CN106128784B - A kind of molybdenum disulfide/graphene hollow compound microsphere and preparation method thereof - Google Patents
A kind of molybdenum disulfide/graphene hollow compound microsphere and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of molybdenum disulfide/graphene composite material and its synthetic method with level porous hollow microspheroidal structure, belongs to the technical field that Micron-nano composites are prepared and synthesized.Silicon dioxide microsphere is prepared first；Then it is allowed to positive electrification in one layer of cationic polyelectrolyte of its surface-assembled；Next silica/graphene oxide complex microsphere is obtained in one layer of graphene oxide of silicon dioxide microsphere surface-assembled of positive electrification；Then the graphene oxide of cladding is simultaneously reduced into simultaneously in its surface deposition, growth molybdenum disulfide nano sheet by graphene using hydro-thermal method and then obtains silica/graphene/carbon/molybdenum disulfide composite microsphere；Finally, silica kernel therein is removed so as to synthesize molybdenum disulfide/graphene hollow compound microsphere with excessive hydrofluoric acid by hydro-thermal method.With big specific capacitance and excellent cycle charge discharge electrical stability when the composite uses as electrode material for super capacitor, wide application prospect is illustrated.
Description
Technical field
The invention belongs to Micron-nano composites to prepare the technical field with synthesis, and in particular to one kind is used as super capacitor
Device electrode material uses and has molybdenum disulfide/graphene composite material of tiny balloon shape structure and preparation method thereof.
Background technology
Due to outstanding physico-chemical property, stratiform transition metal dichalcogenide for example molybdenum disulfide, vanadium disulfide, stannic disulfide,
Tungsten disulfide etc. receives people in ultracapacitor field and more and more paid close attention to.Especially molybdenum disulfide based composites are more
It is to become the focus researched and developed instantly.Many has the molybdenum-disulfide radical electrode of super capacitor of different structure and pattern
For example flower-shaped molybdenum disulfide nano ball of material, mesoporous molybdenum disulfide nano material, molybdenum disulfide tiny balloon, molybdenum disulfide nano
Cluster, molybdenum disulfide/carbon, molybdenum disulfide/stannic disulfide, molybdenum disulfide/tin dioxide composite material etc. are also arisen 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. Acta2015, 186, 391–396. (d) Fang, L.Q.; Liu, G.J.; Zhang,
C.Y.; Wu, J.H.; Wei, Y.L. Int. J. Hydrogen Energy2015, 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. RSC Adv.2015, 5, 89069–89075.].But
Be molybdenum disulfide sill that these have been reported as electrode material for super capacitor in use, its specific capacitance is extremely limited,
Often it is difficult to more than 200 F g‒1, and stability be also often difficult to it is satisfactory.Its reason is that molybdenum disulfide itself is poor
Electric conductivity and easily aggregation causes specific surface area relatively low in material preparation process laminate molybdenum disulfide, so as to largely
The transmission of electronics and the diffusion of electrolyte ion in charge and discharge process are limited, and then have impact on the chemical property of material.Cause
How this, lift the electric conductivity of molybdenum disulfide based composites by using the method for simple economy and construct the layer of uniqueness simultaneously
Secondary property loose structure increase its specific surface area obtain the molybdenum-disulfide radical electrode material for super capacitor of excellent properties seem to
Close important, and this also becomes the difficulties in the current field.
The content of the invention
It is an object of the present invention to provide a kind of curing with bigger serface, satisfactory electrical conductivity and outstanding chemical property
Molybdenum/graphene hollow compound microsphere and its simply and easily synthetic method, it is allowed to produce application in terms of ultracapacitor, and
The species of abundant molybdenum disulfide based composites.
The present invention is achieved by the following technical solutions：
The electronegative silicon dioxide colloid microballoon in surface is prepared first, then by electrostatic interaction in one layer of its surface-assembled
Cationic polyelectrolyte is allowed to positive electrification, next by the self assembly means of ultrasonic wave added again by electrostatic interaction in positive electricity
One layer of graphene oxide of silicon dioxide microsphere Surface coating of change is so as to obtain silica/graphene oxide complex microsphere, so
The graphene oxide of cladding in its surface deposition, growth molybdenum disulfide nano sheet and is reduced into by graphite using hydro-thermal method simultaneously afterwards
Alkene is so as to obtain silica/graphene/carbon/molybdenum disulfide composite microsphere, finally, is answered this with excessive hydrofluoric acid by hydro-thermal method
The silica kernel of compound microballoon, which removes, further synthesizes molybdenum disulfide/graphene hollow compound microsphere, and as
Electrode material for super capacitor uses.A kind of molybdenum disulfide/graphene with level porous hollow microspheroidal structure is compound
The preparation method of material, specifically includes following steps：
(1) size uniform and controllable silicon dioxide colloid microballoon are prepared using the slightly improved St ber methods reported
[(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 carries elecrtonegativity.
