CN105322146B - A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof - Google Patents
A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof Download PDFInfo
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- CN105322146B CN105322146B CN201510621483.1A CN201510621483A CN105322146B CN 105322146 B CN105322146 B CN 105322146B CN 201510621483 A CN201510621483 A CN 201510621483A CN 105322146 B CN105322146 B CN 105322146B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 66
- 239000011733 molybdenum Substances 0.000 title claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 34
- 239000002121 nanofiber Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 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
- 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
- 239000007788 liquid Substances 0.000 claims description 28
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000009987 spinning Methods 0.000 claims description 10
- 230000002045 lasting effect Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 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
- 238000007654 immersion Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 230000005686 electrostatic field Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 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
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- -1 transition metal selenides Chemical class 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 5
- 241000446313 Lamella Species 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000001336 alkenes Chemical class 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002070 nanowire Substances 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 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
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- DORQJBTVNDGTEY-UHFFFAOYSA-N selanylidenemolybdenum Chemical compound [Se].[Mo] DORQJBTVNDGTEY-UHFFFAOYSA-N 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 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 transition metal selenides carbon material technical field, specially a kind of selenizing molybdenum/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 selenizing molybdenum nanometer sheet.Selenizing molybdenum/carbon nano-fiber/graphene composite material morphology controllable prepared by the present invention, with higher specific surface area and excellent electric conductivity, 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 transition metal selenides-carbon material technical field, and in particular to a kind of selenizing molybdenum/carbon Nanowire
Dimension/graphene composite material and preparation method thereof.
Background technology
Graphene is a kind of two-dimensional material for the only one of which atomic thickness being made up of carbon atom, with very excellent thing
Physicochemical performance, such as excellent mechanical property, high electric conductivity and good heat conductivility, it is considered to be most dive now
One of nano material of power.As a kind of one-dimensional carbon nano material, carbon nano-fiber has good mechanical property, larger ratio
The advantages of surface area and good chemical stability, these special natures make it be widely used in catalyst carrier, macromolecule to receive
The fields such as the flexible base material of nano composite material, energy conversion and memory device.Electrostatic spinning is that one kind simply and is effectively made
The technology of standby carbon nano-fiber, spinning is carried out by high-pressure electrostatic by polymer solution, then carries 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 uses electrostatic spinning work
Skill, spinning is carried out by polyacrylonitrile solution, and prepares polyacrylonitrile nanofiber film by pre-oxidation, then by solution
Infusion method wraps up graphene oxide on polyacrylonitrile nanofiber, then prepares carbon nano-fiber/stone by high temperature cabonization
Black alkene composite membrane, and further prepare high-performance composite materials as base material.
It in the transition metal selenium compounds of group of a quasi-representative, its layer is very strong Se-Mo-Se covalent bonds, layer that selenizing molybdenum, which is,
Between be weaker Van der Waals force.Research shows that the active edge of selenizing molybdenum exposure has catalytic activity for hydrogen evolution, therefore in electrochemistry
Catalytic field has extensive use.But, pure selenium molybdenum is easy to reunite, and the inert endothecium structure of its preferred growth, rather than
Active lamella edge, substantial amounts of aggregate also further suppress the exposure at active edge, pure along with its poor electric conductivity
The excellent properties of selenizing molybdenum, which are not typically available, to be made full use of.Therefore, selenizing molybdenum and the base material of other high conductivity are entered
Row high efficiency composition is significant.
The present invention prepares a kind of new selenizing molybdenum/carbon nano-fiber/graphene multiple by simple technological design
Condensation material.The composite has following advantage：Static Spinning carbon nano-fiber has unique three-dimensional porous structure, higher ratio
Surface area and excellent mechanical property；It is overall that graphene parcel carbon nano-fiber can improve carbon nano-fiber/graphene composite film
Electric conductivity, promote electronics quick transmission；Selenizing molybdenum nanometer sheet is equably grown on carbon nano-fiber/graphene, can be had
Effect suppresses the reunion of selenizing molybdenum itself, the active edge of selenizing molybdenum nanometer sheet is more fully exposed；Carbon nano-fiber
Excellent mechanical property makes composite to be applied to catalysis and energy storage device as flexible electrode material；Selenizing molybdenum nanometer
Piece possesses higher catalytic activity and theoretical stored energy capacitance value in itself, can improve the overall catalytic performance of composite and energy is deposited
Store up performance.Therefore, carbon nano-fiber/graphene and selenizing molybdenum nanometer sheet are carried out effectively being combined, it is possible to achieve good between three
Good synergy, to prepare the composite of excellent performance.
The content of the invention
It is compound it is an object of the invention to provide a kind of selenizing of electrochemical performance molybdenum/carbon nano-fiber/graphene
Material and preparation method thereof.
Selenizing molybdenum/carbon nano-fiber/graphene composite material provided by the present invention, its preparing raw material composition includes：It is poly-
Acrylonitrile,N,N-Dimethylformamide, graphene oxide, selenium powder, hydrazine hydrate and molybdate.
Selenizing molybdenum/carbon nano-fiber/graphene composite material provided by the present invention, its preparation process includes：By quiet
Electrospun prepares polyacrylonitrile nanofiber film, wraps up oxidation stone on polyacrylonitrile nanofiber by solution infusion method
Black 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 selenizing molybdenum nanometer sheet, is 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
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）Selenium powder is added in hydrazine hydrate solution, lasting stirring is warming up to certain temperature, after after temperature stabilization, keeps
For a period of time, selenium powder dispersion liquid is prepared；
（7）Selenium powder dispersion liquid and molybdate are dissolved in organic solvent, lasting stirring prepares homogeneous salting liquid；
（8）By the salting liquid prepared and carbon nano-fiber/graphene composite film by solvent thermal reaction, selenizing is obtained
Molybdenum/carbon nano-fiber/graphene composite material.
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 pre-oxidation, the temperature of pre-oxidation is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C
min-1, preoxidation time is 1 ~ 2 h, preferably 1.5 h.
In the present invention, step（4）The solution immersion, the concentration of graphene oxide solution is 0.5 ~ 2 mg mL-1, immersion
Time is 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 selenium powder dispersion liquid preparation process, described concentration of hydrazine hydrate is 30% ~ 80%；
The concentration of the selenium powder dispersion liquid of configuration is 5 ~ 15 mg mL-1, preferably 10 mg mL-1；Warming temperature is 70 ~ 90 DEG C, preferably 80
℃；Soaking time is 1 ~ 3 h, preferably 2 h.
In the present invention, step（7）In described salting liquid preparation process, organic solvent used isN,N-Dimethyl formyl
Amine,N,N-Dimethyl acetamide orN-The thio ammonium tungstate of methyl pyrrolidone；Molybdate is ammonium molybdate or sodium molybdate；The molybdenum of configuration
The concentration of hydrochlorate is 1 ~ 5 mg mL-1；The consumption of selenium powder dispersion liquid should make the mol ratio of selenium and molybdenum be 2:1.
In the present invention, step（8）Described solvent thermal reaction, reaction temperature be 180 ~ 240 DEG C, preferably 200 ~ 220 DEG C, instead
It is 10 ~ 24 h, preferably 12 ~ 15 h between seasonable.
Use SEM（SEM）, X-ray diffractometer（XRD）To characterize selenizing molybdenum/carbon that the present invention is obtained
The structure and morphology of nanofiber/graphene composite material, its result is as follows：
（1）SEM test results show：The diameter of Static Spinning polyacrylonitrile fibre is about 200 ~ 300 nm, and surface is smooth.
In carbon nano-fiber/graphene composite film, graphene sheet layer is closely wrapped on carbon nano-fiber surface.In selenizing molybdenum/carbon
In nanofiber/graphene composite material, selenizing molybdenum nanometer sheet is equably grown on carbon nano-fiber/graphene, effectively suppression
The selenizing molybdenum reunion of itself has been made, the active edge of selenizing molybdenum nanoscale twins is fully exposed.This has benefited from carbon Nanowire
Dimension/graphene three-D space structure and higher specific surface area, more sites are provided for the growth of selenizing molybdenum.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 selenizing molybdenum/carbon nano-fiber/graphite
Alkene composite shows the characteristic peak of selenizing molybdenum, diffraction maximum occurs at 2 θ=13.3 °, 33.9 ° and 55.7 °, corresponds to respectively
In selenizing molybdenum（002）,（100）With（110）Crystal face.Meanwhile, prepared selenizing molybdenum/carbon nano-fiber/graphene composite wood
Material occurs in that the characteristic peak of carbon nano-fiber/graphene at 2 θ=26 °, it was confirmed that carbon nano-fiber/graphene and selenizing molybdenum
Between the two effectively compound.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 selenizing molybdenum nanometer sheet on carbon nano-fiber/graphene is crossed, selenizing molybdenum itself is effectively inhibited
Reunion, the effectively compound of one-dimensional material and two-dimensional material is realized, so as to construct the novel high-performance with multilevel hierarchy
Composite；
（3）Prepared selenizing molybdenum/carbon nano-fiber/graphene composite material has preferable pliability, and higher leads
Electrical and higher catalytic performance and energy stores performance.Carbon nano-fiber/graphene and selenizing molybdenum nanometer sheet are carried out effective
It is compound, both advantages can be enable to give full play to, so as to 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 high performance catalyst material with
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 in the present invention：（A）Polyacrylonitrile nanofiber；（B）Carbon nano-fiber/graphene.
Fig. 2 is the SEM figures of selenizing molybdenum/carbon nano-fiber/graphene composite material in the present invention.
Fig. 3 is the XRD of selenizing molybdenum/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 1mg 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）100 mg selenium powders are added in the hydrazine hydrates of 10 mL 50%, lasting stirring is warming up to 80 DEG C, treats temperature stabilization
Afterwards, 2 h are kept, selenium powder dispersion liquid is prepared；
（7）Selenium powder dispersion liquid made from 5 mL and 76.6 mg sodium molybdates are dissolved in 35 mLN,N-Dimethylformamide is molten
In agent, lasting stirring prepares homogeneous salting liquid；
（8）The salting liquid prepared and carbon nano-fiber/graphene composite film are put into water heating kettle, in 200 DEG C
15 h are reacted, after after Temperature fall, taking out tunica fibrosa and cleaning multiple and dry repeatedly with deionized water and ethanol, are prepared
Selenizing molybdenum/carbon nano-fiber/graphene composite material, is designated as MoSe2/CNF/G-1。
Embodiment 2, the consumption of the selenium powder dispersion liquid in embodiment 1 is changed into 2.5 mL, the consumption of sodium molybdate is changed into 38.3
Mg, remaining equal be the same as Example 1, the composite finally obtained is designated as MoSe2/CNF/G-2.Result of implementation：Selenizing molybdenum nanometer
Piece is equably grown on carbon nano-fiber/graphene；With MoSe2/ CNF/G-1 is compared, MoSe2Selenizing molybdenum in/CNF/G-2
The lamella of nanometer sheet is smaller, and content is also less.
Embodiment 3, the consumption of the selenium powder dispersion liquid in embodiment 1 is changed into 7.5 mL, the consumption of sodium molybdate is changed into 114.9
Mg, remaining equal be the same as Example 1, the composite finally obtained is designated as MoSe2/CNF/G-3.Result of implementation：Selenizing molybdenum nanometer
Piece is equably grown on carbon nano-fiber/graphene；With MoSe2/ CNF/G-1 is compared, MoSe2Selenizing molybdenum in/CNF/G-3
The lamella of nanometer sheet is larger, and content is also more, and a small amount of selenizing molybdenum aggregate occurs.
Embodiment 4, the organic solvent in embodiment 1 is changed toN,N-Dimethyl acetamide, molybdate selects sodium molybdate, its
The concentration of configuration is changed into 5 mg mL-1, remaining equal be the same as Example 1, the composite finally obtained is designated as MoSe2/CNF/G-4。
Result of implementation：Selenizing molybdenum nanometer sheet is equably grown on carbon nano-fiber/graphene；With MoSe2/ CNF/G-1 is compared,
MoSe2The lamella of selenizing molybdenum nanometer sheet in/CNF/G-4 is larger, and thickness does not change.
Embodiment 5, the solvent thermal reaction temperature in embodiment 1 is changed into 240 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 MoSe2/CNF/G-5.Result of implementation：Selenizing molybdenum nanometer sheet is equably given birth to
Length is on carbon nano-fiber/graphene；With MoSe2/ CNF/G-1 is compared, MoSe2The piece of selenizing molybdenum nanometer sheet in/CNF/G-5
Layer is larger, and thickness is larger, and crystallization degree is higher.
Embodiment 6, the concentration of hydrazine hydrate in embodiment 1 is changed into 80%, the selenium powder concentration of configuration is changed into 15 mg mL-1, rise
Temperature is changed into 70 DEG C, and soaking time is 1 h, and remaining equal be the same as Example 1, the composite finally obtained is designated as MoSe2/
CNF/G-6.Result of implementation：Selenizing molybdenum nanometer sheet is equably grown on carbon nano-fiber/graphene；With MoSe2/CNF/G-1
Compare, MoSe2Selenizing molybdenum nanometer sheet in/CNF/G-6 does not change.
Claims (10)
1. a kind of preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material, it is characterised in that：Pass through electrostatic spinning
Polyacrylonitrile nanofiber film is prepared, 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 in graphene/carbon
Growth in situ selenizing molybdenum nanometer sheet, is comprised the following steps that on nanofiber：
（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）Selenium powder is added in hydrazine hydrate solution, lasting stirring is warming up to certain temperature, after after temperature stabilization, is kept for one section
Time, obtain selenium powder dispersion liquid；
（7）Selenium powder dispersion liquid and molybdate are dissolved in organic solvent, lasting stirring obtains homogeneous salting liquid；
（8）By the salting liquid prepared 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, its feature exists
In step（2）During described electrostatic spinning, technological parameter is：The kV of electrostatic field voltage 15 ~ 25, spinning speed 0.2 ~ 0.4
mm min-1, receive the cm of distance 15 ~ 25.
3. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, its feature exists
In step（3）In described preoxidation process, the temperature of pre-oxidation is 250 ~ 300 DEG C, and heating rate is 1 ~ 2 DEG C of min-1, pre- oxygen
The change time is 1 ~ 2 h.
4. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, its feature exists
In step（4）In described solution immersion process, the concentration of graphene oxide solution is 0.5 ~ 2 mg mL-1, soak time is 12
~36 h。
5. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, its feature exists
In step（5）During described high temperature cabonization, the inert gas is high-purity argon gas or high pure nitrogen, and high temperature cabonization temperature is
1000 ~ 1500 DEG C, the high temperature cabonization time is 1 ~ 3 h.
6. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, its feature exists
In step（6）In described selenium powder dispersion liquid preparation process, concentration of hydrazine hydrate is 30% ~ 80%；The selenium powder dispersion liquid of configuration it is dense
Spend for 5 ~ 15 mg mL-1；Warming temperature is 70 ~ 90 DEG C, and soaking time is 1 ~ 3 h.
7. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, its feature exists
In step（7）In described salting liquid preparation process, the organic solvent isN,N-Dimethylformamide orN,N-Dimethyl second
Acid amides；Molybdate is ammonium molybdate or sodium molybdate；The concentration of the molybdate of configuration is 1 ~ 5 mg mL-1；The consumption of selenium powder dispersion liquid should
The mol ratio for making selenium and molybdenum is 2:1.
8. the preparation method of selenizing molybdenum/carbon nano-fiber/graphene composite material according to claim 1, its feature exists
In step（8）Described solvent thermal reaction, reaction temperature is 180 ~ 240 DEG C, and the reaction time is 10 ~ 24 h.
9. a kind of selenizing molybdenum/carbon nano-fiber/graphene prepared by one of the claim 1-8 preparation methods is combined
Material.
10. selenizing molybdenum/carbon nano-fiber/graphene composite material as claimed in claim 9 is used as electrocatalysis material, Yi Jizuo
For the application of lithium ion battery and the electrode material of solar cell.
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