CN105280900A - Tungsten disulfide/graphene nanobelt composite material and preparation method thereof - Google Patents
Tungsten disulfide/graphene nanobelt composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- 239000002127 nanobelt Substances 0.000 title claims abstract description 59
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 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
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 45
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 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 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007970 homogeneous dispersion Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 n Chemical compound 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002086 nanomaterial Substances 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000010792 warming Methods 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
-
- 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 transition metal sulfide-carbon materials, and particularly discloses a tungsten disulfide/graphene nanobelt composite material and a preparation method thereof. A graphene nanobelt disclosed by the invention is prepared through solution oxidation, and the tungsten disulfide/graphene nanobelt composite material is formed by tungsten disulfide nanosheets in an in-situ growth manner on the graphene nanobelt through a one-step solvothermal method. The graphene nanobelt prepared by the invention has the advantages of stable chemical property, high conductivity and the like; and the composite material prepared by the invention has the characteristic of morphology controllability, and the tungsten disulfide nanosheets are uniformly loaded on the graphene nanobelt, so that the adhesion of tungsten disulfide is effectively inhibited, and unique high specific surface area and high conductivity of the graphene nanobelt are fully utilized. The tungsten disulfide/graphene nanobelt composite material prepared by the invention can become an ideal high-performance electrocatalytic material and an electrode material of new energy devices such as lithium ion batteries and solar cells.
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/graphene nano belt composite and preparation method thereof.
Technical background
Graphene nanobelt is a kind of accurate one dimension c-based nanomaterial, and it has the physical and chemical performance of many excellences, as higher conductivity, excellent mechanical property, special edge effect and good chemical stability etc.These special natures make it all have very wide application prospect in fields such as power conversion and storage, electronic sensor, high molecule nano composite materials, become one of study hotspot in carbon nanomaterial field.
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 cannot be fully used.Therefore, by significant for the base material compound of tungsten disulfide and other high conductivity.
The present invention, by simple technological design, prepares a kind of novel tungsten disulfide/graphene nano belt composite.This composite material has following advantage: the edge effect of graphene nanobelt uniqueness more can grow site for the growth of tungsten disulfide nano slices provides, and the active edge of tungsten disulfide nano slices is exposed more fully; The excellent electric conductivity of graphene nanobelt is conducive to the transmission of electronics, can improve the conductivity of composites; The lamella structure of graphene nanobelt is conducive to the migration of electrolyte ion in electrochemical process, thus reduces the contact internal resistance of itself and solution.And tungsten disulfide nano slices itself possesses excellent catalytic activity and stored energy performance, therefore both are carried out effective compound and can realize good synergy, to prepare the composite material of excellent performance.
Summary of the invention
Tungsten disulfide/graphene nano belt composite that the object of the present invention is to provide a kind of electrochemical performance and preparation method thereof.
Tungsten disulfide provided by the present invention/graphene nano belt composite, consists of the tungsten disulfide nano slices of step solvent-thermal method growth in situ on described graphene nanobelt the graphene nanobelt and sulfo-ammonium tungstate with special band edge; Its raw materials composition comprises: carbon nano-tube (single wall or many walls), potassium permanganate, the concentrated sulfuric acid, phosphoric acid, sulfo-ammonium tungstate, and hydrazine hydrate.
