2）Described electrostatic spinning, its technological parameter is：The kV of electrostatic field voltage 15 ~ 25, the mm of spinning speed 0.2 ~ 0.4
min-1, receive the cm of distance 15 ~ 25.
3. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（3）Described pre-oxidation, temperature is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min-1, preoxidation time is 1 ~ 2
h。
4. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（4）Described solution immersion, the concentration of graphene oxide solution is 0.5 ~ 2mg mL-1, soak time is 12 ~ 36
h。
5. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（5）During described high temperature cabonization, the inert gas is high-purity argon gas or high pure nitrogen, high temperature cabonization temperature
For 1000 ~ 1500 DEG C, the high temperature cabonization time is 1 ~ 3 h.
6. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（6）In described salting liquid preparation process, organic solvent used isN,N-Dimethylformamide,N,N-Dimethyl second
Acid amides orN-The thio ammonium tungstate of methyl pyrrolidone；The concentration of the thio ammonium tungstate of configuration is 1 ~ 3 mg mL-1；Described hydration
Hydrazine concentration is 30% ~ 80%, and consumption is 0.1 ~ 0.3 mL.
7. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（7）Described solvent thermal reaction, reaction temperature is 160 ~ 220 DEG C, and the reaction time is 10 ~ 24 h.
8. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, its feature
It is step（8）In described heat treatment process, inert gas used is high-purity argon gas or high pure nitrogen, and heat treatment temperature is
250 ~ 400 DEG C, heat treatment time is 1 ~ 4 h.
9. a kind of tungsten disulfide/carbon nano-fiber/graphene prepared by one of the claim 1-8 preparation methods is multiple
Condensation material.
10. tungsten disulfide/carbon nano-fiber/graphene composite material as claimed in claim 9 is as electrocatalysis material, and
The application of the electrode material of lithium ion battery and solar cell.
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| CN106115786B (en) * | 2016-06-27 | 2017-09-15 | 中国地质大学（北京） | A kind of tungsten disulfide nano slices tubulose aggregation and preparation method thereof |
| CN106229359B (en) * | 2016-07-29 | 2017-08-29 | 中国地质大学（北京） | A kind of efficient photoelectricity treater converter based on carbon fiber@tungsten disulfide nano slices core-shell structures and preparation method thereof |
| CN107034663B (en) * | 2017-04-19 | 2019-10-01 | 江苏大学 | A kind of tungsten disulfide/carbon nano-fiber composite material and its preparation method and application |
| CN109309224B (en) * | 2018-10-30 | 2021-07-27 | 陕西科技大学 | Preparation method of tungsten disulfide/CFC @ C multiphase composite electrode material |
| CN110112005B (en) * | 2019-05-15 | 2021-02-09 | 宁波石墨烯创新中心有限公司 | Composite electrode and manufacturing method and application thereof |
| CN112758985B (en) * | 2019-10-21 | 2022-03-22 | 中国科学院福建物质结构研究所 | WS (WS)2Nitrogen-doped carbon composite material, preparation method and application thereof |
| CN112837941A (en) * | 2021-01-13 | 2021-05-25 | 巫国家 | Preparation method of active carbon fiber porous tungsten disulfide nano composite material |
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