CN109830382A - A kind of preparation method and application of the graphene/carbon nano-tube compounded microbeads with core-shell structure - Google Patents
A kind of preparation method and application of the graphene/carbon nano-tube compounded microbeads with core-shell structure Download PDFInfo
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- CN109830382A CN109830382A CN201910260386.2A CN201910260386A CN109830382A CN 109830382 A CN109830382 A CN 109830382A CN 201910260386 A CN201910260386 A CN 201910260386A CN 109830382 A CN109830382 A CN 109830382A
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Abstract
A kind of preparation method and application of the graphene/carbon nano-tube compounded microbeads with core-shell structure, it is related to a kind of graphene/carbon nano-tube compounded microbeads preparation method and application.The invention aims to solve the problems, such as that the specific volume of existing electrode material for super capacitor is low, and provide a kind of preparation method and application of graphene/carbon nano-tube compounded microbeads with core-shell structure.Method: one, preparation acidification carbon nanotube；Two, dispersed phase solution is prepared；Three, micro fluidic device is connected；Four, solidify；Five, it calcines, obtains the graphene/carbon nano-tube compounded microbeads with core-shell structure.The present invention can get a kind of graphene/carbon nano-tube compounded microbeads with core-shell structure.
Description
Technical field
The present invention relates to a kind of graphene/carbon nano-tube compounded microbeads preparation method and applications.
Background technique
With the surge of portable electronic device market demand and the fast development of hybrid vehicle, to high-energy
The demand of the energy storage device of density and high power density is continuously increased and extremely urgent.Although lithium ion battery has excellent energy
Performance is measured, but their power characteristic is not able to satisfy the requirement of many applications still.Supercapacitor, also referred to as electrochemical capacitor
Device, due to the pulse power, having extended cycle life (> 100000 times), simple operating mechanism and the charge transport of high power etc.
Advantage has attracted more and more concerns.Compared with traditional capacitor, supercapacitor possesses power capabilities and relatively
Big energy density has been applied in various energy storage devices, as Memory Backup system, domestic electronic produce
Product, industrial energy and energy management etc..Carbon-based material including active carbon, carbon nanotube and graphene possesses unique
Structure and excellent physicochemical property, are widely used in always double electric layers supercapacitor.Since active carbon has specific surface area
The advantages such as high and low cost become the most common electrode material of supercapacitor, cannot but there are many in active carbon
The carbon atom being efficiently entering by electrolyte ion, this greatly limits the specific capacitance of activated carbon electrodes, low electric conductivity also hinders
Its use in high power density supercapacitor.Carbon nanotube is due to logical with high conductivity, the transmission of improved charge
Road and effective charge contact area, it is considered to be the optional material of high power electrodes, however SWCNTs is easy to accumulation bunchy,
Therefore only outermost carbon nanotube can generate electrostatic adsorption to ion, and internal carbon is wasted, and leads to carbon
Based super capacitor can not obtain high specific capacitance.On the other hand, 1D carbon nanotube is compared, 2D graphene has and can compare favourably with it
High conductivity, high-specific surface area and outstanding mechanical performance, but in the drying process for preparing grapheme material, due to model
Irreversible reunion easily occurs between graphene sheet layer or is piled into graphite for the effect of De Huali, and the preparation of Graphene electrodes needs
The auxiliary of adhesive is wanted, these factors can generate many adverse effects to its use in supercapacitor, obtain it can not
Obtain higher specific capacitance.
Summary of the invention
The invention aims to solve the problems, such as that the specific volume of existing electrode material for super capacitor is low, and provide a kind of tool
There are a preparation method and application of the graphene/carbon nano-tube compounded microbeads of core-shell structure, and provides a kind of with core-shell structure
The preparation method and application of graphene/carbon nano-tube compounded microbeads.
A kind of preparation method of the graphene/carbon nano-tube compounded microbeads with core-shell structure, is to complete according to the following steps
:
One, preparation acidification carbon nanotube:
Carbon nanotube is immersed in nitration mixture, then temperature be 60 DEG C~80 DEG C and mixing speed be 150r/min~
It is stirred at reflux 1h~5h under 300r/min, then using distilled water as cleaning agent filtering and washing 3 times~5 times, is finally 80 DEG C in temperature
It is dry at~120 DEG C, obtain acidification carbon nanotube；
Two, dispersed phase solution is prepared:
Graphene oxide water solution and acidification carbon nanotube are add to deionized water, then low whipping speed is 200r/
0.5h~12h is stirred to react under min~400r/min, finally ultrasonic power be 50W~100W under ultrasound 15min~
120min obtains dispersed phase；
Solid content is 1mg/mL~15mg/mL in dispersed phase described in step 2；
Graphene oxide and the mass ratio of acidification carbon nanotube are (1~10) in dispersed phase described in step 2: 10；
Three, micro fluidic device is connected:
Dispersed phase is poured into the first syringe of micro fluidic device, then mobile phase is poured into the second syringe, is used
Dispersed phase and mobile phase are advanced to respectively and receive in box by micro-injection pump, obtain graphene/carbon nano-tube compounded microbeads；
Dispersed phase and the fltting speed of mobile phase ratio are (0.1~1) in step 3: 100；
Mobile phase described in step 3 is dimethicone；
Four, solidify:
Graphene/carbon nano-tube compounded microbeads are placed in a vacuum drying oven solidification, solvent is reused and washs 3 times~5 times,
It is finally placed in room temperature and dries, obtain solid graphene/carbon nanotube compounded microbeads；
Solidification temperature described in step 4 is 25 DEG C~60 DEG C, and curing time is 12h~36h；
Five, it calcines:
Solid graphene/carbon nanotube compounded microbeads are put into Muffle furnace, then calcined under an inert atmosphere, are had
The graphene/carbon nano-tube compounded microbeads of core-shell structure；
Calcination temperature described in step 5 is 600 DEG C~1000 DEG C, from room temperature to 600 DEG C~1000 DEG C of heating
Rate is 1 DEG C/min~20 DEG C/min, and the calcination time at 600 DEG C~1000 DEG C is 1h~5h.