(2) gathered by electrostatic interaction in surface one layer of cationic polyelectrolyte of electronegative silicon dioxide microsphere surface-assembled
Diallyldimethylammonium chloride, so as to be allowed to positive electricity.
(3) small size graphene oxide sheet is coated on to the dioxy of positive electrification by the interface self assembly means of ultrasonic wave added
SiClx microsphere surface.Small size graphene oxide sheet of the surface with negative electricity is set to pass through electrostatic under continual strength ultrasound
Effect is self-assembled to the silicon dioxide microsphere surface of the positive electrification in surface in (2), so as to obtain the dioxy with superior water dispersibility
SiClx/graphene oxide complex microsphere (Xiao, W.; Zhang, Y.; Liu, B.ACS Appl. Mater. Interfaces2015, 7, 6041-6046.)。
(4) silica/graphene oxide complex microsphere ultrasonic disperse for preparing step (3) is in water, in ultrasonic bar
The aqueous solution containing sodium molybdate and thiocarbamide is added dropwise in dispersion liquid under part, a small amount of hydrofluoric acid is added and forms homogeneous reaction body
System.
(5) the middle reactant mixture of step (4) is transferred in reactor, in 200oThe h of hydro-thermal reaction 24 under C, then
Natural cooling.Sodium molybdate reacts generation molybdenum disulfide nano sheet with thiocarbamide under hydrogen fluoride catalyzed and deposited, raw in the process
It is longer than substrate microsphere surface, at the same time, is coated on the graphene oxide of substrate microsphere surface by hydrothermal reduction into graphene, enters
And generate intermediate product silica/graphene/carbon/molybdenum disulfide composite microsphere.
(6) silica/graphene/carbon/molybdenum disulfide composite microsphere in step (5) is centrifuged and washed several times
Ultrasonic disperse in water, adds excessive hydrofluoric acid afterwards again afterwards, and gained reactant mixture then is again transferred into reactor
In and in 180oNatural cooling after the h of hydro-thermal reaction 12 under C, in the process hydrogen fluoride fully react and make with silica kernel
Dissolving remove, finally, gained sediment is centrifuged, and washed with ethanol and be dried in vacuo afterwards several times, so as to obtain most
End-product molybdenum disulfide/graphene hollow compound microsphere.
(7) by molybdenum disulfide/graphene hollow compound microsphere in step (6) and acetylene black and Kynoar according to
Agate mortar is placed in after certain mass ratio mixing, appropriate 1-METHYLPYRROLIDONE is then added and uniformly grinds pulp
It, is evenly applied to the surface of nickel foam by thing with banister brush afterwards, and the nickel foam for being then coated with active material is fully dry
Working electrode is obtained after dry.
(8) nickel foam coated with active material is as working electrode using in step (7), and Hg/HgO electrodes are as reference
Electrode, Pt plate electrodes are as auxiliary electrode and using potassium hydroxide aqueous solution as electrolyte, using three-electrode system to step (6)
In synthesized molybdenum disulfide/graphene hollow compound microsphere through row cyclic voltammetric, constant current charge-discharge and electrochemical impedance
Stave is levied, and tests its chemical property as electrode material for super capacitor.
The silicon dioxide microsphere water dispersible of surface negatively charged is preferable in step (1) of the present invention, and its size also has good
Good monodispersity, size tunable scope are 200-500 nm.
In the present invention, ultrasound condition is used, is that continuous acutely strength ultrasound, power are not less than 150W.
In the present invention, small size graphene oxide refers to that radial dimension is less than 200nm graphene oxide sheet.
The purpose for introducing a small amount of hydrofluoric acid in reaction system in step (4) of the present invention is given birth to as sodium molybdate and thiocarbamide reaction
Into the catalyst of molybdenum disulfide nano sheet, wherein concentration of the hydrogen fluoride in reaction system should not be no more than 0.2 mg mL-1,
Because the molybdenum disulfide nano sheet that excessive concentration on the one hand can generate hydro-thermal is difficult to be uniformly deposited on substrate microsphere surface, separately
On the one hand too the hydrofluoric acid of high concentration can thoroughly dissolve substrate microballoon in advance, so as to cause finally to cannot get molybdenum disulfide/stone
Black alkene hollow compound microsphere.
