CN106245104A - A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes - Google Patents
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes Download PDFInfo
- Publication number
- CN106245104A CN106245104A CN201610575282.7A CN201610575282A CN106245104A CN 106245104 A CN106245104 A CN 106245104A CN 201610575282 A CN201610575282 A CN 201610575282A CN 106245104 A CN106245104 A CN 106245104A
- Authority
- CN
- China
- Prior art keywords
- graphene
- method preparing
- electrochemical process
- electrolyte
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
Abstract
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes, first, is dissolved in deionized water by sulfate or carbonate, then drips concentrated sulphuric acid, prepare electrolyte；Wherein, the amount of sulfate or carbonate and the material of concentrated sulphuric acid is 1:1～1:9 than scope；Then, two panels graphite flake is placed in electrolyte, then two panels graphite flake is connected with voltage stabilizing square wave power supply；Being passed through square wave stabilized power source on electrode, start to peel off and timing, to not having solid to depart from electrode, stripping terminates；Being taken off by electrode, electrolyte and Graphene after peeling off separate, and are washed with deionized；Being distributed to the graphene uniform obtained in dispersant, forms stable graphene dispersing solution.The plurality of advantages such as it is simple that the present invention has technique, safely controllable, and repeatability is high, and productivity is high, easy manipulation.The most important thing is, save the energy, environment is not produced any pollution.
Description
Technical field
The present invention relates to field of nano material preparation, relate to the method that electrochemical process prepares high-quality graphene, specifically relate to
And a kind of peel off the dual graphite electrodes method of preparing Graphene based on electrochemical process.
Background technology
Univ Manchester UK A.K.Geim in 2004 teaches seminar and uses micromechanics stripping method successfully to prepare stone
Ink alkene, having broken perfect two dimensional crystal structure can not the judgement of stable existence under non-absolute zero.Then Graphene is excellent
Electrical properties, mechanical property, thermal property, the most studied personnel of optical property find.Additionally, Graphene has super large
Theoretical specific surface area, the excellent properties that monoatomic layer structure is had in addition, using Graphene as the carbon-based material of source material
Significant progress and application are obtained.
The most widely used method preparing Graphene substantially can be divided into following a few class: micromechanics stripping method,
Chemical vapour deposition technique, graphene oxide reducing process, solvent stripping method, electrochemical stripping and longitudinally cutting carbon tube method etc. are several
Kind.Wherein, micromechanics stripping method uses micromechanics stress to overcome Van der Waals force, advantage to be low defect, high electron mobility, but
Its cost is high, productivity is low, is suitable only for basic research；Chemical vapour deposition technique (CVD) is to utilize C, H compound, high temperature pyrolysis
Generation carbon atom is deposited on and sinks to the bottom surface, and prepared quality of graphene is high, but its cost is high, complex process；Oxidation-reduction method is
Utilizing graphite through strong acid or strong oxidizer to GO, be then reduced into RGO, advantage is to prepare Graphene stable dispersion, and shortcoming has useless
Liquid pollutes, existing defects；Solvent stripping method is to utilize solvent to enter graphite layers, ultrasonic stripping, prepares quality of graphene high, scarce
Fall into few, but productivity is the lowest；It is to utilize ionic adsorption that electrochemical process is peeled off, and gas evolution etc. overcomes Van der Waals force, prepared graphite
Alkene electric conductivity is excellent, and defect is few, and yield is high and good dispersion, and this method to prepare Graphene be considered as that most probable realizes stone
Important method prepared by ink alkene industrialization.But the method productivity that existing electrochemistry prepares Graphene is relatively low, mostly uses
Graphite foil is as positive pole, and needs noble metal to make negative pole, and the dependence to noble metal platinum is unfavorable for more greatly industrialized production.Cause
This is efficient, quick, low cost is prepared high-quality Graphene and caused the attention of people.
Summary of the invention
It is an object of the invention to provide a kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes,
On the basis of existing electrochemical stripping Graphene, eliminate noble metal platinum electrode, use dual graphite electrodes electrochemical stripping to prepare
Graphene, Simplified flowsheet, reduce cost, and use square wave power supply checker both positive and negative polarity, recirculation gas stripper graphite foil, improves stone
Ink alkene productivity, it is thus achieved that the graphene product that quality is high and electric conductivity is good.It is simple that the present invention has technique, reproducible, productivity
Height, the plurality of advantages such as easy manipulation.