The principle of the present invention and advantage:
One, the present invention sufficiently combines 1D carbon nanotube and 2D graphene to develop the energy storage devices haveing excellent performance
Excellent attribute, by utilize synergistic effect between the two, realize 3D graphene/carbon nano-tube composite construction building, from
And the electrode material for being used as high-performance super capacitor uses, the present invention is proposed using graphene oxide and carbon nanotube as matrix material
Material, has the graphene/carbon nano-tube compounded microbeads of core-shell structure using the preparation of drop base microflow control technique, and the method for the present invention is new
It is clever unique, the graphene/carbon nano-tube compounded microbeads with core-shell structure are prepared using the shearing force between reverse phase solvent, later
There is the graphene oxide of more hydrophilic radicals to form core-shell structure as moisture moves out on surface；
Two, the graphene/carbon nano-tube compounded microbeads size prepared by the present invention with core-shell structure is uniform, and sphericity is high
And monodispersity is good, is outstanding electrode material for super capacitor；
Three, the capacitor being assembled into using the graphene/carbon nano-tube compounded microbeads prepared by the present invention with core-shell structure
The bulking value of device is 200F/g~300F/g.
The present invention can get a kind of graphene/carbon nano-tube compounded microbeads with core-shell structure.
Detailed description of the invention
Fig. 1 is that the whole ball of the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one amplifies 100 times
SEM figure；
Fig. 2 is that the whole ball of the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one amplifies 300 times
SEM figure；
Fig. 3 is the broken ball amplification 20000 of the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one
SEM figure again；
Fig. 4 is infrared spectrogram, and 1 solid graphene/carbon nanotube for obtaining for one step 4 of embodiment is compound micro- in figure
The infrared spectrogram of pearl, the 2 graphene/carbon nano-tube compounded microbeads with core-shell structure obtained for one step 5 of embodiment；
Fig. 5 is XRD spectra, the 1 solid graphene/carbon nanotube compounded microbeads obtained for one step 4 of embodiment in figure
XRD curve, the XRD song of the 2 graphene/carbon nano-tube compounded microbeads with core-shell structure obtained for one step 5 of embodiment
Line；
Fig. 6 is Raman spectrogram, and 1 solid graphene/carbon nanotube for obtaining for one step 4 of embodiment is compound micro- in figure
The Raman curve of pearl, 2 be the graphene/carbon nano-tube compounded microbeads with core-shell structure that one step 5 of embodiment obtains
XRD curve；
Fig. 7 is XPS figure, the 1 solid graphene/carbon nanotube compounded microbeads obtained for one step 4 of embodiment in figure
XPS curve, the XPS song of the 2 graphene/carbon nano-tube compounded microbeads with core-shell structure obtained for one step 5 of embodiment
Line；
Fig. 8 is the obtained graphene/carbon nano-tube compounded microbeads with core-shell structure of one step 5 of embodiment in difference
Cyclic voltammogram under rate, 1 rate is 10mV/s in figure, and 2 be 20mV/s, and 3 be 50mV/s, and 4 be 100mV/s, and 5 are
200mV/s；
Fig. 9 is the obtained graphene/carbon nano-tube compounded microbeads with core-shell structure of one step 5 of embodiment in difference
Constant current charge-discharge curve graph under current strength, 1 current strength is 0.5A/g in figure, and 2 current strength is 1A/g, 3 electricity
Intensity of flow is 2A/g, and 4 current strength is 3A/g, and 5 current strength is 5A/g；
Figure 10 is the structural schematic diagram of micro fluidic device described in one step 3 of embodiment, and 1 is the first syringe in figure,
2 be the second syringe, and 3 be micro-injection pump, and 4 be threeway, and 5 be reception box.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of graphene/carbon nano-tube compounded microbeads with core-shell structure
Preparation method be completed by the following steps:
One, preparation acidification carbon nanotube:
Carbon nanotube is immersed in nitration mixture, then temperature be 60 DEG C~80 DEG C and mixing speed be 150r/min~
It is stirred at reflux 1h~5h under 300r/min, then using distilled water as cleaning agent filtering and washing 3 times~5 times, is finally 80 DEG C in temperature
It is dry at~120 DEG C, obtain acidification carbon nanotube；
Two, dispersed phase solution is prepared:
Graphene oxide water solution and acidification carbon nanotube are add to deionized water, then low whipping speed is 200r/
0.5h~12h is stirred to react under min~400r/min, finally ultrasonic power be 50W~100W under ultrasound 15min~
120min obtains dispersed phase；
Solid content is 1mg/mL~15mg/mL in dispersed phase described in step 2；
Graphene oxide and the mass ratio of acidification carbon nanotube are (1~10) in dispersed phase described in step 2: 10；