Compared with prior art, the present invention has advantages below and effect：
1st, the molybdenum disulfide/graphene hollow compound microsphere developed in the present invention has unique level porous hollow
Microspheroidal structure, thus larger (up to 63.7 m of specific surface area2 g-1), wherein molybdenum disulfide nano sheet curling, folding, coincidence
There is cavity in pore-forming, inside, be advantageous to the diffusion and transmission of electrolyte ion.
2nd, graphene has outstanding electric conductivity, and so molybdenum disulfide and the compound of graphene cause synthesized two
Molybdenum sulfide/graphene hollow compound microsphere has more preferably electric conductivity than the molybdenum disulfide material of single component.
3rd, because molybdenum disulfide/graphene hollow compound microsphere is with the level porous hollow structure of bigger serface
Excellent chemical property is shown when make it that it is used as electrode material for super capacitor with good electric conductivity.Using
It is 1 A g in current density when three-electrode system is tested-1Its specific capacitance is up to 218.1 F g during lower discharge and recharge-1, it is close in electric current
Spend for 3A g-1Its capacity retention is still up to 91.8% after continuous repeated charge 1000 times down, these indexs obviously higher than
The specific capacitance of most of molybdenum-disulfide radical electrode material for super capacitor and the stability of cycle charge-discharge reported at present.
4th, synthesis involved in the present invention and course of reaction are cheap using water or ethanol as solvent or medium, all raw materials
It is easy to get, particularly in first step hydrothermal reaction process in (i.e. above-mentioned steps 5), molybdenum disulfide nano sheet is on microsphere substrate surface
Deposition, growth and the reduction of crystallization and graphene oxide composition are realized by a step, thus reaction condition is gentle, operation
Method is easy, cost is cheap, less pollution.
Brief description of the drawings
Fig. 1 is that molybdenum disulfide/graphene hollow compound microsphere prepares schematic diagram.
Fig. 2 is the stereoscan photograph of molybdenum disulfide/graphene hollow compound microsphere.
Fig. 3 is the transmission electron microscope photo of molybdenum disulfide/graphene hollow compound microsphere.
Fig. 4 is nitrogen adsorption-desorption isothermal curve figure of molybdenum disulfide/graphene hollow compound microsphere.
Fig. 5 is that the high-resolution-ration transmission electric-lens of molybdenum disulfide/graphene hollow compound microsphere surface molybdenum disulfide nano sheet shine
Piece.
Fig. 6 is the X-ray powder diffraction figure of molybdenum disulfide/graphene hollow compound microsphere.
Fig. 7 is that molybdenum disulfide/graphene hollow compound microsphere is swept when being used as electrode material for super capacitor in difference
Cyclic voltammogram under speed.
Fig. 8 is in different electricity when molybdenum disulfide/graphene hollow compound microsphere uses as electrode material for super capacitor
Constant current charge-discharge figure under current density.
Fig. 9 is the molybdenum disulfide material of molybdenum disulfide/graphene hollow compound microsphere and one-component respectively as super
Electrochemical impedance spectrogram when capacitor electrode material uses.
Figure 10 is its specific capacitance when molybdenum disulfide/graphene hollow compound microsphere uses as electrode material for super capacitor
The curve map changed with repeated charge number.
Embodiment
The present invention is further described in detail by way of example and in conjunction with the accompanying drawings.
Embodiment 1：Method provided by the invention is used to prepare molybdenum disulfide/graphene hollow compound microsphere (Fig. 1)：
(1) slightly improved St ber methods are used to prepare silicon dioxide colloid microballoon [(a) of the average grain diameter for 200nm
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) the silicon dioxide microsphere surface modification prepared by the interface self assembly means of ultrasonic wave added in step (1)
One layer of graphene oxide, obtain silica/graphene oxide complex microsphere (Xiao, W. that average-size is 200 nm;
Zhang, Y.; Liu, B. ACS Appl. Mater. Interfaces2015, 7, 6041-6046.)。
(3) by the silica in 80mg steps (2)/graphene oxide complex microsphere ultrasonic disperse in 55mL water, so
The aqueous solution of 5 mL containing the molybdic acid hydrate sodium of 155 mg bis- and 243 mg thiocarbamides is added dropwise under strength ultrasound afterwards, adds afterwards
30 μ L mass fractions are that 40 wt% hydrofluoric acid forms uniform reaction system.
