CN105322146A - Molybdenum selenide/carbon nanofiber/graphene composite material and preparation method thereof - Google Patents
Molybdenum selenide/carbon nanofiber/graphene composite material and preparation method thereof Download PDFInfo
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- CN105322146A CN105322146A CN201510621483.1A CN201510621483A CN105322146A CN 105322146 A CN105322146 A CN 105322146A CN 201510621483 A CN201510621483 A CN 201510621483A CN 105322146 A CN105322146 A CN 105322146A
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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 83
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- MHWZQNGIEIYAQJ-UHFFFAOYSA-N molybdenum diselenide Chemical compound [Se]=[Mo]=[Se] MHWZQNGIEIYAQJ-UHFFFAOYSA-N 0.000 title abstract 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 36
- 239000002121 nanofiber Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000007772 electrode material Substances 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 3
- 238000007654 immersion Methods 0.000 claims abstract 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 60
- 229910052750 molybdenum Inorganic materials 0.000 claims description 60
- 239000011733 molybdenum Substances 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009938 salting Methods 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
- 238000006243 chemical reaction Methods 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 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
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000003763 carbonization Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002135 nanosheet Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 229910016001 MoSe Inorganic materials 0.000 description 16
- 241000446313 Lamella Species 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- DORQJBTVNDGTEY-UHFFFAOYSA-N selanylidenemolybdenum Chemical compound [Se].[Mo] DORQJBTVNDGTEY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal selenium compounds Chemical class 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
- 229910018113 Se—Mo—Se Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001721 carbon Chemical group 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
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002114 nanocomposite 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
- 229940065287 selenium compound Drugs 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
-
- 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 selenide-carbon materials, and particularly relates to a molybdenum selenide/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 molybdenum selenide nanosheet on the carbon nanofiber/graphene in situ through a one-step solvothermal method. The prepared molybdenum selenide/carbon nanofiber/graphene composite material is controllable in morphology, has relatively high specific surface area and excellent conductivity, 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 transition metal selenides-material with carbon element technical field, be specifically related to a kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof.
Background technology
Graphene is a kind of two-dimensional material only having an atomic thickness be made up of carbon atom, there is very excellent physical and chemical performance, as the mechanical property of excellence, high conductivity and good heat conductivility etc., be considered to one of potential nano material of current most.As a kind of one-dimensional carbon nano material, carbon nano-fiber has the advantages such as good mechanical property, larger specific area and good chemical stability, and 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 prepare polyacrylonitrile nanofiber film by pre-oxidation, then 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.
Selenizing molybdenum is the transition metal selenium compounds of group of a quasi-representative, and be very strong Se-Mo-Se covalent bond in its layer, interlayer is more weak Van der Waals force.Research shows, the active edge that selenizing molybdenum exposes has catalytic activity for hydrogen evolution, therefore has extensive use in electrochemical catalysis field.But pure selenium molybdenum 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 selenium molybdenum cannot be fully used usually.Therefore, the base material of selenizing molybdenum and other high conductivity is carried out high efficiency composition significant.
The present invention, by simple technological design, prepares a kind of novel selenizing molybdenum/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; Selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene, effectively can suppress the reunion of selenizing molybdenum self, and the active edge of selenizing molybdenum nanometer sheet is exposed more fully; 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; Selenizing molybdenum nanometer sheet 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 selenizing molybdenum nanometer sheet are carried out effective compound, synergy good between three can be realized, to prepare the composite material of excellent performance.
Summary of the invention
Selenizing molybdenum/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.
Selenizing molybdenum/carbon nano-fiber/graphene composite material provided by the present invention, its raw materials composition comprises: polyacrylonitrile,
n, N-dimethyl formamide, graphene oxide, selenium powder, hydrazine hydrate and molybdate.
Selenizing molybdenum/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 selenizing molybdenum nanometer sheet 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) selenium powder is joined in hydrazine hydrate solution, Keep agitation, be warming up to uniform temperature, after temperature stabilization, keep a period of time, prepare selenium powder dispersion liquid;
(7) selenium powder dispersion liquid and molybdate are dissolved in organic solvent, Keep agitation, prepare homogeneous salting liquid;
(8) by the salting liquid for preparing and carbon nano-fiber/graphene composite film by solvent thermal reaction, obtain selenizing molybdenum/carbon nano-fiber/graphene composite material.