In order to realize object above, the technical solution adopted in the present invention is:
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes, comprises the following steps:
1) build and prepare the device of Graphene:
First, sulfate or carbonate are dissolved in deionized water, then drip concentrated sulphuric acid, prepare electrolyte；Wherein, sulphuric acid
The amount of salt or carbonate and the material of concentrated sulphuric acid is 1:1～1:9 than scope；
Then, two panels graphite flake is placed in electrolyte, then two panels graphite flake is connected with voltage stabilizing square wave power supply；
2) exfoliated graphite prepares Graphene:
In step 1) in as being passed through square wave stabilized power source on the two panels graphite flake of electrode, start peel off and timing, extremely
Not having solid to depart from electrode, stripping terminates；
3) peel off and obtain the post processing of graphene product:
By step 2) in electrode take off, electrolyte and Graphene after peeling off separate, and use deionized water
Washing；
4) stable graphene dispersing solution is prepared:
By step 3) being distributed in dispersant of the graphene uniform that obtains, form stable graphene dispersing solution.
The present invention is further improved by, and described sulfate is ammonium sulfate, sodium sulfate or potassium sulfate；Described carbonate is
Ammonium carbonate.
The present invention is further improved by, the ratio of described sulfate or carbonate and deionized water be (0.55～
0.7467) g:120mL.
The present invention is further improved by, and the thickness of described graphite flake is 0.246mm, a length of 3cm, and width is
2.5cm。
The present invention is further improved by, and cuts twice along the bottom-up shears of short transverse on every graphite flake.
The present invention is further improved by, and the voltage of described square wave stabilized power source is ± 6V, the cycle is 120s.
The present invention is further improved by, and from starting stripping timing, to the time not having solid to depart from electrode is
10min。
The present invention is further improved by, electrolyte after using vacuum filtration and water system 0.45 μm filter membrane to peel off and
Graphene separates.
The present invention is further improved by, and uses ultrasonic dispersion by step 3) being distributed to of the graphene uniform that obtains
In dispersant；Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, and ultrasonic power is 50%, ultrasonic time
For 10min.
The present invention is further improved by, and described dispersant is DMF, ethanol or acetone.
Compared with prior art, the invention have the benefit that first the graphite flake cut is placed in pre-by the present invention
In the electrolyte first prepared, electrode is connected with voltage stabilizing square wave power supply；Then accessing square wave stabilized power source, timing is shelled
From；Again gained solidliquid mixture sucking filtration is separated, by solid washes clean；Finally, use ultrasonic dispersion by gained Graphene
Solid is distributed in dispersant uniformly, forms stable graphene dispersing solution.The present invention is at existing electrochemical stripping Graphene
On the basis of, eliminate noble metal platinum electrode, use dual graphite electrodes preparing graphene by electrochemical stripping, Simplified flowsheet, reduce
Cost, and use square wave power supply checker both positive and negative polarity, recirculation gas stripper graphite foil, improves Graphene productivity, it is thus achieved that quality is high
The graphene product good with electric conductivity.Scanning electron microscope (SEM) photograph is it can be seen that when amplification is 12000 times, hence it is evident that can see
To having the ito glass surface attachment Graphene of thin layer of obvious crystal grain hole；Penetration of electrons according to Graphene
Property, i.e. through thin graphene layer it can clearly be seen that the hole of ITO, this also can illustrate that Graphene prepared by the present invention has relatively
High quality；In addition Graphene size is 10～20 μm.It is simple that the present invention has technique, safely controllable, and repeatability is high, productivity
Height, the plurality of advantages such as easy manipulation.The most important thing is, save the energy, environment is not produced any pollution.
Further, every graphite flake cuts twice along the bottom-up shears of short transverse, it is therefore an objective to suitably increase
The stripping of the edge length of graphite flake, beneficially Graphene.
Further, by ultrasonic dispersion by step 3) being distributed in dispersant of the graphene uniform that obtains, can shape
Become stable graphene dispersing solution, the most ultrasonic quality that improve Graphene.
Accompanying drawing explanation
Fig. 1 is principle and the connection diagram of bipolar electrode electrochemical stripping Graphene；
Fig. 2 is square wave stabilized power source schematic diagram.
Fig. 3 is the graphene dispersing solution being dispersed in DMF；
When Fig. 4 is mol ratio n (ammonium sulfate): n (sulphuric acid)=1:1 in electrolyte, bipolar electrode electrochemical stripping Graphene
SEM (scanning electron microscope) picture, its enlargement ratio is 12000.