The preparation method of tungsten disulfide provided by the present invention/graphene nano belt composite, prepares graphene nanobelt by solution oxide method; Again by step solvent-thermal method growth in situ tungsten disulfide nano slices on graphene nanobelt; Concrete steps are as follows:
(1) by carbon nanotube dispersed in the concentrated sulfuric acid of 95% ~ 98%, after being uniformly dispersed, adding the phosphoric acid of a certain amount of 85% again, in the process, constantly stirring and obtain homogeneous dispersion liquid;
(2) in above-mentioned dispersion liquid, potassium permanganate is added, Keep agitation;
(3) reaction system is slowly heated up, after temperature stabilization, insulation, and constantly stir;
(4) mixed solution of gained is naturally cooled to room temperature, then pour in the frozen water containing hydrogen peroxide, placement overnight, make its natural subsidence;
(5) the sediment aqueous hydrochloric acid solution obtained is washed repeatedly, then wash repeatedly with the mixed solution of ethanol/ether;
(6) centrifugal drying obtains solid oxidation graphene nanobelt;
(7) stannic oxide/graphene nano band is scattered in organic solvent, ultrasonicly obtains stannic oxide/graphene nano band stable dispersions;
(8) sulfo-ammonium tungstate is dissolved in stannic oxide/graphene nano band dispersion liquid, ultrasonicly makes it be uniformly dispersed, obtain sulfo-ammonium tungstate/stannic oxide/graphene nano band dispersion liquid;
(9) instilled by hydrazine hydrate solution in the mixed dispersion liquid of sulfo-ammonium tungstate and stannic oxide/graphene nano band, ultrasonic disperse is even;
(10) the prepared dispersion liquid containing stannic oxide/graphene nano band, sulfo-ammonium tungstate and hydrazine hydrate is put into water heating kettle, organic solvent thermal response a period of time, by the black precipitate deionized water for preparing and ethanol cyclic washing repeatedly, tungsten disulfide/graphene nano belt composite is namely obtained.
In the present invention, described stannic oxide/graphene nano band cuts off carbon nano-tube by solution oxide method radial direction to prepare, about the method referenced patent US2010/0105834Al.
In the present invention, described organic solvent comprises
n, N-dimethyl formamide,
n, N-dimethylacetylamide and
n-methyl pyrrolidone, preferably
n, N-dimethyl formamide.
In the present invention, the concentration of the carbon nano-tube described in step (1) is 3 ~ 5mgmL
-1, the volume ratio of the concentrated sulfuric acid and phosphoric acid is 8:1 ~ 10:1, is preferably 9:1.
In the present invention, the quality of the potassium permanganate described in step (2) is 2 ~ 5 times of carbon nano-tube consumption, preferably adds potassium permanganate in batches.
In the present invention, the temperature reached after step (3) described intensification is 60 ~ 80 DEG C, and the time of insulation is 2 ~ 3h.
In the present invention, the weight concentration of the aqueous hydrochloric acid solution described in step (5) is 5 ~ 20%.
In the present invention, the concentration of the stannic oxide/graphene nano band dispersion liquid described in step (7) is 0.5 ~ 2mgmL
-1, preferably 1 ~ 1.5mgmL
-1.
In the present invention, the stannic oxide/graphene nano band described in step (8) and the mass ratio of sulfo-ammonium tungstate are 1:1 ~ 1:4.
In the present invention, the concentration of the hydrazine hydrate described in step (9) is 30% ~ 80%, and consumption is 0.1 ~ 0.2mL.
In the present invention, the reaction temperature described in step (10) is 220 ~ 260 DEG C, and the reaction time is 10 ~ 24h.
Use transmission electron microscope (TEM), scanning electron microscopy (SEM), X-ray diffractometer (XRD) to characterize the structure and morphology of tungsten disulfide/graphene nano belt composite that the present invention obtains, its result is as follows:
(1) TEM test result shows, by solution oxide method, the inner wall layer border of graphene nanobelt disappears, and confirms that carbon nano-tube is cut off by radial direction.Prepared graphene nanobelt has high draw ratio and special band edge, and compared to original carbon nanotubes, its size increases, and bandwidth is about 100nm, and its higher specific area is that the growth of tungsten disulfide nano slices provides and more grows site.See accompanying drawing 1.In tungsten disulfide/graphene nano belt composite, tungsten disulfide nano slices grows the surface at graphene nanobelt equably, the tungsten disulfide nano slices number of plies is less, be about 5 ~ 10 layers, this thinner tungsten disulfide nano slices provides more active edge, thus its catalytic activity and stored energy performance are significantly improved.See accompanying drawing 2.