(4) reactant mixture in step (3) is transferred in the reactor that capacity is 100 mL, 200oHydro-thermal under C
Room temperature is naturally cooled to after reacting 24 h, silica/graphene/bis- that black precipitate generates are left in reactor bottom
Molybdenum sulfide complex microsphere.
(5) silica/graphene of generation in step (4)/carbon/molybdenum disulfide composite microsphere is centrifuged, filled with water
Point washing after again ultrasonic disperse into 30 mL water, next add 250 μ L mass fractions be 40 wt% hydrofluoric acid, Zhi Houzai
The mixed liquor is transferred in the reactor that capacity is 50 mL, 180oRoom temperature is naturally cooled to after the h of hydro-thermal reaction 12 under C,
Silica kernel and excessive hydrogen fluoride reaction during this and be dissolved and remove, and then generate molybdenum disulfide/graphene sky
Heart complex microsphere is simultaneously deposited in reactor bottom, is isolated by centrifugation, is dried in vacuo i.e. after fully being washed with ethanol afterwards
Can.
Molybdenum disulfide/graphene hollow compound microsphere prepared by the present embodiment has the porous hollow structure of level,
The molybdenum disulfide nano sheet on surface extremely crimps, and winds, folds, weight synthesising mesoporous (Fig. 2 and Fig. 3)；Its nitrogen adsorption-de-
Attached isothermal curve has an IV types to return stagnant ring (Fig. 4) in the range of relative pressure 0.45-1.0, show again its porous property.This
Outside, the high-resolution-ration transmission electric-lens observation result of the molybdenum disulfide/graphene hollow compound microsphere surface molybdenum disulfide nano sheet shows
Clearly lattice fringe (Fig. 5) is shown, its spacing of lattice is 0.62 nm, corresponding to (002) crystal face of hexagonal phase molybdenum disulfide；
And the powder x-ray diffraction spectrogram of the composite shows that six diffraction maximums are located at 2 respectivelyθ = 14.3o、33.6o、
40.1o、49.1o、59.0oWith 69.4o(Fig. 6), the crystal formation for more having confirmed wherein molybdenum disulfide composition are hexagonal phase.
Embodiment 2：The molybdenum disulfide that embodiment 1 is synthesized/graphene hollow compound microsphere is as electrode of super capacitor
Materials'use tests its chemical property：
(1) molybdenum disulfide/graphene hollow compound microsphere, the 5 mg acetylene synthesized by 40 mg embodiments 1 are weighed respectively
Black and 5 mg Kynoar are simultaneously put into agate mortar after being mixed, and add 350 μ L 1-METHYLPYRROLIDONEs afterwards and fill
Point slurry is ground into, then the slurry is evenly applied to the surface of nickel foam, coated area is the cm of 1 cm × 1, next general
The nickel foam coated with active material is put into vacuum drying chamber, and 60o6 h working electrodes derived above are fully dried under C.
(2) nickel foam coated with active material is as working electrode using in step (1), and Hg/HgO electrodes are as reference
Electrode, Pt plate electrodes are 2 M potassium hydroxide aqueous solution as electrolyte as auxiliary electrode and using concentration, take three electrode bodies
Be to molybdenum disulfide/graphene hollow compound microsphere synthesized in embodiment 1 through row cyclic voltammetric, constant current charge-discharge and
Electrochemical impedance spectroscopy characterizes, and tests its chemical property as electrode material for super capacitor.