When Fig. 5 is mol ratio n (ammonium sulfate): n (sulphuric acid)=1:2 in electrolyte, bipolar electrode electrochemical stripping Graphene
SEM (scanning electron microscope) picture, its enlargement ratio is 12000.
When Fig. 6 is mol ratio n (ammonium sulfate): n (sulphuric acid)=1:5 in electrolyte, bipolar electrode electrochemical stripping Graphene
SEM (scanning electron microscope) picture, its enlargement ratio is 12000.
When Fig. 7 is mol ratio n (ammonium sulfate): n (sulphuric acid)=1:9 in electrolyte, bipolar electrode electrochemical stripping Graphene
SEM (scanning electron microscope) picture, its enlargement ratio is 12000.
Fig. 8 is electrolyte when being mol/L sulphuric acid, the SEM (scanning electron microscope) of bipolar electrode electrochemical stripping Graphene
Picture, its enlargement ratio is 6000.
Fig. 9 is electrolyte when being 0.5mol/L sulphuric acid, the SEM (scanning electron microscopy of bipolar electrode electrochemical stripping Graphene
Mirror) picture, its enlargement ratio is 800.
Figure 10 is electrolyte when being mol ratio n (sodium sulfate): n (sulphuric acid)=1:1, bipolar electrode electrochemical stripping Graphene
SEM (scanning electron microscope) picture, its enlargement ratio is 1000.
Figure 11 is electrolyte when being mol ratio n (ammonium carbonate): n (sulphuric acid)=1:1, bipolar electrode electrochemical stripping Graphene
SEM (scanning electron microscope) picture, its enlargement ratio is 12000.
Detailed description of the invention
The present invention is further described below in conjunction with the accompanying drawings.
Embodiment 1
The present invention comprises the following steps:
1) stripping is prepared Graphene device and is built:
First, the ammonium sulfate of 0.7464g is dissolved in 120mL deionized water, dropping 0.326mL mass fraction be 98% dense
Sulphuric acid, is placed in 250mL beaker, and for electrolyte, wherein, the amount of ammonium sulfate and the material of concentrated sulphuric acid is than for 1:1；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and with shears along stone
Ink sheet short transverse is bottom-up cuts twice；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, using two panels graphite flake and voltage stabilizing square as electrode
Shape ripple power supply connects, and prepares to peel off.
2) exfoliated graphite prepares Graphene:
See Fig. 2, in step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, opens
Beginning to peel off and timing, carry out 10min stopping, stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize sucking filtration and water system 0.45 μm filter membrane will peel off after electrolyte and stone
Ink alkene separates, more fully washs with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Utilize ultrasonic dispersion by step 3) in the DMF being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution, such as Fig. 3.Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, arranges ultrasonic power
50%, ultrasonic time 10min；From figure 3, it can be seen that graphene uniform is dispersed in DMF.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying, utilize scanning electron microscope to see
Examine, obtain Fig. 4.From fig. 4, it can be seen that when scanning electron microscope amplification is 12000 times, hence it is evident that it can be seen that have substantially
The ito glass surface attachment of the crystal grain hole Graphene of thin layer；According to the penetration of electrons of Graphene, i.e. through thin
Graphene layer is it can clearly be seen that the hole of ITO, and this also can illustrate that Graphene prepared by the present invention has higher quality；In addition
Graphene size is 10～20 μm.
Embodiment 2
The present invention comprises the following steps:
1) stripping is prepared Graphene device and is built:
First, the ammonium sulfate of 0.7071g being dissolved in 120mL deionized water, dropping 0.6523mL mass fraction is 98%
Concentrated sulphuric acid, is placed in 250mL beaker, and for electrolyte, wherein, the amount of ammonium sulfate and the material of concentrated sulphuric acid is than for 1:2；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and cuts two with shears
Under；
Finally, according to Fig. 1, graphite flake is placed in electrolyte, electrode is connected with voltage stabilizing square wave power supply, prepare stripping
From.