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 pre-oxidation 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 of step (4) soaks, and the concentration of graphene oxide solution 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 selenium powder dispersion liquid preparation process described in step (6), described concentration of hydrazine hydrate is 30% ~ 80%; The concentration of the selenium powder dispersion liquid of configuration is 5 ~ 15mgmL
-1, preferred 10mgmL
-1; Warming temperature is 70 ~ 90 DEG C, preferably 80 DEG C; Temperature retention time is 1 ~ 3h, preferred 2h.
In the present invention, in the salting liquid preparation process described in step (7), organic solvent used is
n, N-dimethyl formamide,
n, N-dimethylacetylamide or
n-methyl pyrrolidone sulfo-ammonium tungstate; Molybdate is ammonium molybdate or sodium molybdate; The concentration of the molybdate of configuration is 1 ~ 5mgmL
-1; The consumption of selenium powder dispersion liquid should make the mol ratio of selenium and molybdenum be 2:1.
In the present invention, the solvent thermal reaction described in step (8), reaction temperature is 180 ~ 240 DEG C, preferably 200 ~ 220 DEG C, and the reaction time is 10 ~ 24h, preferably 12 ~ 15h.
Use scanning electron microscopy (SEM), X-ray diffractometer (XRD) characterize the structure and morphology of selenizing molybdenum/carbon nano-fiber/graphene composite material that the present invention obtains, and its result is as follows:
(1) SEM test result shows: the diameter of Static Spinning polyacrylonitrile fibre is about 200 ~ 300nm, smooth surface.In carbon nano-fiber/graphene composite film, graphene sheet layer is closely wrapped in carbon nano-fiber on the surface.In selenizing molybdenum/carbon nano-fiber/graphene composite material, selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene, effectively inhibits the reunion of selenizing molybdenum self, and the active edge of selenizing molybdenum nanoscale twins is fully exposed.This has benefited from carbon nano-fiber/Graphene three-D space structure and higher specific area, and the growth for selenizing molybdenum 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 selenizing molybdenum/carbon nano-fiber/graphene composite material demonstrates the characteristic peak of selenizing molybdenum, and in 2 θ=13.3 °, diffraction maximum appears in 33.9 ° and 55.7 ° of places, corresponds respectively to (002) of selenizing molybdenum, (100) and (110) crystal face.Meanwhile, having there is the characteristic peak of carbon nano-fiber/Graphene at ° place, 2 θ=26 in prepared selenizing molybdenum/carbon nano-fiber/graphene composite material, confirms carbon nano-fiber/Graphene and selenizing molybdenum effective compound between the two.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 selenizing molybdenum nanometer sheet on carbon nano-fiber/Graphene, effectively inhibit the reunion of selenizing molybdenum self, achieve effective compound of one-dimensional material and two-dimensional material, thus construct the novel high-performance composite material with multilevel hierarchy;
(3) the selenizing molybdenum/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 selenizing molybdenum nanometer sheet are carried out effective compound, both advantages can be made to be given full play to, thus construct the advanced composite material (ACM) with excellent properties.
Selenizing molybdenum/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 in the present invention: (A) polyacrylonitrile nanofiber; (B) carbon nano-fiber/Graphene.
Fig. 2 is the SEM figure of selenizing molybdenum/carbon nano-fiber/graphene composite material in the present invention.
Fig. 3 is the XRD figure of selenizing of the present invention molybdenum/carbon nano-fiber/graphene composite material.
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) 100mg selenium powder is joined in 10mL50% hydrazine hydrate, Keep agitation, be warming up to 80 DEG C, after temperature stabilization, keep 2h, prepare selenium powder dispersion liquid;
(7) selenium powder dispersion liquid obtained for 5mL and 76.6mg sodium molybdate are dissolved in 35mL
n, N-in solvent dimethylformamide, Keep agitation, prepares homogeneous salting liquid;
(8) 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 selenizing molybdenum/carbon nano-fiber/graphene composite material, be designated as MoSe
2/ CNF/G-1.
embodiment 2,the consumption of the selenium powder dispersion liquid in embodiment 1 is become 2.5mL, and the consumption of sodium molybdate becomes 38.3mg, and all the other are all with embodiment 1, and final obtained composite material is designated as MoSe
2/ CNF/G-2.Result of implementation: selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene; With MoSe
2/ CNF/G-1 compares, MoSe
2the lamella of the selenizing molybdenum nanometer sheet in/CNF/G-2 is less, and content is also less.