Three, micro fluidic device is connected:
Dispersed phase is poured into the first syringe 1 of micro fluidic device, then mobile phase is poured into the second syringe 2, is made
Dispersed phase and mobile phase are advanced to respectively with micro-injection pump 3 and received in box 5, graphene/carbon nano-tube compounded microbeads are obtained；
Dispersed phase and the fltting speed of mobile phase ratio are (0.1~1) in step 3: 100；
Mobile phase described in step 3 is dimethicone；
Four, solidify:
Graphene/carbon nano-tube compounded microbeads are placed in a vacuum drying oven solidification, solvent is reused and washs 3 times~5 times,
It is finally placed in room temperature and dries, obtain solid graphene/carbon nanotube compounded microbeads；
Solidification temperature described in step 4 is 25 DEG C~60 DEG C, and curing time is 12h~36h；
Five, it calcines:
Solid graphene/carbon nanotube compounded microbeads are put into Muffle furnace, then calcined under an inert atmosphere, are had
The graphene/carbon nano-tube compounded microbeads of core-shell structure；
Calcination temperature described in step 5 is 600 DEG C~1000 DEG C, from room temperature to 600 DEG C~1000 DEG C of heating
Rate is 1 DEG C/min~20 DEG C/min, and the calcination time at 600 DEG C~1000 DEG C is 1h~5h.
The principle and advantage of present embodiment:
One, present embodiment sufficiently combines 1D carbon nanotube and 2D stone to develop the energy storage devices haveing excellent performance
The excellent attribute of black alkene realizes the structure of 3D graphene/carbon nano-tube composite construction by utilizing synergistic effect between the two
It builds, so that the electrode material for being used as high-performance super capacitor uses, present embodiment is proposed with graphene oxide and carbon nanometer
Pipe is basis material, has the graphene/carbon nano-tube compounded microbeads of core-shell structure using the preparation of drop base microflow control technique, this
The method novel and unique of embodiment is prepared the graphene/carbon with core-shell structure using the shearing force between reverse phase solvent and is received
Mitron compounded microbeads, rear surface have more hydrophilic radicals graphene oxide nucleocapsid knot is formed as moisture moves out
Structure；
Two, the graphene/carbon nano-tube compounded microbeads size with core-shell structure of present embodiment preparation is uniform, spherical
Degree is high and monodispersity is good, is outstanding electrode material for super capacitor；
Three, it is assembled into using the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by present embodiment
The bulking value of capacitor is 200F/g~300F/g.
Present embodiment can get a kind of graphene/carbon nano-tube compounded microbeads with core-shell structure.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: nitration mixture described in step 1
For mass fraction be 98% sulfuric acid and mass fraction be 65% nitric acid mixed liquor；The sulphur that mass fraction is 98% in nitration mixture
The volume ratio for the nitric acid that acid is 65% with mass fraction is (1~5): 1.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 2
Solid content is 1mg/mL~5mg/mL in the dispersed phase solution stated；In dispersed phase solution described in step 2 graphene oxide with
The mass ratio for being acidified carbon nanotube is (1~4): 10.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: institute in step 2
The viscosity for the dimethicone stated is 100cst~500cst.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: institute in step 3
The micro fluidic device stated includes the first syringe 1, the second syringe 2, micro-injection pump 3, threeway 4 and receives box 5；Described
One syringe 1 and the second syringe 2 are arranged in parallel in micro-injection pump 3, and the first syringe 1 is hung down by conduit and threeway 4
Straight end is connected, and the second syringe 2 is connected by conduit with the horizontal ends of threeway 4, another horizontal ends conduit of threeway 4 with
It receives box 5 to be connected, the material for receiving box 5 is polypropylene, and the material of conduit is polytetrafluoroethylene (PTFE).Other steps and specific implementation
Mode one to four is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 4
The solvent stated is one of n-hexane, hexamethylene, normal heptane and petroleum ether or in which several mixed liquors.Other steps and tool
Body embodiment one to five is identical.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 4
The solidification temperature stated is 25 DEG C~45 DEG C, and curing time is 12h~for 24 hours.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: institute in step 5
The inert atmosphere stated is nitrogen, helium or argon gas.Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: institute in step 5
The calcination temperature stated be 700 DEG C~800 DEG C, from room temperature to 700 DEG C~800 DEG C of heating rate be 2 DEG C/min~5 DEG C/
