CN105322147A - Tungsten disulfide/carbon nanofiber/graphene composite material and preparation method thereof - Google Patents
Tungsten disulfide/carbon nanofiber/graphene composite material and preparation method thereof Download PDFInfo
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- CN105322147A CN105322147A CN201510622958.9A CN201510622958A CN105322147A CN 105322147 A CN105322147 A CN 105322147A CN 201510622958 A CN201510622958 A CN 201510622958A CN 105322147 A CN105322147 A CN 105322147A
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- graphene composite
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 34
- 239000002121 nanofiber Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 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
- 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 21
- 239000007788 liquid Substances 0.000 claims description 14
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000005686 electrostatic field Effects 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- VRJMFRRFFQFIBZ-UHFFFAOYSA-N CN(CCC1)C1=O.NS(O)(=O)=O Chemical compound CN(CCC1)C1=O.NS(O)(=O)=O VRJMFRRFFQFIBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- -1 n Chemical compound 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 150000001875 compounds Chemical class 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003068 static effect Effects 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
- 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
- 238000001035 drying Methods 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial 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
- 230000001052 transient effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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 the technical field of transitional metal sulfide-carbon materials, and particularly relates to a tungsten disulfide/carbon nanofiber/graphene composite material and a preparation method thereof. The preparation method comprises the following steps: preparing a polyacrylonitrile nanofiber membrane in an electrostatic spinning manner; wrapping a polyacrylonitrile nanofiber with a graphene oxide through a solution immersion method; preparing a carbon nanofiber/graphene composite membrane through a high-temperature carbonization; and finally growing a tungsten disulfide nanosheet on the carbon nanofiber/graphene in situ through a one-step solvothermal method. The prepared tungsten disulfide/carbon nanofiber/graphene composite material has the advantages of stable chemical property, good conductivity, excellent mechanical property and the like, and can be used as an ideal high-performance electric catalytic material and an electrode material for new energy devices of a lithium-ion battery, a solar battery and the like.
Description
Technical field
The invention belongs to transient metal sulfide-material with carbon element technical field, be specifically related to a kind of tungsten disulfide/carbon nano-fiber/graphene composite material and preparation method thereof.
Technical background
Carbon nano-fiber has acted on the physical and chemical performance of carbon nanomaterial excellence, as the mechanical property of excellence, high specific area and good chemical stability etc., these special natures make it be widely used in the fields such as the flexible base material of catalyst carrier, high molecule nano composite material, power conversion and memory device.Electrostatic spinning is a kind of technology simply and effectively preparing carbon nano-fiber, by high-pressure electrostatic, polymer solution is carried out spinning, then carry out pre-oxidation and high temperature cabonization can prepare the Static Spinning carbon nanofiber membrane with three-dimensional porous structure and high-specific surface area.This patent adopts electrostatic spinning process, polyacrylonitrile solution is carried out spinning and prepares polyacrylonitrile nanofiber film by pre-oxidation, on polyacrylonitrile nanofiber, graphene oxide is wrapped up through solution infusion method, prepare carbon nano-fiber/graphene composite film by high temperature cabonization again, and prepare high-performance composite materials further as base material.
Tungsten disulfide is the Transition-metal dichalcogenide of a quasi-representative, and it belongs to hexagonal crystal system, and be very strong S-W-S covalent bond in layer, interlayer is more weak Van der Waals force, and thickness in monolayer is about 0.65nm.The tungsten disulfide nano slices layer of individual layer can obtain by the method for tape stripping or lithium ion intercalation.Research shows, the active edge that tungsten disulfide exposes has catalytic activity for hydrogen evolution, therefore has extensive use in electrochemical catalysis field.But pure tungsten disulfide is easy to reunite, and the endothecium structure of its preferred growth inertia, but not active lamella edge, a large amount of aggregates also further suppress the exposure at active edge, adds the conductivity that it is poor, and the excellent properties of pure tungsten disulfide often cannot be fully used.Therefore, the base material of tungsten disulfide and other high conductivity is carried out high efficiency composition significant.