2) exfoliated graphite prepares Graphene:
In step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, i.e. two interpolars electricity
Pressure switches positive elecrtonegativity for the every 60s in 6V the two poles of the earth.Starting to peel off and timing, carry out 10min stopping, stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize sucking filtration and water system 0.45 μm filter membrane will peel off after electrolyte and stone
Ink alkene separates, more fully washs with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Utilize ultrasonic dispersion by step 3) in the DMF being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution.Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, arrange ultrasonic power 50%,
Ultrasonic time 10min.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying, utilize scanning electron microscope to see
Examine, obtain Fig. 5.From fig. 5, it can be seen that when scanning electron microscope amplification is 12000 times, hence it is evident that it can be seen that have crystal grain
The ito glass surface attachment of the hole Graphene of thin layer；According to the penetration of electrons of adhesive layer, i.e. through thin graphite
Alkene layer is it can clearly be seen that the hole of ITO, and this also can illustrate that Graphene prepared by the present invention has higher quality；The most here
The Graphene size prepared is about ten several microns, has good edge.
Embodiment 3
The present invention comprises the following steps:
1) stripping is prepared Graphene device and is built:
First, the ammonium sulfate of 0.6286g is dissolved in 120mL deionized water, dropping 1.305mL mass fraction be 98% dense
Sulphuric acid, is placed in 250mL beaker, and for electrolyte, wherein the amount of ammonium sulfate and the material of concentrated sulphuric acid is than for 1:5；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and cuts two with shears
Under；
Finally, according to Fig. 1, graphite flake is placed in electrolyte, electrode is connected with voltage stabilizing square wave power supply, prepare stripping
From.
2) exfoliated graphite prepares Graphene:
In step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, starts to peel off also
Timing, carries out 10min stopping, and stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize sucking filtration and water system 0.45 μm filter membrane will peel off after electrolyte and stone
Ink alkene separates, and fully washs with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Ultrasonic method is utilized to disperse step 3) in the DMF being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution.Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, arrange ultrasonic power 50%,
Ultrasonic time 10min.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying, utilize scanning electron microscope to see
Examine, obtain Fig. 6.From fig. 6, it can be seen that when scanning electron microscope amplification is 12000 times, hence it is evident that it can be seen that have crystal grain
The ito glass surface attachment of the hole Graphene of thin layer；According to the penetration of electrons of adhesive layer, i.e. through thin graphite
Alkene layer is it can clearly be seen that the hole of ITO, and this also can illustrate that Graphene prepared by the present invention has higher quality；The most here
The Graphene size prepared is about ten several microns, has good edge and fold.
Embodiment 4
The present invention comprises the following steps:
1) stripping is prepared Graphene device and is built:
First, the ammonium sulfate of 0.55g being dissolved in 120mL deionized water, dropping 1.957mL mass fraction is the dense sulfur of 98%
Acid, is placed in 250mL beaker, and for electrolyte, wherein the amount of ammonium sulfate and the material of concentrated sulphuric acid is than for 1:9；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and with shears along high
Direction is bottom-up cuts twice for degree；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, using two panels graphite flake and voltage stabilizing square as electrode
Shape ripple power supply connects, and prepares to peel off.
2) exfoliated graphite prepares Graphene:
In step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, starts to peel off also
Timing, carries out 10min stopping, and stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize vacuum filtration and water system 0.45 μm filter membrane will peel off after electrolyte
Separate with Graphene, fully wash with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Utilize ultrasonic dispersion by step 3) in the DMF being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution.Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, arrange ultrasonic power 50%,
Ultrasonic time 10min.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying, utilize scanning electron microscope to see
Examine, obtain Fig. 7.From figure 7 it can be seen that have the ito glass surface attachment graphite of thin layer of obvious crystal grain hole
Alkene；According to the penetration of electrons of adhesive layer, i.e. through thin graphene layer it can clearly be seen that the hole of ITO, this also can illustrate
Graphene prepared by the present invention has higher quality；But the Graphene size prepared here is substantially more much smaller than before, it is about
Several microns.
Embodiment 5 is added without sulfate or carbonate
The present invention comprises the following steps:
1) stripping is prepared Graphene device and is built:
First, in 120mL deionized water, the concentrated sulphuric acid of dropping 1.957mL 0.5mol/L, it is placed in 250mL beaker,
For electrolyte；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and cuts two with shears
Under；
Finally, according to Fig. 1 and Fig. 2, graphite flake is placed in electrolyte, electrode is connected with voltage stabilizing square wave power supply,
Prepare to peel off.