Min, the calcination time at 700 DEG C~800 DEG C are 2h~3h.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: present embodiment is a kind of graphene/carbon nano-tube compounded microbeads with core-shell structure
It is used as electrode material for super capacitor.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of the graphene/carbon nano-tube compounded microbeads with core-shell structure, is by following
What step was completed:
One, preparation acidification carbon nanotube:
Carbon nanotube is immersed in nitration mixture, then is stirred at reflux in the case where temperature is 70 DEG C and mixing speed is 200r/min
2h, then using distilled water as cleaning agent filtering and washing 3 times, dry 8h at being finally 100 DEG C in temperature obtains acidification carbon nanotube；
The mixing for the nitric acid that nitration mixture described in step 1 is the sulfuric acid that mass fraction is 98% and mass fraction is 65%
Liquid；The volume ratio for the nitric acid that the sulfuric acid and mass fraction that mass fraction is 98% in nitration mixture are 65% is 3:1；
Two, dispersed phase solution is prepared:
Graphene oxide water solution and acidification carbon nanotube are add to deionized water, then low whipping speed is 300r/
8h is stirred to react under min, finally the ultrasound 30min in the case where ultrasonic power is 100W, obtains dispersed phase；
Solid content is 5mg/mL in dispersed phase described in step 2；
Graphene oxide and the mass ratio of acidification carbon nanotube are 3:10 in dispersed phase described in step 2；
Three, micro fluidic device is connected:
Dispersed phase is poured into the first syringe 1 of micro fluidic device, then mobile phase is poured into the second syringe 2, is made
Dispersed phase solution and mobile phase are advanced to respectively with micro-injection pump 3 and received in box 5, it is compound to obtain graphene/carbon nano-tube
Microballon；
Dispersed phase and the fltting speed of mobile phase ratio are 0.5:100 in step 3；
Mobile phase described in step 3 is dimethicone, viscosity 500cst；
Four, solidify:
Graphene/carbon nano-tube compounded microbeads are placed in a vacuum drying oven solidification, reuse n-hexane washing 3 times, most
It is placed on drying in room temperature and for 24 hours, obtains solid graphene/carbon nanotube compounded microbeads；
Solidification temperature described in step 4 is 45 DEG C, and curing time is for 24 hours；
Five, it calcines:
Solid graphene/carbon nanotube compounded microbeads are put into Muffle furnace, then calcined in a nitrogen atmosphere, are had
The graphene/carbon nano-tube compounded microbeads of core-shell structure；
Calcination temperature described in step 5 is 700 DEG C, is 5 DEG C/min from room temperature to 700 DEG C of heating rate,
Calcination time at 700 DEG C is 2h.
Graphene oxide described in one step 2 of embodiment is prepared according to the following steps:
5.0g crystalline flake graphite and 2.0g KCl are mixed to be placed in ice-water bath and are cooled to 0 DEG C, adds 80mL mass point
The sulfuric acid that number is 98%, then 9.0g potassium permanganate is added in three times, then 2h is reacted in ice-water bath, it is finally stirred at 40 DEG C anti-
10h is answered, after reaction, 10.0g potassium permanganate is added into system, then continue to stir 15h at being 40 DEG C in temperature, then by body
System is cooled to room temperature, then the hydrogenperoxide steam generator that 5mL mass fraction is 30% is added into system, after reaction at room temperature
It stands for 24 hours, is then centrifuged again, remove centrifugate, obtain centrifugation product；Make to be centrifuged wash with distilled water product 3 times, then will
Centrifugation product is fitted into bag filter, then the ultrasound 2h in the case where ultrasonic power is 100W, will be equipped with the saturating of centrifugation product after ultrasound
Analysis bag, which is put into deionized water, to be impregnated for 24 hours, and graphene oxide water solution is obtained；The concentration of the graphene oxide water solution is
8mg/mL。
Micro fluidic device described in one step 3 of embodiment includes the first syringe 1, the second syringe 2, micro-injection
Pump 3, threeway 4 and reception box 5；First syringe 1 and the second syringe 2 is arranged in parallel in micro-injection pump 3, and first
Syringe 1 is connected by conduit with the vertical end of threeway 4, and the second syringe 2 is connected by conduit with the horizontal ends of threeway 4
It connects, another horizontal ends conduit of threeway 4 is connected with box 5 is received, and the material for receiving box 5 is polypropylene, and the material of conduit is
Polytetrafluoroethylene (PTFE).
Fig. 1 is that the whole ball of the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one amplifies 100 times
SEM figure；
From fig. 1, it can be seen that the graphene/carbon nano-tube compounded microbeads form with core-shell structure prepared by embodiment one is good
Good, size uniformity, average grain diameter is 115 μm.
