CN106128784A - A kind of molybdenum bisuphide/Graphene hollow compound microsphere and preparation method thereof - Google Patents
A kind of molybdenum bisuphide/Graphene hollow compound microsphere and preparation method thereof Download PDFInfo
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- CN106128784A CN106128784A CN201610748848.1A CN201610748848A CN106128784A CN 106128784 A CN106128784 A CN 106128784A CN 201610748848 A CN201610748848 A CN 201610748848A CN 106128784 A CN106128784 A CN 106128784A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of molybdenum bisuphide/graphene composite material with level porous hollow microspheroidal structure and synthetic method thereof, belong to the technical field of Micron-nano composites preparation and synthesis.First silicon dioxide microsphere is prepared；Then it is allowed to positive electrification at one layer of cationic polyelectrolyte of its surface-assembled；Next the one layer of graphene oxide of silicon dioxide microsphere surface-assembled in positive electrification obtains silicon dioxide/graphene oxide complex microsphere；Then hydro-thermal method is used at its surface deposition, growth molybdenum disulfide nano sheet and the graphene oxide of cladding to be reduced into Graphene simultaneously and then obtains silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere；Finally, by silicon dioxide kernel therein removal thus molybdenum bisuphide/Graphene hollow compound microsphere is synthesized by hydro-thermal method excessive hydrogen fluoric acid.This composite has big ratio electric capacity and excellent cycle charge discharge electrical stability as electrode material for super capacitor when using, illustrate wide application prospect.
Description
Technical field
The invention belongs to the technical field of Micron-nano composites preparation and synthesis, be specifically related to a kind of as super capacitor
Device electrode material uses and the molybdenum bisuphide/graphene composite material with tiny balloon shape structure and preparation method thereof.
Background technology
Due to outstanding physico-chemical property, stratiform transition metal dichalcogenide such as molybdenum bisuphide, vanadium disulfide, stannic disulfide,
Tungsten disulfides etc. receive people in ultracapacitor field and more and more pay close attention to.Especially molybdenum bisuphide based composites is more
It is to become the focus instantly researched and developed.Many has the molybdenum-disulfide radical electrode of super capacitor of different structure and pattern
Material the most flower-shaped molybdenum disulfide nano ball, mesoporous molybdenum disulfide nano material, molybdenum bisuphide tiny balloon, molybdenum disulfide nano
Cluster, molybdenum bisuphide/carbon, molybdenum bisuphide/stannic disulfide, molybdenum bisuphide/tin dioxide composite material etc. also arise at the historic moment [(a)
Wang, X.；Ding, J.；Yao, S.；Wu, X.；Feng, Q.；Wang, Z.；Geng, B.J.Mater.Chem.A2014,2,
15958-15963. (b) Zhou, X.；Xu, B.；Lin, Z；Shu, D.；Ma, L.J.Nanosci.Nanotechnol.2014,14,
7250-7254. (c) Wang, L.；Ma, Y.；Yang M.；Qi, Y.Electrochim.Acta 2015,186,391-396. (d)
Fang, L.Q.；Liu, G.J.；Zhang, C.Y.；Wu, J.H.；Wei, Y.L.Iht.J.Hydrogen Energy 2015,40,
10150-10157. (e) Ilanchezhiyan, P；Kumar, G.M.；Kang, T.W.J.Alloys Compd.2015,634,
104-108. (f) Wang, L.；Ma, Y.；Yang, M.；Qi, Y.RSCAdv.2015,5,89069-89075.].But these are
When the molybdenum bisuphide sill being in the news uses as electrode material for super capacitor, it is more extremely limited than electric capacity, it tends to be difficult to
More than 200Fg-1, and stability is also often difficult to satisfactory.Its reason be the poor electric conductivity of molybdenum bisuphide itself and
Easily assembling at material preparation process laminate molybdenum bisuphide causes specific surface area relatively low, thus largely limits charge and discharge
The transmission of electronics and the diffusion of electrolyte ion in electric process, and then have impact on the chemical property of material.Therefore, how to pass through
The method using simple economy promotes the electric conductivity of molybdenum bisuphide based composites and constructs the level porous knot of uniqueness simultaneously
Structure increases its specific surface area and seems most important to the molybdenum-disulfide radical electrode material for super capacitor obtaining excellent properties, and
This also becomes the difficulties in this field at present.