The present invention, by simple technological design, prepares a kind of novel tungsten disulfide/carbon nano-fiber/graphene composite material.This composite material has following advantage: Static Spinning carbon nano-fiber has unique three-dimensional porous structure, higher specific area and excellent mechanical property; Graphene parcel carbon nano-fiber can improve the conductivity of carbon nano-fiber/graphene composite film entirety, promotes the fast transport of electronics; Tungsten disulfide nano slices grows equably on carbon nano-fiber/Graphene, effectively can suppress the reunion of tungsten disulfide self, makes the active edge of tungsten disulfide nano slices obtain more fully exposing; The mechanical property of carbon nano-fiber excellence makes composite material can be used as flexible electrode material and is applied to catalysis and energy storage device; Tungsten disulfide nano slices itself possesses higher catalytic activity and theoretical stored energy capacitance value, can improve catalytic performance and the stored energy performance of composites.Therefore, carbon nano-fiber/Graphene and tungsten disulfide nano slices are carried out effective compound, synergy good between three can be realized, to prepare the composite material of excellent performance.
Summary of the invention
Tungsten disulfide/carbon nano-fiber/graphene composite material that the object of the present invention is to provide a kind of electrochemical performance and preparation method thereof.
Tungsten disulfide/carbon nano-fiber/graphene composite material provided by the present invention, its raw materials composition comprises: polyacrylonitrile,
n, N-dimethyl formamide, graphene oxide, sulfo-ammonium tungstate and hydrazine hydrate.
Tungsten disulfide/carbon nano-fiber/graphene composite material provided by the present invention, its preparation process comprises: prepare polyacrylonitrile nanofiber film by electrostatic spinning, on polyacrylonitrile nanofiber, graphene oxide is wrapped up through solution infusion method, carbon nano-fiber/graphene composite film is prepared again by high temperature cabonization, finally by step solvent-thermal method growth in situ tungsten disulfide nano slices on graphene/carbon nanofiber, concrete steps are as follows:
(1) polyacrylonitrile powder is joined
n, N-in solvent dimethylformamide, Keep agitation, obtains homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, obtain polyacrylonitrile nanofiber film;
(3) polyacrylonitrile spinning film is carried out pre-oxidation in air atmosphere, obtain the polyacrylonitrile nanofiber film after pre-oxidation;
(4) the polyacrylonitrile nanofiber film after gained pre-oxidation is soaked in graphene oxide solution, obtain polyacrylonitrile nanofiber/graphene oxide composite membrane;
(5) gained polyacrylonitrile nanofiber/graphene composite film is carried out high temperature cabonization under inert gas shielding, obtain carbon nano-fiber/graphene composite film;
(6) sulfo-ammonium tungstate and hydrazine hydrate are dissolved in organic solvent, obtain homogeneous salting liquid;
(7) by the above-mentioned salting liquid that obtains and carbon nano-fiber/graphene composite film by solvent thermal reaction, obtain tungsten disulfide/carbon nano-fiber/graphene composite material;
(8) the above-mentioned tungsten disulfide/carbon nano-fiber/graphene composite material obtained is heat-treated, to improve the crystal structure of tungsten disulfide under inert gas shielding.
In the present invention, the electrostatic spinning process described in step (2), its adjusting process parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
In the present invention, the preoxidation process described in step (3), the temperature of pre-oxidation is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min
-1, preoxidation time is 1 ~ 2h, preferred 1.5h.
In the present invention, the described solution immersion process of step (4), the concentration of graphene oxide is 0.5 ~ 2mgmL
-1, soak time is 12 ~ 36h.
In the present invention, in the high temperature cabonization process described in step (5), inert gas used is high-purity argon gas or high pure nitrogen, and high temperature cabonization temperature is 1000 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3h, preferred 2h.