(2) SEM test result shows: in tungsten disulfide/graphene nano belt composite, tungsten disulfide nano slices grows equably on graphene nanobelt, restrained effectively the reunion of tungsten disulfide self, the active edge of tungsten disulfide nano slices layer is exposed fully.This has benefited from the band edge structure of graphene nanobelt and high specific area, gives its adjustability more flexibly, and this is also that it is different from the principal character of Sheet Graphite alkene.See accompanying drawing 3.
(3) XRD test result shows, prepared stannic oxide/graphene nano band has a stronger diffraction maximum in 2 θ=10 °, illustrate that nanobelt structure is successfully peeled off or cut off into carbon nano-tube.Graphene nanobelt after reduction has a wider diffraction maximum in 2 θ=26 °, correspond to (002) crystal face.Prepared tungsten disulfide/graphene nano belt composite demonstrates the characteristic peak of tungsten disulfide, and in 2 θ=14 °, 33 °, diffraction maximum appears in 40 ° and 59 ° of places, corresponds respectively to (002) of tungsten disulfide, (101), (103) and (100) crystal face.See accompanying drawing 4.
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;
The first, the substrate of selection is graphene nanobelt.The draw ratio of its uniqueness and marginal texture impart its high specific area, and provide more site for tungsten disulfide nano slices growth.Graphene nanobelt has excellent conductivity, and its lamellar structure makes electronics and ion in electro-catalysis process to transmit effective and rapidly, can further improve catalytic activity and the stored energy performance of tungsten disulfide;
The second, achieved the compound of quasi one-dimensional material and two-dimensional material by simple solvent thermal process, both advantages are given full play to, thus constructs the composite material with excellent properties.
Tungsten disulfide prepared by the present invention/graphene nano belt composite, can be used as the ideal electrode material of high performance catalyst material and the novel energy such as lithium ion battery, solar cell.
Accompanying drawing explanation
Fig. 1 is the TEM figure of material in the present invention.Wherein, (A) multi-walled carbon nano-tubes, (B) graphene nanobelt.
Fig. 2 is the TEM figure of tungsten disulfide of the present invention/graphene nano belt composite.
Fig. 3 is the SEM figure of tungsten disulfide of the present invention/graphene nanobelt composite material.
Fig. 4 is the XRD figure of tungsten disulfide of the present invention/graphene nano belt composite.
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) 150mg multi-walled carbon nano-tubes is scattered in the concentrated sulfuric acid of 98%, after being uniformly dispersed, adding the phosphoric acid of 85% again, constantly stir in the process and obtain homogeneous dispersion liquid;
(2) in above-mentioned dispersion liquid, add 750mg potassium permanganate, add in batches, constantly stir;
(3) reaction system is slowly warming up to 70 DEG C, after temperature stabilization, insulation a period of time, and constantly stir;
(4) mixed dispersion liquid of gained is naturally cooled to room temperature, then pour in the frozen water containing 7mL50% hydrogen peroxide, placement overnight, make its natural subsidence;
(5) by the sediment that obtains with 10% aqueous hydrochloric acid solution washing repeatedly, then to wash repeatedly with the mixed solution of ethanol/ether;
(6) centrifugal drying obtains solid oxidation graphene nanobelt;
(7) stannic oxide/graphene nano band is scattered in
n, N-in dimethyl formamide, the ultrasonic 1mgmL obtaining stable dispersion
-1stannic oxide/graphene nano band;
(8) 11mg sulfo-ammonium tungstate is dissolved in 10mL stannic oxide/graphene nano band dispersion liquid, ultrasonicly makes it be uniformly dispersed;
(9) by the hydrazine hydrate of 0.2mL50%, in the mixed dispersion liquid of instillation stannic oxide/graphene nano band and sulfo-ammonium tungstate, ultrasonic disperse is even;
(10) the prepared dispersion liquid containing stannic oxide/graphene nano band, sulfo-ammonium tungstate and hydrazine hydrate is put into water heating kettle, hydro-thermal reaction 12h at 240 DEG C, by the black precipitate deionized water for preparing and ethanol cyclic washing repeatedly, tungsten disulfide nano slices/graphene nano belt composite can be obtained
be designated as GNRWS 2 -1.
embodiment 2,the quality of the sulfo-ammonium tungstate in embodiment 1 is become 22mg, and all the other are all with embodiment 1, and final obtained composite material is designated as GNRWS
2-2.
embodiment 3,the quality of the sulfo-ammonium tungstate in embodiment 1 is become 44mg, and all the other are all with embodiment 1, and final obtained composite material is designated as GNRWS
2-3.