Fig. 7 is the molybdenum disulfide/graphene hollow compound microsphere prepared in embodiment 1 as electrode material for super capacitor
In the different cyclic voltammograms swept under speed during use.It can be seen that all curves are showed close to rectangle and symmetrical shape
Shape, illustrate the electrode material that molybdenum disulfide/graphene hollow compound microsphere is electric double layer capacitance feature.Fig. 8 is prepared by embodiment 1
Molybdenum disulfide/graphene hollow compound microsphere when being used as electrode material for super capacitor under different current densities
Constant current charge-discharge figure, can therefrom extrapolate its specific capacitance with the increase of current density gradually reduces, it is shown in the figure most
The A g of low current density 1-1Under, its specific capacitance is up to 218.1 F g-1, hence it is evident that higher than the most of molybdenum disulfide reported at present
Specific capacitance of the based super capacitor electrode material under this current density.Fig. 9 is molybdenum disulfide/graphene prepared by embodiment 1
The electrochemical impedance when molybdenum disulfide of hollow compound microsphere and one-component uses respectively as electrode material for super capacitor
Spectrogram, it is evident that the diameter of the former intercept to real axis and high-frequency region semi arch is respectively less than the latter, illustrate the former internal resistance and
Charge transfer impedance is much smaller than the latter, that is to say, that the molybdenum disulfide that molybdenum disulfide is formed with graphene after compound/graphene is empty
Heart complex microsphere electric conductivity is better than the molybdenum disulfide material of one-component.Figure 10 is molybdenum disulfide/graphene prepared by embodiment 1
In 3 A g when hollow compound microsphere uses as electrode material for super capacitor-1Current density under its specific capacitance with filling repeatedly
The curve map of discharge time change, therefrom it can be seen that its specific capacitance downward trend is very slow, and in repeated charge
Its capacity retention is still up to 91.8% after 1000 times, equally surpasses apparently higher than the most of molybdenum-disulfide radical reported at present
Capacity retention of the level capacitor electrode material after repeated charge, illustrates the molybdenum disulfide/graphene hollow compound microsphere
With more lasting stability, so as to show wide application prospect.
Claims (1)
1. a kind of preparation method of molybdenum disulfide/graphene composite material with level porous hollow microspheroidal structure, its
It is characterised by, synthesis step is as follows：
(1) controllable, uniform in size, surface negatively charged the silicon dioxide microsphere of size is prepared using St ber methods；
(2) by electrostatic interaction in electronegative one layer of cationic polyelectrolyte polydiene propyl group of silicon dioxide microsphere surface-assembled
Alkyl dimethyl ammonium chloride, so as to be allowed to positive electricity；
(3) small size graphene oxide sheet is coated on to the silica of positive electrification by the interface self assembly means of ultrasonic wave added
Microsphere surface；Small size graphene oxide sheet of the surface with negative electricity is set to pass through electrostatic interaction under continual strength ultrasound
The silicon dioxide microsphere surface of the positive electrification in surface is self-assembled to, so as to obtain silica/graphene oxide complex microsphere；
(4) by silica/graphene oxide complex microsphere ultrasonic disperse in water, sodium molybdate and sulphur will be contained under ultrasound
The aqueous solution of urea is added dropwise in dispersion liquid, is added hydrofluoric acid and is formed homogeneous reaction system；
(5) reactant mixture is transferred in reactor, in 200oUnder C the h of hydro-thermal reaction 24 generate intermediate product silica/
Graphene/carbon/molybdenum disulfide composite microsphere, then natural cooling；Sodium molybdate reacts with thiocarbamide under hydrogen fluoride catalyzed in the process
Generation molybdenum disulfide nano sheet simultaneously deposits, is grown on substrate microsphere surface, at the same time, is coated on the oxidation of substrate microsphere surface
Graphene into graphene, and then generates intermediate product silica/graphene/carbon/molybdenum disulfide composite microsphere by hydrothermal reduction；
(6) intermediate product silica/graphene/carbon/molybdenum disulfide composite microsphere centrifuged and after washing several times again
Ultrasonic disperse adds excessive hydrofluoric acid afterwards in water, then by gained reactant mixture be again transferred in reactor and in
180 oNatural cooling after the h of hydro-thermal reaction 12 under C, in the process hydrogen fluoride fully reacted with silica kernel and be allowed to dissolve
Remove, finally, gained sediment is centrifuged, and washed with ethanol and be dried in vacuo afterwards several times, so as to obtain final product
Molybdenum disulfide/graphene hollow compound microsphere.
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| CN105098151B (en) * | 2015-06-19 | 2017-05-24 | 上海交通大学 | Molybdenum disulfide-carbon hollow ball hybrid material and preparation method thereof |
| CN104934602B (en) * | 2015-06-19 | 2017-03-08 | 上海交通大学 | A kind of molybdenum bisuphide/carbon composite and preparation method thereof |
| CN105609737A (en) * | 2016-02-21 | 2016-05-25 | 钟玲珑 | Preparation process for graphene/silicon dioxide hollow sphere/sulfur composite material |
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| CN108417404B (en) | 2019-03-15 |
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