Fig. 2 is that the whole ball of the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one amplifies 300 times
SEM figure；
The graphene/carbon nano-tube with core-shell structure for being it clear that prepared by embodiment one from Fig. 2 is compound
Microballon forms unique core-shell structure, surface be fold, at carinate graphene packed structures, shell thickness is about 6 μm.
Fig. 3 is the broken ball amplification 20000 of the graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one
SEM figure again；
As can be seen from Figure 3, this uniqueness of graphene/carbon nano-tube compounded microbeads with core-shell structure prepared by embodiment one
Three-dimensional appearance provides huge specific surface area, is beneficial to improve the conduction of electronics when being used as electrode material for super capacitor
Rate.
Fig. 4 is infrared spectrogram, and 1 solid graphene/carbon nanotube for obtaining for one step 4 of embodiment is compound micro- in figure
The infrared spectrogram of pearl, the 2 graphene/carbon nano-tube compounded microbeads with core-shell structure obtained for one step 5 of embodiment；
As can be seen from Figure 4, the graphene/carbon nano-tube compounded microbeads with core-shell structure obtained after calcining exist
1718cm-1、1231cm-1And 1086cm-1C=O, C-OH and C-O stretching vibration absworption peak at place disappear, it was confirmed that oxygen-containing function
The removal of group.
Fig. 5 is XRD spectra, the 1 solid graphene/carbon nanotube compounded microbeads obtained for one step 4 of embodiment in figure
XRD curve, the XRD song of the 2 graphene/carbon nano-tube compounded microbeads with core-shell structure obtained for one step 5 of embodiment
Line；
As can be seen from Figure 5, what the diffraction maximum at 2 θ=11.22 ° belonged to that one step 5 of embodiment obtains has nucleocapsid knot
(001) crystal face of GO in the graphene/carbon nano-tube compounded microbeads of structure, this peak disappears after firing, 2 θ=26 ° and 42.9 °
Locate existing diffraction maximum and belong to C (002) and C (101) reflection, shows that graphene oxide is successfully reduced to stone by high-temperature calcination
Black alkene.
Fig. 6 is Raman spectrogram, and 1 solid graphene/carbon nanotube for obtaining for one step 4 of embodiment is compound micro- in figure
The Raman curve of pearl, 2 be the graphene/carbon nano-tube compounded microbeads with core-shell structure that one step 5 of embodiment obtains
XRD curve；
As can be seen from Figure 6, in 1328cm-1And 1574cm-1There is the peak feature D and G relevant to carbon material in place, it is evident that micro-
The ID/IG value of pearl is increased to that treated 1.62 by 1.32 before high-temperature process, this result shows that high temperature cabonization in graphene
Biggish defect concentration is introduced with carbon nano tube surface.
Fig. 7 is XPS figure, the 1 solid graphene/carbon nanotube compounded microbeads obtained for one step 4 of embodiment in figure
XPS curve, the XPS song of the 2 graphene/carbon nano-tube compounded microbeads with core-shell structure obtained for one step 5 of embodiment
Line；
As can be seen from Figure 7, through high-temperature calcination, O1s peak intensity is significantly reduced and C1s peak intensity is remarkably reinforced；Oxygen element content
4.24at% is reduced to by 16.66at%, while C/O ratio is increased to 22.58 from 5, it is consistent with FT-IR result.
Data in Fig. 7 are listed in table 1.
Table 1
It is assembled into using the graphene/carbon nano-tube compounded microbeads with core-shell structure that one step 5 of embodiment obtains super
Grade capacitor devices are completed by the following steps:
It is added in the graphene/carbon nano-tube compounded microbeads with core-shell structure obtained to one step 5 of 3g embodiment
100mL deionized water reuses the polytetrafluoroethylsolution solution that mass fraction is 8% and is tuned into paste, then paste is had nucleocapsid
The graphene/carbon nano-tube compounded microbeads blade coating of structure in the nickel foam with a thickness of 1.5mm, coating having a size of 1cm × 4cm,
Forced air drying 6h at being again 60 DEG C in temperature, finally nickel foam is made with a thickness of 0.5mm on twin-roll machine, obtains with nucleocapsid knot
The graphene/carbon nano-tube compounded microbeads electrode slice of structure, to the graphene/carbon nano-tube compounded microbeads electrode with core-shell structure
Piece is tested, as shown in Figure 8；Two panels had into folder among the graphene/carbon nano-tube compounded microbeads electrode slice of core-shell structure
Upper battery separator paper, is assembled into ultracapacitor device, impregnates 120min in the KOH solution of 6mol/L, carries out to capacitor
Test, as shown in Figure 9；
Fig. 8 is the obtained graphene/carbon nano-tube compounded microbeads with core-shell structure of one step 5 of embodiment in difference
Cyclic voltammogram under rate, 1 rate is 10mV/s in figure, and 2 be 20mV/s, and 3 be 50mV/s, and 4 be 100mV/s, and 5 are
200mV/s；
As it can be observed in the picture that CV curve remains well in the potential range of -1~0 V with the increase of sweep speed
Class rectangle shape, while not observing apparent redox peaks, this is the result shows that nucleocapsid microballon electrode material only has
There is electric double layer capacitance characteristic, is mainly had an effect by way of Electrostatic Absorption with electrode material due to electrolyte ion, and
Non- generation electrochemical reaction.In addition, the electrode material, in scanning voltage inverse change, electric current energy moment is reversed, show electrode
With fast-response and good cyclic reversibility.