Summary of the invention
It is an object of the present invention to provide and a kind of there is bigger serface, satisfactory electrical conductivity and the curing of outstanding chemical property
Molybdenum/Graphene hollow compound microsphere and simply and easily synthetic method, be allowed in terms of ultracapacitor produce application, and
The kind of abundant molybdenum bisuphide based composites.
The present invention is achieved by the following technical solutions.First surface electronegative silicon dioxide colloid microsphere is prepared,
Then it is allowed to positive electrification, next by ultrasonic wave added by electrostatic interaction at one layer of cationic polyelectrolyte of its surface-assembled
Self assembly means thus obtain at one layer of graphene oxide of silicon dioxide microsphere Surface coating of positive electrification again by electrostatic interaction
To silicon dioxide/graphene oxide complex microsphere, then use hydro-thermal method at its surface deposition, growth molybdenum disulfide nano sheet also
The graphene oxide of cladding is reduced into Graphene simultaneously thus obtains silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere,
After, by hydro-thermal method excessive hydrogen fluoric acid, the silicon dioxide kernel removal of this composite inorganic membranes is synthesized curing further
Molybdenum/Graphene hollow compound microsphere, and use as electrode material for super capacitor, specifically include following steps:
(1) use that has reported to improve a littleMethod prepares size uniform and controlled silicon dioxide colloid microsphere [(a)
Wang, W.；Gu, B.；Liang, L.；Hamilton, W.A.J.Phys.Chem.B2003,107,3400-3404. (b) Wang,
W.；Gu, B.；Liang, L.；Hamilton, W.A.J.Phys.Chem.B2003,107,12113-12117.], its surface with
Elecrtonegativity.
(2) by electrostatic interaction on surface one layer of cationic polyelectrolyte polydiene of electronegative silicon dioxide microsphere surface-assembled
Diallyidimethylammonium chloride, thus it is allowed to positive electricity.
(3) by the interface self assembly means of ultrasonic wave added, small size graphene oxide sheet is coated on the silicon dioxide of positive electrification
Microsphere surface.Surface is i.e. made to pass through electrostatic interaction with the small size graphene oxide sheet of negative electricity under continual strength is ultrasonic
Be self-assembled to the silicon dioxide microsphere surface of the just electrification of surface in (2), thus obtain having the silicon dioxide of superior water dispersibility/
Graphene oxide complex microsphere (Xiao, W.；Zhang, Y.；Liu, B.ACS Appl.Mater.Interfaces2015,7,
6041-6046.)。
(4) silicon dioxide step (3) prepared/graphene oxide complex microsphere ultrasonic disperse is in water, under ultrasound condition
Aqueous solution containing sodium molybdate and thiourea is added dropwise in dispersion liquid, adds a small amount of Fluohydric acid. and form homogeneous reaction system.
(5) the middle reactant mixture of step (4) is transferred in reactor, hydro-thermal reaction 24h at 200 DEG C, the coldest
But.Sodium molybdate and thiourea react generation molybdenum disulfide nano sheet under hydrogen fluoride catalyzed and deposit, are grown on base in the process
End microsphere surface, meanwhile, the graphene oxide being coated on substrate microsphere surface is become Graphene by hydrothermal reduction, and then generates
Intermediate product silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere.
(6) by the silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere centrifugation in step (5) and wash several times after again
Secondary ultrasonic disperse, in water, adds excessive hydrogen fluoric acid afterwards, is then again transferred in reactor also by gained reactant mixture
Natural cooling after hydro-thermal reaction 12h at 180 DEG C, fluohydric acid gas fully reacts with silicon dioxide kernel and is allowed to dissolve in the process
Remove, finally, by gained precipitate centrifugation, and be dried with washing with alcohol final vacuum several times, thus obtain end product
Molybdenum bisuphide/Graphene hollow compound microsphere.
