CN106245104B - A method of preparing graphene based on electrochemical process stripping dual graphite electrodes - Google Patents
A method of preparing graphene based on electrochemical process stripping dual graphite electrodes Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Abstract
A method of graphene being prepared based on electrochemical process stripping dual graphite electrodes, first, sulfate or carbonate is dissolved in deionized water, the concentrated sulfuric acid is then added dropwise, electrolyte is made；Wherein, the amount ratio ranging from 1 of the substance of sulfate or carbonate and the concentrated sulfuric acid:1~1:9；Then, two panels graphite flake is placed in electrolyte, then two panels graphite flake is connect with voltage stabilizing rectangular wave power supply；It is passed through rectangular wave stabilized power source on the electrode, starts stripping and timing, until no solid is detached from electrode, stripping terminates；Electrode is taken off, by after stripping electrolyte and graphene detach, and be washed with deionized；By being distributed in dispersant for obtained graphene uniform, stable graphene dispersing solution is formed.The present invention has many advantages, such as simple for process, safely controllable, repeatability is high, yield height, easy manipulation.Most of all, it is energy saving, do not generate any pollution to environment.
Description
Technical field
The present invention relates to field of nano material preparation, are related to the method that electrochemical process prepares high-quality graphene, specifically relate to
A kind of and method preparing graphene based on electrochemical process stripping dual graphite electrodes.
Background technology
Univ Manchester UK A.K.Geim professors seminar successfully prepares stone using micromechanics stripping method within 2004
Black alkene has broken the judgement that perfect two dimensional crystal structure can not possibly be stabilized under non-absolute zero.Then graphene is excellent
Electrical properties, mechanical property, thermal property, optical property in succession be studied personnel find.In addition, graphene has super large
Theoretical specific surface area, excellent properties possessed by monoatomic layer structure in addition, using graphene as the carbon-based material of source material
Significant progress and application are obtained.
The current widely used method for preparing graphene can substantially be divided into following a few classes：Micromechanics stripping method,
Chemical vapour deposition technique, graphene oxide reduction method, solvent stripping method, electrochemical stripping and longitudinally cutting carbon tube method etc. are several
Kind.Wherein, micromechanics stripping method overcomes Van der Waals force, advantage to be low defect, high electron mobility using micromechanics stress, but
Its of high cost, low yield, is suitable only for basic research；Chemical vapour deposition technique (CVD) is to utilize C, H compound, high temperature pyrolysis
Generation carbon atom, which is deposited on, sinks to the bottom surface, and quality of graphene obtained is high, but its of high cost, complex process；Oxidation-reduction method is
It is then reduced into RGO, advantage is that graphene stable dispersion is made, and disadvantage has useless to GO through strong acid or strong oxidizer using graphite
Liquid pollution, existing defects；Solvent stripping method is to enter graphite layers using solvent, and it is high, scarce that quality of graphene is made in ultrasound stripping
It falls into less, but yield is very low；Electrochemical process stripping is that ionic adsorption, gas evolution etc. is utilized to overcome Van der Waals force, graphite obtained
Alkene electric conductivity is excellent, and defect is few, yield height and good dispersion, and it is considered as that most probable realizes stone that this method, which prepares graphene,
Important method prepared by black alkene industrialization.But the method yield that existing electrochemistry prepares graphene is relatively low, mostly uses
Graphite foil needs noble metal to make cathode as anode, bigger to the dependence of noble metal platinum to be unfavorable for industrialized production.Cause
The graphene that this efficient, quick, low cost prepares high quality attracts people's attention.
Invention content
The method that dual graphite electrodes prepare graphene is removed based on electrochemical process the purpose of the present invention is to provide a kind of,
On the basis of existing electrochemical stripping graphene, noble metal platinum electrode is eliminated, is prepared using dual graphite electrodes electrochemical stripping
Graphene simplifies technique, reduces cost, and use rectangular wave power supply checker positive and negative anodes, and recirculation gas stripper graphite foil improves stone
Black alkene yield obtains quality height and graphene product with good conductivity.The present invention has simple for process, reproducible, yield
Height, many advantages, such as being easy to manipulate.