Fig. 9 is the obtained graphene/carbon nano-tube compounded microbeads with core-shell structure of one step 5 of embodiment in difference
Constant current charge-discharge curve graph under current strength, 1 current strength is 0.5A/g in figure, and 2 current strength is 1A/g, 3 electricity
Intensity of flow is 2A/g, and 4 current strength is 3A/g, and 5 current strength is 5A/g.
It can be seen in figure 9 that all GV curves are rendered as the triangular shaped of distortion, and with current density
Increase, discharge time is gradually reduced.In addition, being calculated through formula, the graphite with core-shell structure that one step 5 of embodiment obtains
It is corresponding than electricity under 0.5,1,2,3 and 5 A/g current densities that alkene/carbon nanotube compounded microbeads are assembled into ultracapacitor device
Capacitance is respectively 281,238,174,86 and 32 F/g.
Figure 10 is the structural schematic diagram of micro fluidic device described in one step 3 of embodiment, and 1 is the first syringe in figure,
2 be the second syringe, and 3 be micro-injection pump, and 4 be threeway, and 5 be reception box.
Embodiment two: a kind of preparation method of the graphene/carbon nano-tube compounded microbeads with core-shell structure, is by following
What step was completed:
One, preparation acidification carbon nanotube:
Carbon nanotube is immersed in nitration mixture, then is stirred at reflux in the case where temperature is 70 DEG C and mixing speed is 200r/min
3h, then using distilled water as cleaning agent filtering and washing 3 times, dry 8h at being finally 100 DEG C in temperature obtains acidification carbon nanotube；
The mixing for the nitric acid that nitration mixture described in step 1 is the sulfuric acid that mass fraction is 98% and mass fraction is 65%
Liquid；The volume ratio for the nitric acid that the sulfuric acid and mass fraction that mass fraction is 98% in nitration mixture are 65% is 2:1；
Two, dispersed phase solution is prepared:
Graphene oxide water solution and acidification carbon nanotube are add to deionized water, then low whipping speed is 300r/
6h is stirred to react under min, finally the ultrasound 45min in the case where ultrasonic power is 100W, obtains dispersed phase；
Solid content is 3mg/mL in dispersed phase described in step 2；
Graphene oxide and the mass ratio of acidification carbon nanotube are 1:2 in dispersed phase described in step 2；
Three, micro fluidic device is connected:
Dispersed phase is poured into the first syringe 1 of micro fluidic device, then mobile phase is poured into the second syringe 2, is made
Dispersed phase solution and mobile phase are advanced to respectively with micro-injection pump 3 and received in box 5, it is compound to obtain graphene/carbon nano-tube
Microballon；
Dispersed phase and the fltting speed of mobile phase ratio are 1:100 in step 3；
Mobile phase described in step 3 is dimethicone, viscosity 500cst；
Four, solidify:
Graphene/carbon nano-tube compounded microbeads are placed in a vacuum drying oven solidification, reuse n-hexane washing 3 times, most
It is placed on drying in room temperature and for 24 hours, obtains solid graphene/carbon nanotube compounded microbeads；
Solidification temperature described in step 4 is 35 DEG C, and curing time is for 24 hours；
Five, it calcines:
Solid graphene/carbon nanotube compounded microbeads are put into Muffle furnace, then calcined in a nitrogen atmosphere, are had
The graphene/carbon nano-tube compounded microbeads of core-shell structure；
Calcination temperature described in step 5 is 800 DEG C, is 10 DEG C/min from room temperature to 800 DEG C of heating rate,
Calcination time at 700 DEG C is 1h.