In the present invention, in the salting liquid preparation process described in step (6), described organic solvent is
n, N-dimethyl formamide,
n, N-dimethylacetylamide or
n-methyl pyrrolidone sulfo-ammonium tungstate; The concentration of the sulfo-ammonium tungstate of configuration is 1 ~ 3mgmL
-1, preferred 2mgmL
-1; Described concentration of hydrazine hydrate is 30% ~ 80%, and consumption is 0.1 ~ 0.3mL.
In the present invention, the solvent thermal reaction described in step (7), reaction temperature is 160 ~ 220 DEG C, preferably 180 ~ 200 DEG C, and the reaction time is 10 ~ 24h, preferably 12 ~ 15h.
In the present invention, in the heat treatment process described in step (8), inert gas used is high-purity argon gas or high pure nitrogen, and heat treatment temperature is 250 ~ 400 DEG C, preferably 300 ~ 350 DEG C, and heat treatment time is 1 ~ 4h, preferably 2 ~ 3h.
Use scanning electron microscopy (SEM), X-ray diffractometer (XRD) characterize the structure and morphology of tungsten disulfide/carbon nano-fiber/graphene composite material that the present invention obtains, and its result is as follows:
(1) SEM test result shows: in carbon nano-fiber/graphene composite film, and graphene sheet layer is closely wrapped in carbon nano-fiber on the surface, and the diameter of carbon nano-fiber is about 200 ~ 300nm.In tungsten disulfide/carbon nano-fiber/graphene composite material, tungsten disulfide nano slices grows equably on carbon nano-fiber/Graphene, effectively inhibits the reunion of tungsten disulfide self, and the active edge of tungsten disulfide nano slices layer is fully exposed.This has benefited from carbon nano-fiber/Graphene three-D space structure and higher specific area, and the growth for tungsten disulfide provides more site.See accompanying drawing 1 and accompanying drawing 2;
(2) XRD test result shows, prepared carbon nano-fiber/graphene composite film has a wider diffraction maximum at ° place, 2 θ=26, corresponding to (002) crystal face of carbon nano-fiber and Graphene.Prepared tungsten disulfide/carbon nano-fiber/graphene composite material demonstrates the characteristic peak of tungsten disulfide, in 2 θ=13.3 °, and 33.8 °, there is diffraction maximum in 39.6 ° and 59.9 ° of places, correspond respectively to (002) of tungsten disulfide, (101), (103) and (100) crystal face.Meanwhile, having there is the characteristic peak of carbon nano-fiber/Graphene at ° place, 2 θ=26 in prepared tungsten disulfide/carbon nano-fiber/graphene composite material, confirms effective compound of carbon nano-fiber/Graphene and tungsten disulfide.See accompanying drawing 3.
The invention has the advantages that:
(1) preparation process is simple, is easy to operation, is a kind of convenient effective preparation method;
(2) experimental design is ingenious.Soaked and high temperature cabonization technology by electrostatic spinning, solution, prepare the carbon nano-fiber/graphene composite film with three-dimensional porous structure and high-specific surface area simply and effectively, and as base material, by step solvent-thermal method growth in situ tungsten disulfide nano slices on carbon nano-fiber/Graphene, effectively inhibit the reunion of tungsten disulfide self, achieve the high efficiency composition of one-dimensional material and two-dimensional material, thus construct the composite material with multilevel hierarchy;
(3) tungsten disulfide/carbon nano-fiber/graphene composite material prepared by has good pliability, higher conductivity and higher catalytic performance and stored energy performance.Carbon nano-fiber/Graphene and tungsten disulfide nano slices are carried out effective compound, both advantages can be made to be given full play to, thus construct novel high-performance composite material.
Tungsten disulfide/carbon nano-fiber/graphene composite material prepared by the present invention, can be used as the ideal electrode material of high performance catalyst material and the new energy devices such as lithium ion battery, solar cell.
Accompanying drawing explanation
Fig. 1 is the SEM figure of carbon nano-fiber/graphene composite material in the present invention.