In order to achieve the goal above, the technical solution adopted in the present invention is：
A method of graphene being prepared based on electrochemical process stripping dual graphite electrodes, is included the following steps：
1) device for preparing graphene is built：
First, sulfate or carbonate are dissolved in deionized water, the concentrated sulfuric acid is then added dropwise, electrolyte is made；Wherein, sulfuric acid
The amount ratio ranging from 1 of the substance of salt or carbonate and the concentrated sulfuric acid:1~1:9；
Then, two panels graphite flake is placed in electrolyte, then two panels graphite flake is connect with voltage stabilizing rectangular wave power supply；
2) exfoliated graphite prepares graphene：
It is passed through rectangular wave stabilized power source on two panels graphite flake in step 1) as electrode, starts stripping and timing, until
There is no solid to be detached from electrode, stripping terminates；
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, by after stripping electrolyte and graphene detach, deionized water is used in combination
Washing；
4) stable graphene dispersing solution is prepared：
By being distributed in dispersant for graphene uniform that step 3) obtains, stable graphene dispersing solution is formed.
The present invention, which further improves, to be, the sulfate is ammonium sulfate, sodium sulphate or potassium sulfate；The carbonate is
Ammonium carbonate.
The present invention, which further improves, to be, the sulfate or carbonate and the ratio of deionized water be (0.55~
0.7467)g：120mL.
The present invention, which further improves, to be, the thickness of the graphite flake is 0.246mm, length 3cm, and width is
2.5cm。
The present invention, which further improves, to be, is cut under two with scissors every graphite flake upper edge short transverse is bottom-up.
The present invention, which further improves, to be, the voltage of the rectangular wave stabilized power source is ± 6V, period 120s.
The present invention, which further improves, to be, from stripping and timing is started, until the time that no solid is detached from electrode is
10min。
The present invention further improve is, using vacuum filtration and 0.45 μm of filter membrane of water system by after stripping electrolyte and
Graphene is detached.
The present invention, which further improves, to be, using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains
In dispersant；Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument, ultrasonic power 50%, ultrasonic time using general power 300W
For 10min.
The present invention, which further improves, to be, the dispersant is n,N-Dimethylformamide, alcohol or acetone.
Compared with prior art, the device have the advantages that：The graphite flake cut is placed in pre- by the present invention first
In the electrolyte first prepared, electrode and voltage stabilizing rectangular wave power supply are connected；Then rectangular wave stabilized power source, timing stripping are accessed
From；Gained solidliquid mixture is filtered again and is detached, by solid washes clean；Finally, using ultrasonic dispersion by gained graphene
Solid is uniformly distributed in dispersant, forms stable graphene dispersing solution.The present invention is in existing electrochemical stripping graphene
On the basis of, noble metal platinum electrode is eliminated, using dual graphite electrodes preparing graphene by electrochemical stripping, simplifies technique, reduces
Cost, and rectangular wave power supply checker positive and negative anodes are used, recirculation gas stripper graphite foil improves graphene yield, and it is high to obtain quality
With graphene product with good conductivity.Scanning electron microscope (SEM) photograph can be seen that when amplification factor is 12000 times, hence it is evident that can see
It is attached to a thin layer of graphene on the ito glass surface with apparent crystal grain hole；According to the penetration of electrons of graphene
Property, i.e., can clearly be seen that the hole of ITO through thin graphene layer, this can also illustrate graphene prepared by the present invention have compared with
High quality；In addition graphene size is 10~20 μm.The present invention has simple for process, safely controllable, repeatability height, yield
Height, many advantages, such as being easy to manipulate.Most of all, it is energy saving, do not generate any pollution to environment.
Further, it is cut under two with scissors every graphite flake upper edge short transverse is bottom-up, it is therefore an objective to appropriate to increase
The edge length of graphite flake is conducive to the stripping of graphene.
Further, being distributed to graphene uniform that step 3) obtains in dispersant by ultrasonic dispersion, can shape
At stable graphene dispersing solution, while ultrasound improves the quality of graphene.
Description of the drawings
Fig. 1 is the principle and connection diagram of bipolar electrode electrochemical stripping graphene；
Fig. 2 is rectangular wave stabilized power source schematic diagram.