2) exfoliated graphite prepares Graphene:
In step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, starts to peel off also
Timing, carries out 10min stopping, and stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize sucking filtration and water system 0.45 μm filter membrane will peel off after electrolyte and stone
Ink alkene separates, and fully washs with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Utilize ultrasonic disperse by step 3) in the DMF being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution.Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, arranges ultrasonic power 50%, surpasses
Sound time 10min.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying, utilize scanning electron microscope to see
Examine, obtain Fig. 8 and Fig. 9.From figure 8, it is seen that have the ito glass surface attachment thin layer of obvious crystal grain hole
Graphene；Can be seen that the penetration of electrons of adhesive layer, i.e. through thin graphene layer it can clearly be seen that the hole of ITO simultaneously
Hole.From fig. 9, it can be seen that substantial amounts of Graphene occurs in that reunion, dispersibility and the stability of Graphene will be caused necessarily by this
Impact.
Embodiment 6
1) stripping is prepared Graphene device and is built:
First, the sodium sulfate of 0.7464g is dissolved in 120mL deionized water, dropping 0.326mL mass fraction be 98% dense
Sulphuric acid, is placed in 250mL beaker, and for electrolyte, wherein, the amount of sodium sulfate and the material of concentrated sulphuric acid is than for 1:1；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and with shears along stone
Ink sheet short transverse is bottom-up cuts twice；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, using two panels graphite flake and voltage stabilizing square as electrode
Shape ripple power supply connects, and prepares to peel off.
2) exfoliated graphite prepares Graphene:
See Fig. 2, in step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, opens
Beginning to peel off and timing, carry out 10min stopping, stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize sucking filtration and water system 0.45 μm filter membrane will peel off after electrolyte and stone
Ink alkene separates, and fully washs with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Utilize ultrasonic dispersion by step 3) in the ethanol being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution.Wherein, ultrasonic dispersion uses general power 300W ultrasonic cleaning instrument, arrange ultrasonic power 50%,
Ultrasonic time 10min.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying.By SEM (scanning electron microscopy
Mirror) observe to obtain Figure 10, figure has the ito glass surface attachment Graphene of thin layer of obvious crystal grain hole；Simultaneously
Can be seen that the penetration of electrons of adhesive layer, i.e. through thin graphene layer it can clearly be seen that the hole of ITO.
Embodiment 7
1) stripping is prepared Graphene device and is built:
First, the ammonium carbonate of 0.7464g is dissolved in 120mL deionized water, dropping 0.326mL mass fraction be 98% dense
Sulphuric acid, is placed in 250mL beaker, and for electrolyte, the amount of ammonium carbonate and the material of concentrated sulphuric acid is than for 1:1；
Then, the graphite flake that 0.246mm is thick is cut into the small pieces of 3*2.5cm, is fixed on fixture, and with shears along stone
Ink sheet short transverse is bottom-up cuts twice；
Finally, according to Fig. 1, two panels graphite flake is placed in electrolyte, using two panels graphite flake and voltage stabilizing square as electrode
Shape ripple power supply connects, and prepares to peel off.
2) exfoliated graphite prepares Graphene:
See Fig. 2, in step 1) in electrode on be passed through voltage for ± 6V, the cycle is 120s square wave stabilized power source, opens
Beginning to peel off and timing, carry out 10min stopping, stripping terminates.
3) peel off and obtain the post processing of graphene product:
By in step 2) in electrode take off, utilize sucking filtration and water system 0.45 μm filter membrane will peel off after electrolyte and stone
Ink alkene separates, and fully washs with deionized water to remove salt ion etc. contained therein.
4) stable graphene dispersing solution is prepared:
Utilize ultrasonic dispersion by step 3) in the acetone being distributed to 15mL of graphene uniform that obtains, stable to be formed
Graphene dispersing solution.
5) prepared graphene dispersing solution is spin-coated on ITO sheet surface, 80 DEG C of drying.By SEM (scanning electron microscopy
Mirror) observe to obtain Figure 11, figure has the ito glass surface attachment Graphene of thin layer of obvious crystal grain hole；Simultaneously
Can be seen that the penetration of electrons of adhesive layer, i.e. through thin graphene layer it can clearly be seen that the hole of ITO.