Fig. 2 is the SEM figure of tungsten disulfide/carbon nano-fiber/graphene composite material in the present invention.
Fig. 3 is the XRD figure of tungsten disulfide/carbon nano-fiber/graphene composite material of the present invention.
Embodiment
Below in conjunction with instantiation, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition, after the content of having read the present invention's instruction, those skilled in the art can make various change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1,the present embodiment comprises the following steps:
(1) 1g polyacrylonitrile powder is joined 5mL
n, N-in solvent dimethylformamide, Keep agitation, prepares homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, its adjusting process parameter is: electrostatic field voltage 20kV, spinning speed 0.3mmmin
-1, receiving range 20cm, prepares polyacrylonitrile nanofiber film;
(3) the polyacrylonitrile spinning film obtained is carried out pre-oxidation in air atmosphere, the temperature of pre-oxidation is 250 DEG C, and heating rate is 1 DEG C of min
-1, preoxidation time is 1.5h, prepares the polyacrylonitrile nanofiber film after pre-oxidation;
(4) by the polyacrylonitrile nanofiber film after gained pre-oxidation at 1mgmL
-1soak 24h in graphene oxide solution, prepare polyacrylonitrile nanofiber/graphene oxide composite membrane;
(5) gained polyacrylonitrile nanofiber/graphene oxide composite membrane is carried out high temperature cabonization in high pure nitrogen, high temperature cabonization temperature is 1200 DEG C, and the high temperature cabonization time is 2h, prepares carbon nano-fiber/graphene composite film;
(6) 20mg sulfo-ammonium tungstate and 0.1mL50% hydrazine hydrate are dissolved in 10mL
n, N-in solvent dimethylformamide, prepare homogeneous salting liquid;
(7) salting liquid prepared and carbon nano-fiber/graphene composite film are put into water heating kettle, 15h is reacted in 200 DEG C, after Temperature fall, take out tunica fibrosa and repeatedly clean repeatedly and drying with deionized water and ethanol, prepare tungsten disulfide/carbon nano-fiber/graphene composite material, be designated as WS
2/ CNF/G-1;
(8) tungsten disulfide/carbon nano-fiber/graphene composite material prepared is heat-treated, to improve the crystal structure of tungsten disulfide under inert gas shielding.Heat treatment temperature is 350 DEG C, and heat treatment time is 3h.
embodiment 2,the quality of the sulfo-ammonium tungstate in embodiment 1 is become 10mg, and all the other are all with embodiment 1, and final obtained composite material is designated as WS
2/ CNF/G-2.Result of implementation: tungsten disulfide nano slices grows equably on carbon nano-fiber/Graphene; With WS
2/ CNF/G-1 compares, WS
2the lamella of the tungsten disulfide nano slices in/CNF/G-2 is less, and content is also less.
embodiment 3,the quality of the sulfo-ammonium tungstate in embodiment 1 is become 30mg, and all the other are all with embodiment 1, and final obtained composite material is designated as WS
2/ CNF/G-3.Result of implementation: tungsten disulfide nano slices grows equably on carbon nano-fiber/Graphene; With WS
2/ CNF/G-1 compares, WS
2the lamella of the tungsten disulfide nano slices in/CNF/G-3 is comparatively large, and content is also more, and occurs a small amount of tungsten disulfide aggregate.
embodiment 4,solvent thermal reaction temperature in embodiment 1 is become 220 DEG C, and the reaction time becomes 24h, and all the other are all with embodiment 1, and final obtained composite material is designated as WS
2/ CNF/G-4.Result of implementation: tungsten disulfide nano slices grows equably on carbon nano-fiber/Graphene; With WS
2/ CNF/G-1 compares, WS
2the lamella of the tungsten disulfide nano slices in/CNF/G-4 is comparatively large, and crystallization degree is higher.
embodiment 5,organic solvent in embodiment 1 is changed into
n, N-dimethylacetylamide, the concentration of hydrazine hydrate selects 80%, and its consumption becomes 0.3mL, and all the other are all with embodiment 1, and final obtained composite material is designated as WS
2/ CNF/G-5.Result of implementation: tungsten disulfide nano slices grows equably on carbon nano-fiber/Graphene; With WS
2/ CNF/G-1 compares, WS
2tungsten disulfide nano slices in/CNF/G-5 does not change.