Graphene oxide described in two step 2 of embodiment is prepared according to the following steps:
5.0g crystalline flake graphite and 2.0g KCl are mixed to be placed in ice-water bath and are cooled to 0 DEG C, adds 80mL mass point
The sulfuric acid that number is 98%, then 9.0g potassium permanganate is added in three times, then 2h is reacted in ice-water bath, it is finally stirred at 40 DEG C anti-
10h is answered, after reaction, 10.0g potassium permanganate is added into system, then continue to stir 15h at being 40 DEG C in temperature, then by body
System is cooled to room temperature, then the hydrogenperoxide steam generator that 5mL mass fraction is 30% is added into system, after reaction at room temperature
It stands for 24 hours, is then centrifuged again, remove centrifugate, obtain centrifugation product；Make to be centrifuged wash with distilled water product 3 times, then will
Centrifugation product is fitted into bag filter, then the ultrasound 2h in the case where ultrasonic power is 100W, will be equipped with the saturating of centrifugation product after ultrasound
Analysis bag, which is put into deionized water, to be impregnated for 24 hours, and graphene oxide water solution is obtained；The concentration of the graphene oxide water solution is
8mg/mL。
Micro fluidic device described in two step 3 of embodiment includes the first syringe 1, the second syringe 2, micro-injection
Pump 3, threeway 4 and reception box 5；First syringe 1 and the second syringe 2 is arranged in parallel in micro-injection pump 3, and first
Syringe 1 is connected by conduit with the vertical end of threeway 4, and the second syringe 2 is connected by conduit with the horizontal ends of threeway 4
It connects, another horizontal ends conduit of threeway 4 is connected with box 5 is received, and the material for receiving box 5 is polypropylene, and the material of conduit is
Polytetrafluoroethylene (PTFE).
Embodiment three: a kind of preparation method of the graphene/carbon nano-tube compounded microbeads with core-shell structure, is by following
What step was completed:
One, preparation acidification carbon nanotube:
Carbon nanotube is immersed in nitration mixture, then is stirred at reflux in the case where temperature is 80 DEG C and mixing speed is 200r/min
1h, then using distilled water as cleaning agent filtering and washing 3 times, it is dry at being finally 100 DEG C in temperature, obtain acidification carbon nanotube；
The mixing for the nitric acid that nitration mixture described in step 1 is the sulfuric acid that mass fraction is 98% and mass fraction is 65%
Liquid；The volume ratio for the nitric acid that the sulfuric acid and mass fraction that mass fraction is 98% in nitration mixture are 65% is 4:1；
Two, dispersed phase solution is prepared:
Graphene oxide water solution and acidification carbon nanotube are add to deionized water, then low whipping speed is 300r/
10h is stirred to react under min, finally the ultrasound 60min in the case where ultrasonic power is 100W, obtains dispersed phase；
Solid content is 10mg/mL in dispersed phase described in step 2；
Graphene oxide and the mass ratio of acidification carbon nanotube are 4:10 in dispersed phase described in step 2；
Three, micro fluidic device is connected:
Dispersed phase is poured into the first syringe 1 of micro fluidic device, then mobile phase is poured into the second syringe 2, is made
Dispersed phase solution and mobile phase are advanced to respectively with micro-injection pump 3 and received in box 5, it is compound to obtain graphene/carbon nano-tube
Microballon；
Dispersed phase and the fltting speed of mobile phase ratio are 0.2:150 in step 3；
Mobile phase described in step 3 is dimethicone, viscosity 500cst；
Four, solidify:
Graphene/carbon nano-tube compounded microbeads are placed in a vacuum drying oven solidification, reuse n-hexane washing 3 times, most
It is placed on drying in room temperature and for 24 hours, obtains solid graphene/carbon nanotube compounded microbeads；
Solidification temperature described in step 4 is 45 DEG C, and curing time is for 24 hours；
Five, it calcines:
Solid graphene/carbon nanotube compounded microbeads are put into Muffle furnace, then calcined in a nitrogen atmosphere, are had
The graphene/carbon nano-tube compounded microbeads of core-shell structure；
Calcination temperature described in step 5 is 750 DEG C, is 3 DEG C/min from room temperature to 750 DEG C of heating rate,
Calcination time at 700 DEG C is 1h.
Graphene oxide described in three step 2 of embodiment is prepared according to the following steps:
5.0g crystalline flake graphite and 2.0g KCl are mixed to be placed in ice-water bath and are cooled to 0 DEG C, adds 80mL mass point
The sulfuric acid that number is 98%, then 9.0g potassium permanganate is added in three times, then 2h is reacted in ice-water bath, it is finally stirred at 40 DEG C anti-
10h is answered, after reaction, 10.0g potassium permanganate is added into system, then continue to stir 15h at being 40 DEG C in temperature, then by body
System is cooled to room temperature, then the hydrogenperoxide steam generator that 5mL mass fraction is 30% is added into system, after reaction at room temperature
It stands for 24 hours, is then centrifuged again, remove centrifugate, obtain centrifugation product；Make to be centrifuged wash with distilled water product 3 times, then will
Centrifugation product is fitted into bag filter, then the ultrasound 2h in the case where ultrasonic power is 100W, will be equipped with the saturating of centrifugation product after ultrasound
Analysis bag, which is put into deionized water, to be impregnated for 24 hours, and graphene oxide water solution is obtained；The concentration of the graphene oxide water solution is
8mg/mL。
Micro fluidic device described in three step 3 of embodiment includes the first syringe 1, the second syringe 2, micro-injection
Pump 3, threeway 4 and reception box 5；First syringe 1 and the second syringe 2 is arranged in parallel in micro-injection pump 3, and first
Syringe 1 is connected by conduit with the vertical end of threeway 4, and the second syringe 2 is connected by conduit with the horizontal ends of threeway 4
It connects, another horizontal ends conduit of threeway 4 is connected with box 5 is received, and the material for receiving box 5 is polypropylene, and the material of conduit is
Polytetrafluoroethylene (PTFE).