embodiment 3,the consumption of the selenium powder dispersion liquid in embodiment 1 is become 7.5mL, and the consumption of sodium molybdate becomes 114.9mg, and all the other are all with embodiment 1, and final obtained composite material is designated as MoSe
2/ CNF/G-3.Result of implementation: selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene; With MoSe
2/ CNF/G-1 compares, MoSe
2the lamella of the selenizing molybdenum nanometer sheet in/CNF/G-3 is comparatively large, and content is also more, and occurs a small amount of selenizing molybdenum aggregate.
embodiment 4,organic solvent in embodiment 1 is changed into
n, N-dimethylacetylamide, molybdate selects sodium molybdate, and the concentration of its configuration becomes 5mgmL
-1, all the other are all with embodiment 1, and final obtained composite material is designated as MoSe
2/ CNF/G-4.Result of implementation: selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene; With MoSe
2/ CNF/G-1 compares, MoSe
2the lamella of the selenizing molybdenum nanometer sheet in/CNF/G-4 is comparatively large, and thickness does not change.
embodiment 5,solvent thermal reaction temperature in embodiment 1 is become 240 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 MoSe
2/ CNF/G-5.Result of implementation: selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene; With MoSe
2/ CNF/G-1 compares, MoSe
2the lamella of the selenizing molybdenum nanometer sheet in/CNF/G-5 is comparatively large, and thickness is comparatively large, and crystallization degree is higher.
embodiment 6,concentration of hydrazine hydrate in embodiment 1 is become 80%, and the selenium powder concentration of configuration becomes 15mgmL
-1, warming temperature becomes 70 DEG C, and temperature retention time is 1h, and all the other are all with embodiment 1, and final obtained composite material is designated as MoSe
2/ CNF/G-6.Result of implementation: selenizing molybdenum nanometer sheet grows equably on carbon nano-fiber/Graphene; With MoSe
2/ CNF/G-1 compares, MoSe
2selenizing molybdenum nanometer sheet in/CNF/G-6 does not change.
Claims (10)
1. the preparation method of selenizing molybdenum/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 selenizing molybdenum nanometer sheet 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) selenium powder is joined in hydrazine hydrate solution, Keep agitation, be warming up to uniform temperature, after temperature stabilization, keep a period of time, obtain selenium powder dispersion liquid;
(7) selenium powder dispersion liquid and molybdate are dissolved in organic solvent, Keep agitation, obtain homogeneous salting liquid;
(8) by the salting liquid for preparing and carbon nano-fiber/graphene composite film by solvent thermal reaction, obtain selenizing molybdenum/carbon nano-fiber/graphene composite material.
2. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that in the electrostatic spinning process described in step (2), technological parameter is: electrostatic field voltage 15 ~ 25kV, spinning speed 0.2 ~ 0.4mmmin
-1, receiving range 15 ~ 25cm.
3. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that in the preoxidation process described in step (3), and 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.
4. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that in the solution immersion process described in step (4), and the concentration of graphene oxide solution is 0.5 ~ 2mgmL
-1, soak time is 12 ~ 36h.
5. the preparation method of selenizing molybdenum/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 selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that in the selenium powder dispersion liquid preparation process described in step (6), concentration of hydrazine hydrate is 30% ~ 80%; The concentration of the selenium powder dispersion liquid of configuration is 5 ~ 15mgmL
-1; Warming temperature is 70 ~ 90 DEG C, and temperature retention time is 1 ~ 3h.
7. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, is characterized in that in the salting liquid preparation process described in step (7), described organic solvent is
n, N-dimethyl formamide,
n, N-dimethylacetylamide or
n-methyl pyrrolidone sulfo-ammonium tungstate; Molybdate is ammonium molybdate or sodium molybdate; The concentration of the molybdate of configuration is 1 ~ 5mgmL
-1; The consumption of selenium powder dispersion liquid should make the mol ratio of selenium and molybdenum be 2:1.
8. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, it is characterized in that the solvent heat described in step (8) is anti-, reaction temperature is 180 ~ 240 DEG C, and the reaction time is 10 ~ 24h.
9. the selenizing molybdenum/carbon nano-fiber/graphene composite material prepared by the described preparation method of one of claim 1-8.
10. selenizing molybdenum/carbon nano-fiber/graphene composite material as claimed in claim 9 is as high-performance electric catalysis material, and the application of electrode material as lithium ion battery and solar cell.
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