Fig. 3 is the graphene dispersing solution being dispersed in DMF；
Fig. 4 is molar ratio n (ammonium sulfate) in electrolyte：N (sulfuric acid)=1:When 1, bipolar electrode electrochemical stripping graphene
SEM (scanning electron microscope) picture, enlargement ratio 12000.
Fig. 5 is molar ratio n (ammonium sulfate) in electrolyte：N (sulfuric acid)=1:When 2, bipolar electrode electrochemical stripping graphene
SEM (scanning electron microscope) picture, enlargement ratio 12000.
Fig. 6 is molar ratio n (ammonium sulfate) in electrolyte：N (sulfuric acid)=1:When 5, bipolar electrode electrochemical stripping graphene
SEM (scanning electron microscope) picture, enlargement ratio 12000.
Fig. 7 is molar ratio n (ammonium sulfate) in electrolyte：N (sulfuric acid)=1:When 9, bipolar electrode electrochemical stripping graphene
SEM (scanning electron microscope) picture, enlargement ratio 12000.
Fig. 8 is electrolyte when being mol/L sulfuric acid, the SEM (scanning electron microscope) of bipolar electrode electrochemical stripping graphene
Picture, enlargement ratio 6000.
Fig. 9 is electrolyte when being 0.5mol/L sulfuric acid, the SEM (scanning electron microscopies of bipolar electrode electrochemical stripping graphene
Mirror) picture, enlargement ratio 800.
Figure 10 is that electrolyte is molar ratio n (sodium sulphate)：N (sulfuric acid)=1：When 1, bipolar electrode electrochemical stripping graphene
SEM (scanning electron microscope) picture, enlargement ratio 1000.
Figure 11 is that electrolyte is molar ratio n (ammonium carbonate)：N (sulfuric acid)=1：When 1, bipolar electrode electrochemical stripping graphene
SEM (scanning electron microscope) picture, enlargement ratio 12000.
Specific implementation mode
The following further describes the present invention with reference to the drawings.
Embodiment 1
The present invention includes the following steps：
1) stripping prepares graphene device and builds：
First, the ammonium sulfate of 0.7464g is dissolved in 120mL deionized waters, be added dropwise 0.326mL mass fractions be 98% it is dense
Sulfuric acid is placed in 250mL beakers, is electrolyte, wherein the amount ratio of the substance of ammonium sulfate and the concentrated sulfuric acid is 1:1；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, are used in combination scissors along stone
Ink sheet short transverse is bottom-up to cut under two；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, it will be as the two panels graphite flake of electrode and voltage stabilizing square
Shape wave power supply connects, and prepares stripping.
2) exfoliated graphite prepares graphene：
Referring to Fig. 2, it is ± 6V that voltage is passed through on the electrode in step 1), and the period is 120s rectangular wave stabilized power sources, is opened
Begin to remove and timing, progress 10min stoppings, stripping terminate.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using filtering and 0.45 μm of filter membrane of water system is by the electrolyte and stone after stripping
Black alkene is detached, then is fully washed with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared：
Using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains in the DMF of 15mL, to form stabilization
Graphene dispersing solution, such as Fig. 3.Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument using general power 300W, and ultrasonic power is arranged
50%, ultrasonic time 10min；From figure 3, it can be seen that graphene uniform is dispersed in DMF.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying are seen using scanning electron microscope
It examines, obtains Fig. 4.From fig. 4, it can be seen that when scanning electron microscope amplification factor is 12000 times, hence it is evident that it can be seen that with apparent
The ito glass surface of crystal grain hole is attached to a thin layer of graphene；According to the penetration of electrons of graphene, that is, penetrate thin
Graphene layer can clearly be seen that the hole of ITO, this can also illustrate that graphene prepared by the present invention has higher quality；In addition
Graphene size is 10~20 μm.
Embodiment 2
The present invention includes the following steps：
1) stripping prepares graphene device and builds：
First, the ammonium sulfate of 0.7071g is dissolved in 120mL deionized waters, it is 98% that 0.6523mL mass fractions, which are added dropwise,
The concentrated sulfuric acid is placed in 250mL beakers, is electrolyte, wherein the amount ratio of the substance of ammonium sulfate and the concentrated sulfuric acid is 1:2；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, scissors are used in combination to cut two
Under；
Finally, according to Fig. 1, graphite flake is placed in electrolyte, electrode and voltage stabilizing rectangular wave power supply are connected, prepares stripping
From.
2) exfoliated graphite prepares graphene：
It is ± 6V that voltage is passed through on electrode in step 1), and the period is 120s rectangular wave stabilized power sources, i.e. two interpolars electricity
Pressure is that the two poles of the earth 6V switch positive elecrtonegativity per 60s.Start stripping and timing, carry out 10min stoppings, stripping terminates.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using filtering and 0.45 μm of filter membrane of water system is by the electrolyte and stone after stripping
Black alkene is detached, then is fully washed with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared：
Using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains in the DMF of 15mL, to form stabilization
Graphene dispersing solution.Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument using general power 300W, setting ultrasonic power 50%,
Ultrasonic time 10min.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying are seen using scanning electron microscope
It examines, obtains Fig. 5.From fig. 5, it can be seen that when scanning electron microscope amplification factor is 12000 times, hence it is evident that it can be seen that with crystal grain
The ito glass surface of hole is attached to a thin layer of graphene；According to the penetration of electrons of adhesive layer, that is, penetrate thin graphite
Alkene layer can clearly be seen that the hole of ITO, this can also illustrate that graphene prepared by the present invention has higher quality；In addition here
Graphene size obtained is about more than ten micron, has good edge.
Embodiment 3
The present invention includes the following steps：
1) stripping prepares graphene device and builds：
First, the ammonium sulfate of 0.6286g is dissolved in 120mL deionized waters, be added dropwise 1.305mL mass fractions be 98% it is dense
Sulfuric acid is placed in 250mL beakers, is electrolyte, and wherein the amount ratio of the substance of ammonium sulfate and the concentrated sulfuric acid is 1:5；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, scissors are used in combination to cut two
Under；
Finally, according to Fig. 1, graphite flake is placed in electrolyte, electrode and voltage stabilizing rectangular wave power supply are connected, prepares stripping
From.
2) exfoliated graphite prepares graphene：
It is ± 6V that voltage is passed through on electrode in step 1), and the period is 120s rectangular wave stabilized power sources, starts stripping simultaneously
Timing, carries out 10min stoppings, and stripping terminates.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using filtering and 0.45 μm of filter membrane of water system is by the electrolyte and stone after stripping
Black alkene is detached, and is fully washed with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared：
Using ultrasonic method dispersion being distributed to graphene uniform that step 3) obtains in the DMF of 15mL, to form stabilization
Graphene dispersing solution.Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument using general power 300W, setting ultrasonic power 50%,
Ultrasonic time 10min.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying are seen using scanning electron microscope
It examines, obtains Fig. 6.From fig. 6, it can be seen that when scanning electron microscope amplification factor is 12000 times, hence it is evident that it can be seen that with crystal grain
The ito glass surface of hole is attached to a thin layer of graphene；According to the penetration of electrons of adhesive layer, that is, penetrate thin graphite
Alkene layer can clearly be seen that the hole of ITO, this can also illustrate that graphene prepared by the present invention has higher quality；In addition here
Graphene size obtained is about more than ten micron, has good edge and fold.
Embodiment 4
The present invention includes the following steps：
1) stripping prepares graphene device and builds：
First, the ammonium sulfate of 0.55g is dissolved in 120mL deionized waters, the dense sulphur that 1.957mL mass fractions are 98% is added dropwise
Acid is placed in 250mL beakers, is electrolyte, and wherein the amount ratio of the substance of ammonium sulfate and the concentrated sulfuric acid is 1:9；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, are used in combination scissors along high
Direction is bottom-up cuts under two for degree；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, it will be as the two panels graphite flake of electrode and voltage stabilizing square
Shape wave power supply connects, and prepares stripping.
2) exfoliated graphite prepares graphene：
It is ± 6V that voltage is passed through on electrode in step 1), and the period is 120s rectangular wave stabilized power sources, starts stripping simultaneously
Timing, carries out 10min stoppings, and stripping terminates.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using vacuum filtration and 0.45 μm of filter membrane of water system by the electrolyte after stripping
It is detached, is fully washed with deionized water to remove salt ion etc. contained therein with graphene.
4) stable graphene dispersing solution is prepared：
Using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains in the DMF of 15mL, to form stabilization
Graphene dispersing solution.Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument using general power 300W, setting ultrasonic power 50%,
Ultrasonic time 10min.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying are seen using scanning electron microscope
It examines, obtains Fig. 7.From figure 7 it can be seen that being attached to a thin layer of graphite on the ito glass surface with apparent crystal grain hole
Alkene；According to the penetration of electrons of adhesive layer, i.e., it can clearly be seen that the hole of ITO through thin graphene layer, this can also illustrate
Graphene prepared by the present invention has higher quality；But graphene size obtained is apparent much smaller than before here, about
Several microns.
Embodiment 5 is added without sulfate or carbonate
The present invention includes the following steps：
1) stripping prepares graphene device and builds：
First, in 120mL deionized waters, the concentrated sulfuric acid of 1.957mL 0.5mol/L is added dropwise, is placed in 250mL beakers,
For electrolyte；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, scissors are used in combination to cut two
Under；
Finally, according to Fig. 1 and Fig. 2, graphite flake is placed in electrolyte, electrode and voltage stabilizing rectangular wave power supply are connected,
Prepare stripping.
2) exfoliated graphite prepares graphene：
It is ± 6V that voltage is passed through on electrode in step 1), and the period is 120s rectangular wave stabilized power sources, starts stripping simultaneously
Timing, carries out 10min stoppings, and stripping terminates.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using filtering and 0.45 μm of filter membrane of water system is by the electrolyte and stone after stripping
Black alkene is detached, and is fully washed with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared：
It is stable to be formed using ultrasonic disperse being distributed to graphene uniform that step 3) obtains in the DMF of 15mL
Graphene dispersing solution.Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument using general power 300W, and setting ultrasonic power 50% surpasses
Sound time 10min.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying are seen using scanning electron microscope
It examines, obtains Fig. 8 and Fig. 9.From figure 8, it is seen that being attached on the ito glass surface with apparent crystal grain hole a thin layer of
Graphene；Simultaneously it can be seen that the penetration of electrons of adhesive layer, i.e., can clearly be seen that the hole of ITO through thin graphene layer
Hole.From fig. 9, it can be seen that reuniting occurs in a large amount of graphene, this will cause centainly the dispersibility of graphene and stability
It influences.
Embodiment 6
1) stripping prepares graphene device and builds：
First, the sodium sulphate of 0.7464g is dissolved in 120mL deionized waters, be added dropwise 0.326mL mass fractions be 98% it is dense
Sulfuric acid is placed in 250mL beakers, is electrolyte, wherein the amount ratio of the substance of sodium sulphate and the concentrated sulfuric acid is 1:1；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, are used in combination scissors along stone
Ink sheet short transverse is bottom-up to cut under two；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, it will be as the two panels graphite flake of electrode and voltage stabilizing square
Shape wave power supply connects, and prepares stripping.
2) exfoliated graphite prepares graphene：
Referring to Fig. 2, it is ± 6V that voltage is passed through on the electrode in step 1), and the period is 120s rectangular wave stabilized power sources, is opened
Begin to remove and timing, progress 10min stoppings, stripping terminate.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using filtering and 0.45 μm of filter membrane of water system is by the electrolyte and stone after stripping
Black alkene is detached, and is fully washed with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared：
Using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains in the alcohol of 15mL, to form stabilization
Graphene dispersing solution.Wherein, ultrasonic dispersion is cleaned by ultrasonic instrument using general power 300W, setting ultrasonic power 50%,
Ultrasonic time 10min.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying.Pass through SEM (scanning electron microscopies
Mirror) observe to obtain Figure 10, in figure a thin layer of graphene is attached on the ito glass surface with apparent crystal grain hole；Simultaneously
It can be seen that the penetration of electrons of adhesive layer, i.e., can clearly be seen that the hole of ITO through thin graphene layer.
Embodiment 7
1) stripping prepares graphene device and builds：
First, the ammonium carbonate of 0.7464g is dissolved in 120mL deionized waters, be added dropwise 0.326mL mass fractions be 98% it is dense
Sulfuric acid is placed in 250mL beakers, and for electrolyte, the amount ratio of the substance of ammonium carbonate and the concentrated sulfuric acid is 1:1；
Then, the small pieces that the graphite flake of 0.246mm thickness is cut into 3*2.5cm, are fixed on fixture, are used in combination scissors along stone
Ink sheet short transverse is bottom-up to cut under two；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, it will be as the two panels graphite flake of electrode and voltage stabilizing square
Shape wave power supply connects, and prepares stripping.
2) exfoliated graphite prepares graphene：
Referring to Fig. 2, it is ± 6V that voltage is passed through on the electrode in step 1), and the period is 120s rectangular wave stabilized power sources, is opened
Begin to remove and timing, progress 10min stoppings, stripping terminate.
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, using filtering and 0.45 μm of filter membrane of water system is by the electrolyte and stone after stripping
Black alkene is detached, and is fully washed with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared：
Using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains in the acetone of 15mL, to form stabilization
Graphene dispersing solution.
5) graphene dispersing solution obtained is spin-coated on ITO pieces surface, 80 DEG C of drying.Pass through SEM (scanning electron microscopies
Mirror) observe to obtain Figure 11, in figure a thin layer of graphene is attached on the ito glass surface with apparent crystal grain hole；Simultaneously
It can be seen that the penetration of electrons of adhesive layer, i.e., can clearly be seen that the hole of ITO through thin graphene layer.
As shown in Fig. 3~Fig. 8, the ITO of test substrate selection, obviously it can be seen that the crystal grain of ITO and crystal grain gap in figure,
Crystal grain and gap are observed that through graphene, the number of plies that can obtain graphene is very low simultaneously.Simultaneously in testing
It was found that when the amount ratio of sulfate and the substance of sulfuric acid is higher than 1:When 9, electrolyte obtains the size and thickness of graphene to stripping
It influences and little；But occurs accumulating between graphene film and piece when sulfuric acid concentration is excessively high and more difficult be uniformly dispersed.Furthermore, it was found that
With the increase of concentrated sulfuric acid ratio, charge stripping efficiency is gradually accelerated, when the amount ratio of sulfate and sulfuric acid substance is 1:When 1, efficiency
For 0.01g/min.Therefore combine the graphene quality of yield and stripping, it is believed that 1:9 be the amount of sulfuric acid and the most suitable substance of ammonium sulfate.
The thickness of graphite flake, size are adjustable in the present invention.In addition the period of voltage stabilizing rectangular wave power supply can be fitted
Work as transfer, splitting time is also adjustable.
Claims (7)
1. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes, which is characterized in that include the following steps：
1) device for preparing graphene is built：
First, sulfate or carbonate are dissolved in deionized water, the concentrated sulfuric acid is then added dropwise, electrolyte is made；Wherein, sulfate or
The amount ratio ranging from 1 of the substance of carbonate and the concentrated sulfuric acid:1~1:9；
Then, two panels graphite flake is placed in electrolyte, then two panels graphite flake is connect with voltage stabilizing rectangular wave power supply；
2) exfoliated graphite prepares graphene：
It is passed through rectangular wave stabilized power source on two panels graphite flake in step 1) as electrode, starts stripping and timing, until not having
Solid is detached from electrode, and stripping terminates；
3) stripping obtains the post-processing of graphene product：
Electrode in step 2) is taken off, by after stripping electrolyte and graphene detach, and be washed with deionized；
4) stable graphene dispersing solution is prepared：
By being distributed in dispersant for graphene uniform that step 3) obtains, stable graphene dispersing solution is formed；
The sulfate is ammonium sulfate, sodium sulphate or potassium sulfate；The carbonate is ammonium carbonate；
It is cut under two with scissors every graphite flake upper edge short transverse is bottom-up；
The voltage of the rectangular wave stabilized power source is ± 6V, period 120s.
2. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes according to claim 1, special
Sign is that the sulfate or carbonate and the ratio of deionized water are (0.55~0.7467) g：120mL.
3. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes according to claim 1, special
Sign is that the thickness of the graphite flake is 0.246mm, length 3cm, width 2.5cm.
4. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes according to claim 1, special
Sign is, from stripping and timing is started, until the time that no solid is detached from electrode is 10min.
5. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes according to claim 1, special
Sign is, using vacuum filtration and 0.45 μm of filter membrane of water system by after stripping electrolyte and graphene detach.
6. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes according to claim 1, special
Sign is, using ultrasonic dispersion being distributed to graphene uniform that step 3) obtains in dispersant；Wherein, ultrasonic dispersion
It is cleaned by ultrasonic instrument, ultrasonic power 50%, ultrasonic time 10min using general power 300W.
7. a kind of method preparing graphene based on electrochemical process stripping dual graphite electrodes according to claim 1, special
Sign is that the dispersant is n,N-Dimethylformamide, alcohol or acetone.
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| RU2675146C2 (en) * | 2017-02-21 | 2018-12-17 | Владимир Васильевич Журавлев | Graphene, graphene films and coatings production method |
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| CN110526235B (en) * | 2018-05-23 | 2021-05-14 | 浙江大学 | Method for preparing in-situ oxygen-doped three-dimensional graphene through electrochemical stripping |
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| CN109678142B (en) * | 2018-12-24 | 2021-01-19 | 华中科技大学 | Functionalized porous graphene and preparation method thereof |
| US20200239324A1 (en) * | 2019-01-28 | 2020-07-30 | ITI Technolgies, Inc. | Solubility Enhancing Composition |
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| CN112291868B (en) * | 2020-09-14 | 2021-12-14 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
| CN113479868A (en) * | 2021-08-02 | 2021-10-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing graphene through bipolar electrochemical stripping of organic acid ammonium fused salt |
| CN114590802B (en) * | 2021-12-08 | 2023-04-18 | 超威电源集团有限公司 | Method and device for preparing graphene through electrolysis |
| CN114684814A (en) * | 2022-04-24 | 2022-07-01 | 江苏大学 | Preparation method of self-supporting flexible graphene film and application of self-supporting flexible graphene film to flexible supercapacitor |
| CN114572973B (en) * | 2022-05-03 | 2024-04-09 | 营口理工学院 | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
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| CN102167313B (en) * | 2011-04-25 | 2012-08-22 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| JP5924712B2 (en) * | 2012-10-24 | 2016-05-25 | 国立研究開発法人物質・材料研究機構 | Graphene ultra-thin piece and its manufacturing apparatus, manufacturing method, and capacitor and its manufacturing method |
| CN102923697B (en) * | 2012-11-19 | 2014-10-01 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| US8920614B2 (en) * | 2012-12-18 | 2014-12-30 | Chung-Shan Institute Of Science And Technology | Device designed for continuous production of graphene flakes by electrochemical method |
| CN103466603B (en) * | 2013-08-09 | 2016-01-27 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of graphene dispersing solution and graphene film |
| CN103991862B (en) * | 2013-12-27 | 2016-02-03 | 杭州金马能源科技有限公司 | Electrochemistry efficiently peels off the method preparing high-quality graphene |
| CN104556018B (en) * | 2015-01-23 | 2019-10-01 | 青岛科技大学 | A kind of preparation method of high-quality graphene conductive film |
| CN104876211A (en) * | 2015-04-14 | 2015-09-02 | 苏州大学 | Method for preparing graphene by rotationally shearing in electric field environment |
| CN104961123B (en) * | 2015-06-18 | 2017-11-17 | 湖南大学 | A kind of native graphite ore deposit peels off method of purification |
| CN105417537A (en) * | 2015-12-31 | 2016-03-23 | 焦云 | Device for quickly stripping graphene through synergistic effect of ultrasound and electric field and method for quickly stripping graphene by utilizing same |
| CN105645390A (en) * | 2015-12-31 | 2016-06-08 | 焦云 | Device for quickly peeling graphene under ultrasonic and electric field synergistic effect and method for quickly peeling graphene by using same |
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