As shown in Fig. 3～Fig. 8, the ITO that test substrate selects, substantially it can be seen that the crystal grain of ITO and crystal grain gap in figure,
Simultaneously through Graphene it is observed that crystal grain and gap, the number of plies that can obtain Graphene is the lowest.The most in testing
Find that, when the amount ratio of sulfate with the material of sulphuric acid is higher than 1:9, electrolyte obtains size and the thickness of Graphene to peeling off
Impact is the most little；But occur between graphene film and sheet when sulfuric acid concentration is too high piling up and more difficult being uniformly dispersed.Furthermore, it was found that
Along with the increase of concentrated sulphuric acid ratio, charge stripping efficiency is gradually accelerated, when the amount ratio of sulfate Yu sulphuric acid material is 1:1, and efficiency
For 0.01g/min.Therefore combining the Graphene quality of productivity and stripping, it is believed that 1:9 is sulphuric acid and the amount of the most suitable material of ammonium sulfate.
The thickness of graphite flake, the equal adjustable of size in the present invention.In addition the cycle of voltage stabilizing square wave power supply all can fit
Working as transfer, splitting time is the most adjustable.
Claims (10)
1. the method preparing Graphene based on electrochemical process stripping dual graphite electrodes, it is characterised in that comprise the following steps:
1) build and prepare the device of Graphene:
First, sulfate or carbonate are dissolved in deionized water, then drip concentrated sulphuric acid, prepare electrolyte；Wherein, sulfate or
The amount of carbonate and the material of concentrated sulphuric acid is 1:1～1:9 than scope；
Then, two panels graphite flake is placed in electrolyte, then two panels graphite flake is connected with voltage stabilizing square wave power supply；
2) exfoliated graphite prepares Graphene:
In step 1) in as being passed through square wave stabilized power source on the two panels graphite flake of electrode, start peel off and timing, to not having
Solid departs from electrode, and stripping terminates；
3) peel off and obtain the post processing of graphene product:
By step 2) in electrode take off, electrolyte and Graphene after peeling off separate, and are washed with deionized；
4) stable graphene dispersing solution is prepared:
By step 3) being distributed in dispersant of the graphene uniform that obtains, form stable graphene dispersing solution.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levying and be, described sulfate is ammonium sulfate, sodium sulfate or potassium sulfate；Described carbonate is ammonium carbonate.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levying and be, the ratio of described sulfate or carbonate and deionized water is (0.55～0.7467) g:120mL.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levying and be, the thickness of described graphite flake is 0.246mm, a length of 3cm, and width is 2.5cm.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levy and be, every graphite flake cuts twice along the bottom-up shears of short transverse.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levying and be, the voltage of described square wave stabilized power source is ± 6V, the cycle is 120s.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levy and be, from starting stripping timing, be 10min to the time not having solid to depart from electrode.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levying and be, electrolyte and Graphene after using vacuum filtration and water system 0.45 μm filter membrane to peel off separate.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levy and be, use ultrasonic dispersion by step 3) being distributed in dispersant of the graphene uniform that obtains；Wherein, ultrasonic dispersion
Using general power 300W ultrasonic cleaning instrument, ultrasonic power is 50%, ultrasonic time is 10min.
A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes the most according to claim 1, it is special
Levying and be, described dispersant is DMF, ethanol or acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610575282.7A CN106245104B (en) | 2016-07-20 | 2016-07-20 | A method of preparing graphene based on electrochemical process stripping dual graphite electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610575282.7A CN106245104B (en) | 2016-07-20 | 2016-07-20 | A method of preparing graphene based on electrochemical process stripping dual graphite electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106245104A true CN106245104A (en) | 2016-12-21 |
| CN106245104B CN106245104B (en) | 2018-07-17 |
Family
ID=57613504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610575282.7A Expired - Fee Related CN106245104B (en) | 2016-07-20 | 2016-07-20 | A method of preparing graphene based on electrochemical process stripping dual graphite electrodes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106245104B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106865536A (en) * | 2017-03-25 | 2017-06-20 | 哈尔滨摆渡新材料有限公司 | A kind of method and device for preparing Graphene |