Claims (10)
1. a kind of preparation method of the graphene/carbon nano-tube compounded microbeads with core-shell structure, it is characterised in that one kind has
The preparation method of the graphene/carbon nano-tube compounded microbeads of core-shell structure is completed by the following steps:
One, preparation acidification carbon nanotube:
Carbon nanotube is immersed in nitration mixture, then is 60 DEG C~80 DEG C in temperature and mixing speed is 150r/min~300r/min
Under be stirred at reflux 1h~5h, then using distilled water as cleaning agent filtering and washing 3 times~5 times, finally in the case where temperature is 80 DEG C~120 DEG C
It is dry, obtain acidification carbon nanotube；
Two, dispersed phase solution is prepared:
By graphene oxide water solution and acidification carbon nanotube be add to deionized water, then low whipping speed be 200r/min~
0.5h~12h is stirred to react under 400r/min, finally ultrasound 15min~120min in the case where ultrasonic power is 50W~100W, obtains
Dispersed phase；
Solid content is 1mg/mL~15mg/mL in dispersed phase described in step 2；
Graphene oxide and the mass ratio of acidification carbon nanotube are (1~10) in dispersed phase described in step 2: 10；
Three, micro fluidic device is connected:
Dispersed phase is poured into the first syringe (1) of micro fluidic device, then mobile phase is poured into the second syringe (2), is made
Dispersed phase and mobile phase are advanced to respectively with micro-injection pump (3) and received in box (5), it is compound to obtain graphene/carbon nano-tube
Microballon；
Dispersed phase and the fltting speed of mobile phase ratio are (0.1~1) in step 3: 100；
Mobile phase described in step 3 is dimethicone；
Four, solidify:
Graphene/carbon nano-tube compounded microbeads are placed in a vacuum drying oven solidification, reuse solvent washing 3 times~5 times, finally
It is placed in room temperature and dries, obtain solid graphene/carbon nanotube compounded microbeads；
Solidification temperature described in step 4 is 25 DEG C~60 DEG C, and curing time is 12h~36h；
Five, it calcines:
Solid graphene/carbon nanotube compounded microbeads are put into Muffle furnace, then calcined under an inert atmosphere, are obtained with nucleocapsid
The graphene/carbon nano-tube compounded microbeads of structure；
Calcination temperature described in step 5 is 600 DEG C~1000 DEG C, from room temperature to 600 DEG C~1000 DEG C of heating rate
For 1 DEG C/min~20 DEG C/min, the calcination time at 600 DEG C~1000 DEG C is 1h~5h.
2. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that the nitric acid that nitration mixture described in step 1 is the sulfuric acid that mass fraction is 98% and mass fraction is 65% is mixed
Close liquid；The volume ratio for the nitric acid that the sulfuric acid and mass fraction that mass fraction is 98% in nitration mixture are 65% is (1~5): 1.
3. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that solid content is 1mg/mL~5mg/mL in dispersed phase solution described in step 2；Dispersion described in step 2
Graphene oxide and the mass ratio of acidification carbon nanotube are (1~4) in phase solution: 10.
4. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that the viscosity of dimethicone described in step 2 is 100cst~500cst.
5. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that micro fluidic device described in step 3 includes the first syringe (1), the second syringe (2), micro-injection pump
(3), threeway (4) and reception box (5)；First syringe (1) and the second syringe (2) is arranged in parallel in micro-injection pump
(3) in, the first syringe (1) is connected by conduit with the vertical end of threeway (4), and the second syringe (2) passes through conduit and three
The horizontal ends of logical (4) are connected, and another horizontal ends of threeway (4) are connected with conduit with box (5) are received, and receive the material of box (5)
Matter is polypropylene, and the material of conduit is polytetrafluoroethylene (PTFE).
6. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that solvent described in step 4 is one of n-hexane, hexamethylene, normal heptane and petroleum ether or in which several
Mixed liquor.
7. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that solidification temperature described in step 4 is 25 DEG C~45 DEG C, curing time is 12h~for 24 hours.
8. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that inert atmosphere described in step 5 is nitrogen, helium or argon gas.
9. a kind of preparation method of graphene/carbon nano-tube compounded microbeads with core-shell structure according to claim 1,
It is characterized in that calcination temperature described in step 5 is 700 DEG C~800 DEG C, from room temperature to 700 DEG C~800 DEG C of heating
Rate is 2 DEG C/min~5 DEG C/min, and the calcination time at 700 DEG C~800 DEG C is 2h~3h.
10. a kind of application of the graphene/carbon nano-tube compounded microbeads with core-shell structure as described in claim 1, special
Sign is that a kind of graphene/carbon nano-tube compounded microbeads with core-shell structure are used as electrode material for super capacitor.
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