Claims (10)
1. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material, it is characterized in that: prepare polyacrylonitrile nanofiber film by electrostatic spinning, on polyacrylonitrile nanofiber, graphene oxide is wrapped up through solution infusion method, carbon nano-fiber/graphene composite film is prepared again by high temperature cabonization, finally by step solvent-thermal method growth in situ tungsten disulfide nano slices on graphene/carbon nanofiber, concrete steps are as follows:
(1) polyacrylonitrile powder is joined
n, N-in solvent dimethylformamide, Keep agitation, obtains homogeneous thickness dispersion liquid;
(2) the polyacrylonitrile dispersion liquid obtained is carried out electrostatic spinning, obtain polyacrylonitrile nanofiber film;
(3) polyacrylonitrile spinning film is carried out pre-oxidation in air atmosphere, obtain the polyacrylonitrile nanofiber film after pre-oxidation;
(4) the polyacrylonitrile nanofiber film after gained pre-oxidation is soaked in graphene oxide solution, obtain polyacrylonitrile nanofiber/graphene oxide composite membrane;
(5) gained polyacrylonitrile nanofiber/graphene composite film is carried out high temperature cabonization under inert gas shielding, obtain carbon nano-fiber/graphene composite film;
(6) sulfo-ammonium tungstate and hydrazine hydrate are dissolved in organic solvent, obtain homogeneous salting liquid;
(7) by the above-mentioned salting liquid that obtains and carbon nano-fiber/graphene composite film by solvent thermal reaction, obtain tungsten disulfide/carbon nano-fiber/graphene composite material;
(8) the above-mentioned tungsten disulfide/carbon nano-fiber/graphene composite material obtained is heat-treated, to improve the crystal structure of tungsten disulfide under inert gas shielding.
2. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, it is characterized in that the electrostatic spinning described in step (2), its technological parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
3. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that the pre-oxidation described in step (3), and temperature is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min
-1, preoxidation time is 1 ~ 2h.
4. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, it is characterized in that the solution described in step (4) soaks, the concentration of graphene oxide solution is 0.5 ~ 2mgmL
-1, soak time is 12 ~ 36h.
5. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, it is characterized in that in the high temperature cabonization process described in step (5), described inert gas is high-purity argon gas or high pure nitrogen, high temperature cabonization temperature is 1000 ~ 1500 DEG C, and the high temperature cabonization time is 1 ~ 3h.
6. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that in the salting liquid preparation process described in step (6), organic solvent used is
n, N-dimethyl formamide,
n, N-dimethylacetylamide or
n-methyl pyrrolidone sulfo-ammonium tungstate; The concentration of the sulfo-ammonium tungstate of configuration is 1 ~ 3mgmL
-1; Described concentration of hydrazine hydrate is 30% ~ 80%, and consumption is 0.1 ~ 0.3mL.
7. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that the solvent thermal reaction described in step (7), and reaction temperature is 160 ~ 220 DEG C, and the reaction time is 10 ~ 24h.
8. the preparation method of tungsten disulfide/carbon nano-fiber/graphene composite material according to claim 1, it is characterized in that in the heat treatment process described in step (8), inert gas used is high-purity argon gas or high pure nitrogen, and heat treatment temperature is 250 ~ 400 DEG C, and heat treatment time is 1 ~ 4h.
9. tungsten disulfide/carbon nano-fiber/the graphene composite material prepared by the described preparation method of one of claim 1-8.
10. tungsten disulfide/carbon nano-fiber/graphene composite material as claimed in claim 9 is as high-performance electric catalysis material, and the application of the electrode material of lithium ion battery and solar cell.
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