| RU2675146C2 (en) * | 2017-02-21 | 2018-12-17 | Владимир Васильевич Журавлев | Graphene, graphene films and coatings production method |
| CN109316976A (en) * | 2018-10-25 | 2019-02-12 | 长春工业大学 | A kind of electrochemical process preparation bionical graphene composite film of super-hydrophobic super-oleophylic |
| CN109368626A (en) * | 2018-12-17 | 2019-02-22 | 安阳工学院 | A kind of electrolyte for electrochemical stripping two-dimension nano materials |
| CN109678142A (en) * | 2018-12-24 | 2019-04-26 | 华中科技大学 | A kind of function dough porous graphene and preparation method thereof |
| CN109796012A (en) * | 2019-04-10 | 2019-05-24 | 任国峰 | A kind of graphene and preparation method thereof prepared by electrochemical process |
| CN110526235A (en) * | 2018-05-23 | 2019-12-03 | 浙江大学 | A method of oxygen doping three-dimensional grapheme in situ is prepared by electrochemical stripping |
| CN110980706A (en) * | 2019-11-25 | 2020-04-10 | 陕西理工大学 | Method for preparing boron-doped graphene by electrochemical stripping of double graphite electrodes |
| CN112291868A (en) * | 2020-09-14 | 2021-01-29 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
| CN112978721A (en) * | 2019-12-02 | 2021-06-18 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene by double-pulse electrochemical technology |
| 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 |
| EP3917888A4 (en) * | 2019-01-28 | 2022-03-02 | ITI Technologies, Inc. | Solubility enhancing composition |
| CN114572973A (en) * | 2022-05-03 | 2022-06-03 | 营口理工学院 | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
| CN114590802A (en) * | 2021-12-08 | 2022-06-07 | 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 |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| CN103466603A (en) * | 2013-08-09 | 2013-12-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene dispersion liquid, and preparation method of graphene film |
| US20140166475A1 (en) * | 2012-12-18 | 2014-06-19 | Chung-Shan Institute Of Science And Technology | Device designed for continuous production of graphene flakes by electrochemical method |
| CN103991862A (en) * | 2013-12-27 | 2014-08-20 | 杭州金马能源科技有限公司 | Method for preparing high-quality graphene through electrochemical high-efficiency exfoliation |
| CN104556018A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Preparation method of high quality graphene conductive film |
| CN104768871A (en) * | 2012-10-24 | 2015-07-08 | 独立行政法人物质·材料研究机构 | Ultrathin graphene piece, manufacturing device for ultrathin graphene piece, manufacturing method for ultrathin graphene piece, capacitor, and manufacturing method for capacitor |
| CN104876211A (en) * | 2015-04-14 | 2015-09-02 | 苏州大学 | Method for preparing graphene by rotationally shearing in electric field environment |
| CN104961123A (en) * | 2015-06-18 | 2015-10-07 | 湖南大学 | Natural graphite ore stripping and purifying method |
| 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 |
-
2016
- 2016-07-20 CN CN201610575282.7A patent/CN106245104B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
| CN104768871A (en) * | 2012-10-24 | 2015-07-08 | 独立行政法人物质·材料研究机构 | Ultrathin graphene piece, manufacturing device for ultrathin graphene piece, manufacturing method for ultrathin graphene piece, capacitor, and manufacturing method for capacitor |
| CN102923697A (en) * | 2012-11-19 | 2013-02-13 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| US20140166475A1 (en) * | 2012-12-18 | 2014-06-19 | Chung-Shan Institute Of Science And Technology | Device designed for continuous production of graphene flakes by electrochemical method |
| CN103466603A (en) * | 2013-08-09 | 2013-12-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of graphene dispersion liquid, and preparation method of graphene film |
| CN103991862A (en) * | 2013-12-27 | 2014-08-20 | 杭州金马能源科技有限公司 | Method for preparing high-quality graphene through electrochemical high-efficiency exfoliation |
| CN104556018A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | 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 |
| CN104961123A (en) * | 2015-06-18 | 2015-10-07 | 湖南大学 | Natural graphite ore stripping and purifying method |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| JILEI LIU,ET AL.,: ""Improved synthesis of graphene flakes from the multiple electrochemical exfoliation of graphite rod"", 《NANO ENERGY》 * |
| KHALED PARVEZ,ET AL.,: ""Exfoliation of graphite into graphene in aqueous solutions of inorganic salts"", 《JOURANL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2675146C2 (en) * | 2017-02-21 | 2018-12-17 | Владимир Васильевич Журавлев | Graphene, graphene films and coatings production method |
| CN106865536A (en) * | 2017-03-25 | 2017-06-20 | 哈尔滨摆渡新材料有限公司 | A kind of method and device for preparing Graphene |