(7) by molybdenum bisuphide/Graphene hollow compound microsphere in step (6) and acetylene black and Kynoar according to certain
Mass ratio mixing is placed on agate mortar, is subsequently adding appropriate N-Methyl pyrrolidone and uniformly grinds to form slurry, afterwards
It is evenly applied to the surface of nickel foam with banister brush, and the nickel foam being then coated with active material obtains the most after drying
Working electrode.
(8) step (7) to be coated with the nickel foam of active material as working electrode, Hg/HgO electrode as reference electrode,
Pt plate electrode, as auxiliary electrode and using potassium hydroxide aqueous solution as electrolyte, uses three-electrode system to institute in step (6)
Molybdenum bisuphide/Graphene the hollow compound microsphere of synthesis is through row cyclic voltammetric, constant current charge-discharge and electrochemical impedance stave
Levy, test its chemical property as electrode material for super capacitor.
In step of the present invention (1), the silicon dioxide microsphere water dispersible of surface negatively charged is preferable, and its size also has good
Good monodispersity, size tunable scope is 200-500nm.
In the present invention, used ultrasound condition, it is the most acutely strength ultrasonic, power is not less than 150W.
In the present invention, small size graphene oxide refers to that radial dimension is less than the graphene oxide sheet of 200nm.
In step of the present invention (4), the purpose at the reaction system a small amount of Fluohydric acid. of introducing is to react raw as sodium molybdate and thiourea
Becoming the catalyst of molybdenum disulfide nano sheet, wherein fluohydric acid gas concentration in reaction system should not be no more than 0.2mg mL-1, because of
On the one hand the molybdenum disulfide nano sheet that hydro-thermal can be made to generate for excessive concentration is difficult to be uniformly deposited on substrate microsphere surface, another
The Fluohydric acid. of aspect too high concentration can shift to an earlier date and thoroughly dissolves substrate microsphere, thus causes finally can not get molybdenum bisuphide/graphite
Alkene hollow compound microsphere.
Compared with prior art, the present invention has the following advantages and effect:
1, the molybdenum bisuphide developed in the present invention/Graphene hollow compound microsphere has the level porous hollow microsphere of uniqueness
Shape structure, thus relatively big (the up to 63.7m of specific surface area2g-1), wherein molybdenum disulfide nano sheet crimps, folds, overlap pore-forming, interior
There is cavity in portion, is advantageous to diffusion and the transmission of electrolyte ion.
2, Graphene has outstanding electric conductivity, and so molybdenum bisuphide and the compound of Graphene make synthesized curing
Molybdenum/Graphene hollow compound microsphere has more preferably electric conductivity than the molybdenum bisuphide material of single component.
3, owing to molybdenum bisuphide/Graphene hollow compound microsphere is with the level porous hollow structure of bigger serface and good
Good electric conductivity makes it show the chemical property of excellence as electrode material for super capacitor when using.Using three electricity
During the test of polar body system, it is 1Ag in electric current density-1During lower discharge and recharge, it is up to 218.1Fg than electric capacity-1, it is 3Ag in electric current density-1
Its capacity retention still up to 91.8% after the most continuous repeated charge 1000 times, these indexs are obviously higher than reporting at present
The ratio electric capacity of most of molybdenum-disulfide radical electrode material for super capacitor in road and the stability of cycle charge-discharge.
4, synthesis involved in the present invention and course of reaction are all using water or ethanol as solvent or medium, and all cheaper starting materials are easy
, particularly in first step hydrothermal reaction process in (i.e. above-mentioned steps 5), molybdenum disulfide nano sheet sinking on microsphere substrate surface
The reduction of long-pending, growth and crystallization and graphene oxide composition is realized by a step, thus reaction condition is gentle, operation side
Method is easy, with low cost, less pollution.
Accompanying drawing explanation
Fig. 1 be molybdenum bisuphide/Graphene hollow compound microsphere prepare schematic diagram.
Fig. 2 is the stereoscan photograph of molybdenum bisuphide/Graphene hollow compound microsphere.
Fig. 3 is the transmission electron microscope photo of molybdenum bisuphide/Graphene hollow compound microsphere.
Fig. 4 is the nitrogen adsorption-desorption isothermal curve figure of molybdenum bisuphide/Graphene hollow compound microsphere.
Fig. 5 is that the high-resolution-ration transmission electric-lens of molybdenum bisuphide/Graphene hollow compound microsphere surface molybdenum disulfide nano sheet shines
Sheet.
Fig. 6 is the X-ray powder diffraction figure of molybdenum bisuphide/Graphene hollow compound microsphere.
Fig. 7 is that molybdenum bisuphide/Graphene hollow compound microsphere is swept in difference when using as electrode material for super capacitor
Cyclic voltammogram under Su.
Fig. 8 be molybdenum bisuphide/Graphene hollow compound microsphere when using as electrode material for super capacitor at different electricity
Constant current charge-discharge figure under current density.
Fig. 9 is that the molybdenum bisuphide material of molybdenum bisuphide/Graphene hollow compound microsphere and one-component is respectively as super
Electrochemical impedance spectrogram when capacitor electrode material uses.
Figure 10 is that it compares electric capacity to molybdenum bisuphide/Graphene hollow compound microsphere when using as electrode material for super capacitor
Curve chart with the change of repeated charge number of times.
Detailed description of the invention
Below by embodiment and combine accompanying drawing the present invention is further described in detail.
Embodiment 1: the method that the present invention provides is used for preparing molybdenum bisuphide/Graphene hollow compound microsphere (Fig. 1):
(1) employing improves a littleMethod prepare silicon dioxide colloid microsphere that mean diameter is 200nm [(a) Wang,
W.；Gu, B.；Liang, L.；Hamilton, W.A.J.Phys.Chem.B2003,107,3400-3404. (b) Wang, W.；Gu,
B.；Liang, L.；Hamilton, W.A.J.Phys.Chem.B2003,107,12113-12117.].
(2) one layer is modified by the interface self assembly means of ultrasonic wave added silicon dioxide microsphere surface of preparation in step (1)
Graphene oxide, obtains silicon dioxide that average-size is 200nm/graphene oxide complex microsphere (Xiao, W.；Zhang, Y.；
Liu, B.ACS Appl.Mater.Interfaces 2015,7,6041-6046.).
(3) by the silicon dioxide in 80mg step (2)/graphene oxide complex microsphere ultrasonic disperse in 55mL water, then exist
It is added dropwise over 5mL under the most ultrasonic and contains 155mg bis-molybdic acid hydrate sodium and the aqueous solution of 243mg thiourea, add 30 μ L matter afterwards
Amount mark is that the Fluohydric acid. of 40wt% forms uniform reaction system.
(4) reactant mixture in step (3) is transferred in the reactor that capacity is 100mL, hydro-thermal reaction 24h at 200 DEG C
After naturally cool to room temperature, bottom reactor, leave silicon dioxide/Graphene/molybdenum bisuphide that black precipitate i.e. generates multiple
Close microsphere.
(5) silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere centrifugation that will generate in step (4), fully washs with water
After ultrasonic disperse is in 30mL water again, next adding 250 μ L mass fractions is the Fluohydric acid. of 40wt%, the most again by this mixing
Liquid is transferred in the reactor that capacity is 50mL, naturally cools to room temperature at 180 DEG C after hydro-thermal reaction 12h, and in the process two
Silicon oxide kernel with excess hydrogen fluoride reaction and be dissolved and remove, and then generate molybdenum bisuphide/Graphene hollow compound microsphere
And it is deposited in bottom reactor, it is isolated by centrifugal, fully washs final vacuum afterwards with ethanol and be dried.
Molybdenum bisuphide prepared by the present embodiment/Graphene hollow compound microsphere has the porous hollow structure of level, surface
Molybdenum disulfide nano sheet extremely crimp, and be wound around, fold, weight synthesising mesoporous (Fig. 2 and Fig. 3)；Its nitrogen adsorption-desorption etc.
Temperature curve has an IV type to return stagnant ring (Fig. 4) in the range of relative pressure 0.45-1.0, show again its porous character.Additionally,
The high-resolution-ration transmission electric-lens observed result of this molybdenum bisuphide/Graphene hollow compound microsphere surface molybdenum disulfide nano sheet demonstrates
Lattice fringe (Fig. 5) clearly, its spacing of lattice is 0.62nm, corresponding to (002) crystal face of hexagonal phase molybdenum bisuphide；And should
The powder X-ray diffraction spectrogram of composite demonstrate six diffraction maximums lay respectively at 2 θ=14.3 °, 33.6 °, 40.1 °,
49.1 °, 59.0 ° and 69.4 ° (Fig. 6), the crystal formation more having confirmed wherein molybdenum bisuphide composition is hexagonal phase.
Embodiment 2: molybdenum bisuphide embodiment 1 synthesized/Graphene hollow compound microsphere is as electrode of super capacitor
Materials'use tests its chemical property:
(1) molybdenum bisuphide synthesized by 40mg embodiment 1/Graphene hollow compound microsphere, 5mg acetylene black and 5mg are weighed respectively
Kynoar also puts into agate mortar after being mixed, and adds 350 μ L N-Methyl pyrrolidone afterwards and is fully ground into
Slurry, is then evenly applied to the surface of nickel foam by this slurry, and coated area is 1cm × 1cm, next this is coated with activity
The nickel foam of material puts into vacuum drying oven, is fully dried 6h working electrode derived above at 60 DEG C.
(2) step (1) to be coated with the nickel foam of active material as working electrode, Hg/HgO electrode as reference electrode,
Pt plate electrode as electrolyte, takes three-electrode system to reality as auxiliary electrode the potassium hydroxide aqueous solution using concentration as 2M
Execute molybdenum bisuphide/Graphene hollow compound microsphere synthesized in example 1 through row cyclic voltammetric, constant current charge-discharge and electrochemistry
Impedance spectrum characterizes, and tests its chemical property as electrode material for super capacitor.
Fig. 7 is that in embodiment 1, the molybdenum bisuphide/Graphene hollow compound microsphere of preparation uses as electrode material for super capacitor
Time cyclic voltammogram under difference sweeps speed.It can be seen that all curves all present the shape close to rectangle and symmetry,
The electrode material that molybdenum bisuphide/Graphene hollow compound microsphere is electric double layer capacitance feature is described.Fig. 8 is embodiment 1 preparation
Perseverance under different electric current densities when molybdenum bisuphide/Graphene hollow compound microsphere uses as electrode material for super capacitor
Current charge-discharge electrograph, it is gradually lowered than electric capacity therefrom can to extrapolate the increase along with electric current density, minimum shown in the figure
Electric current density 1Ag-1Under, it is up to 218.1Fg than electric capacity-1, hence it is evident that super higher than the most of molybdenum-disulfide radical reported at present
Capacitor electrode material ratio electric capacity under this electric current density.Fig. 9 is that the molybdenum bisuphide/Graphene of embodiment 1 preparation is hollow multiple
Electrochemical impedance spectrogram when the molybdenum bisuphide of conjunction microsphere and one-component uses respectively as electrode material for super capacitor, very
Substantially, the former is respectively less than the latter to the intercept of real axis and the diameter of high-frequency region semi arch, illustrates that the former internal resistance and electric charge pass
Pass impedance much smaller than the latter, say, that molybdenum bisuphide/Graphene Hollow Compound that molybdenum bisuphide is formed after compound with Graphene
Microsphere electric conductivity is better than the molybdenum bisuphide material of one-component.Figure 10 is that the molybdenum bisuphide/Graphene of embodiment 1 preparation is hollow multiple
Close when microsphere uses as electrode material for super capacitor at 3Ag-1Electric current density under its than electric capacity with repeated charge number of times
The curve chart of change, therefrom it can be seen that it is very slower than electric capacity downward trend, and after repeated charge 1000 times its
Capacity retention is still up to 91.8%, equally apparently higher than the most of molybdenum-disulfide radical super capacitor electrode reported at present
Pole material capacity retention after repeated charge, illustrates that this molybdenum bisuphide/Graphene hollow compound microsphere has and more holds
Long stability, thus shown wide application prospect.
Claims (3)
1. molybdenum bisuphide/graphene composite material with level porous hollow microspheroidal structure, it is characterised in that material
The composition of material is molybdenum bisuphide and redox graphene, and the microscopic appearance of material shows as by the nanometer crimping, being wound around, fold
Sheet is interlaced, overlapping, the tiny balloon of Adhesion formation, and the crystalline phase of its surface molybdenum disulfide nano sheet is hexagonal phase, and this is combined
There is when material uses as electrode material for super capacitor big ratio electric capacity and excellent cycle charge discharge electrical stability.
The preparation method of a kind of molybdenum bisuphide/Graphene hollow compound microsphere the most as claimed in claim 1, it is characterised in that close
Become step as follows:
(1) the St ber method improved is used to prepare the silicon dioxide microsphere of size controlled size uniform outer surface negatively charged；
(2) by electrostatic interaction at one layer of cationic polyelectrolyte polydiene third of electronegative silicon dioxide microsphere surface-assembled
Base alkyl dimethyl ammonium chloride, thus it is allowed to positive electricity；
(3) by the interface self assembly means of ultrasonic wave added, small size graphene oxide sheet is coated on the titanium dioxide of positive electrification
Silicon microsphere surface,
I.e. make under continual strength is ultrasonic surface with negative electricity small size graphene oxide sheet by electrostatic interaction from group
It is loaded on the silicon dioxide microsphere surface of surface just electrification, thus obtains silicon dioxide/graphene oxide complex microsphere；
(4) by silicon dioxide/graphene oxide complex microsphere ultrasonic disperse in water, will be containing sodium molybdate and sulfur under ultrasonic
The aqueous solution of urea is added dropwise in dispersion liquid, adds a small amount of Fluohydric acid. and forms homogeneous reaction system；
(5) reactant mixture is transferred in reactor, in 200oUnder C hydro-thermal reaction 24 h generate intermediate product silicon dioxide/
Graphene/carbon/molybdenum disulfide composite microsphere, then natural cooling；Sodium molybdate and thiourea react under hydrogen fluoride catalyzed in the process
Generate molybdenum disulfide nano sheet and deposit, be grown on substrate microsphere surface, meanwhile, being coated on the oxidation of substrate microsphere surface
Graphene is become Graphene by hydrothermal reduction, and then generates intermediate product silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere；
(6) by intermediate product silicon dioxide/Graphene/carbon/molybdenum disulfide composite microsphere centrifugation and wash several times after again
Ultrasonic disperse in water, afterwards add excessive hydrogen fluoric acid, then gained reactant mixture is again transferred in reactor and in
180 oNatural cooling after hydro-thermal reaction 12 h under C, fluohydric acid gas fully reacts with silicon dioxide kernel and is allowed to dissolve in the process
Remove, finally, by gained precipitate centrifugation, and be dried with washing with alcohol final vacuum several times, thus obtain end product
Molybdenum bisuphide/Graphene hollow compound microsphere.
3. the synthetic method of molybdenum bisuphide/Graphene hollow compound microsphere as claimed in claim 2, it is characterised in that with dioxy
SiClx colloid micro ball is prepared as template, all courses of reaction all using water or ethanol as medium, particularly first step water
In this critical process of thermal response, i.e. step described in claim 2 (5), molybdenum disulfide nano sheet sinking at substrate microsphere surface
The reduction of long-pending, crystallization and growth and wherein graphene oxide composition is that a step realizes.
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| CN111106346A (en) * | 2019-12-17 | 2020-05-05 | 合肥国轩高科动力能源有限公司 | SnS2rGO modified sulfur cathode material and preparation method and application thereof |
| CN111106346B (en) * | 2019-12-17 | 2022-03-11 | 合肥国轩高科动力能源有限公司 | SnS2rGO modified sulfur cathode material and preparation method and application thereof |
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| CN108417404A (en) | 2018-08-17 |
| CN106128784B (en) | 2018-03-30 |
| CN108417404B (en) | 2019-03-15 |
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