Claims (10)
1. a preparation method for tungsten disulfide/graphene nano belt composite, is characterized in that: prepare graphene nanobelt by solution oxide method; Again by step solvent-thermal method growth in situ tungsten disulfide nano slices on graphene nanobelt; Concrete steps are as follows:
(1) by carbon nanotube dispersed in the concentrated sulfuric acid of 95% ~ 98%, after being uniformly dispersed, adding the phosphoric acid of a certain amount of 85% again, in the process, constantly stirring and obtain homogeneous dispersion liquid;
(2) in above-mentioned dispersion liquid, potassium permanganate is added, Keep agitation;
(3) reaction system is slowly warmed up to 60 ~ 80 DEG C, after temperature stabilization, insulation 2 ~ 3h, and constantly stir;
(4) mixed solution of gained is naturally cooled to room temperature, then pour in the frozen water containing hydrogen peroxide, placement overnight, make its natural subsidence;
(5) the sediment aqueous hydrochloric acid solution obtained is washed repeatedly, then wash repeatedly with the mixed solution of ethanol/ether;
(6) centrifugal drying obtains solid oxidation graphene nanobelt;
(7) stannic oxide/graphene nano band is scattered in organic solvent, ultrasonicly obtains stannic oxide/graphene nano band stable dispersions;
(8) sulfo-ammonium tungstate is dissolved in stannic oxide/graphene nano band dispersion liquid, ultrasonicly makes it be uniformly dispersed, obtain sulfo-ammonium tungstate/stannic oxide/graphene nano band dispersion liquid;
(9) instilled by hydrazine hydrate solution in the mixed dispersion liquid of sulfo-ammonium tungstate and stannic oxide/graphene nano band, ultrasonic disperse is even;
(10) the prepared dispersion liquid containing stannic oxide/graphene nano band, sulfo-ammonium tungstate and hydrazine hydrate is put into water heating kettle, organic solvent thermal response, reaction temperature is 220 ~ 260 DEG C, reaction time is 10 ~ 24h, by the black precipitate deionized water for preparing and ethanol cyclic washing repeatedly, tungsten disulfide/graphene nano belt composite is namely obtained.
2. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, described organic solvent is
n, N-dimethyl formamide,
n, N-dimethylacetylamide or
n-methyl pyrrolidone.
3. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, the concentration of the carbon nano-tube described in step (1) is 3 ~ 5mgmL
-1, the volume ratio of the concentrated sulfuric acid and phosphoric acid is 8:1 ~ 10:1.
4. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, the quality of the potassium permanganate described in step (2) is 2 ~ 5 times of carbon nano-tube consumption.
5. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, the aqueous hydrochloric acid solution weight concentration described in step (5) is 5 ~ 20%.
6. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, the concentration of the stannic oxide/graphene nano band dispersion liquid described in step (7) is 0.5 ~ 2mgmL
-1.
7. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, the mass ratio of the stannic oxide/graphene nano band described in step (8) and sulfo-ammonium tungstate is 1:1 ~ 1:4.
8. the preparation method of tungsten disulfide according to claim 1/graphene nano belt composite, is characterized in that, the concentration of hydrazine hydrate described in step (9) is 30% ~ 80%, and consumption is 0.1 ~ 0.2mL.
9. the tungsten disulfide that the preparation method as described in one of claim 1 ~ 8 prepares/graphene nano belt composite.
10. tungsten disulfide/graphene nano belt composite 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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