| CN110526235A (en) * | 2018-05-23 | 2019-12-03 | 浙江大学 | A method of oxygen doping three-dimensional grapheme in situ is prepared by electrochemical stripping |
| 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 |
| CN109316976B (en) * | 2018-10-25 | 2021-05-11 | 长春工业大学 | Super-hydrophobic super-oleophylic bionic graphene composite membrane prepared by electrochemical method |
| CN109316976A (en) * | 2018-10-25 | 2019-02-12 | 长春工业大学 | A kind of electrochemical process preparation bionical graphene composite film of super-hydrophobic super-oleophylic |
| CN109368626A (en) * | 2018-12-17 | 2019-02-22 | 安阳工学院 | A kind of electrolyte for electrochemical stripping two-dimension nano materials |
| CN109678142A (en) * | 2018-12-24 | 2019-04-26 | 华中科技大学 | A kind of function dough porous graphene and preparation method thereof |
| CN109678142B (en) * | 2018-12-24 | 2021-01-19 | 华中科技大学 | Functionalized porous graphene and preparation method thereof |
| EP3917888A4 (en) * | 2019-01-28 | 2022-03-02 | ITI Technologies, Inc. | Solubility enhancing composition |
| CN109796012A (en) * | 2019-04-10 | 2019-05-24 | 任国峰 | A kind of graphene and preparation method thereof prepared by electrochemical process |
| CN110980706A (en) * | 2019-11-25 | 2020-04-10 | 陕西理工大学 | Method for preparing boron-doped graphene by electrochemical stripping of double graphite electrodes |
| CN112978721A (en) * | 2019-12-02 | 2021-06-18 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene by double-pulse electrochemical technology |
| CN112291868A (en) * | 2020-09-14 | 2021-01-29 | 兰州大学 | Self-annealing graphene self-supporting high-temperature electrothermal film and preparation method thereof |
| 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 |
| CN114590802A (en) * | 2021-12-08 | 2022-06-07 | 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 |
| CN114572973A (en) * | 2022-05-03 | 2022-06-03 | 营口理工学院 | Method for preparing graphene composite aerogel by intercalation-in-situ polymerization synergistic method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106245104B (en) | 2018-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106245104A (en) | A kind of method preparing Graphene based on electrochemical process stripping dual graphite electrodes | |
| CN106520079B (en) | Graphene heat-conducting film and preparation method thereof | |
| CN108117065B (en) | Method for preparing graphene by adopting alternate current stripping | |
| CN102923697B (en) | Method for preparing graphene energy storing material through electrochemical cathodic disbonding | |
| TWI522314B (en) | Large-scale production apparatus for preparing graphene and graphene oxide and the method thereof | |
| CN103991862A (en) | Method for preparing high-quality graphene through electrochemical high-efficiency exfoliation | |
| CN106744841B (en) | Preparation method of three-dimensional porous graphene film constructed by single-layer graphene | |
| KR20150094668A (en) | Method and apparatus for transfer of films among substrates | |
| CN104773730A (en) | Method for preparing graphene | |
| CN104876211A (en) | Method for preparing graphene by rotationally shearing in electric field environment | |
| CN110316729B (en) | Method for preparing graphene based on high-concentration organic salt aqueous solution electrochemical intercalation | |
| CN107967998B (en) | Preparation method of graphene foam nickel electrode | |
| CN109850882A (en) | A kind of graphene electrochemistry transfer method of more support membrane auxiliary | |
| CN107954420B (en) | A kind of method that Anodic removing graphite prepares three-dimensional grapheme | |
| CN106629676A (en) | Alkaline-electrolyte-based graphene preparation method | |
| CN110817816A (en) | Large-area thin-layer high-quality black phosphorus nanosheet and electrochemical stripping preparation method thereof | |
| CN111217361B (en) | Method for preparing graphene nanosheet through electrochemical cathode stripping | |
| CN105417537A (en) | Device for quickly stripping graphene through synergistic effect of ultrasound and electric field and method for quickly stripping graphene by utilizing same | |
| KR20160002009A (en) | Graphene nanosheets, graphene powder, graphene ink, graphene substrate, and method for manufacturing the graphene nanosheets | |
| KR101653181B1 (en) | Method for production of graphene | |
| CN109052495B (en) | NiPS3Nanosheet and preparation method thereof | |
| CN107104001A (en) | A kind of method for improving specific capacitance in graphenic surface adsorption of hydrolyzation polyimide molecule | |
| CN205328621U (en) | Supersound and electric field synergism peel off device of graphite alkene fast | |
| CN205328623U (en) | Supersound and electric field synergism peel off device of graphite alkene fast | |
| CN205328622U (en) | Supersound and electric field synergism peel off device of graphite alkene fast |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180717 Termination date: 20210720 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |