CN108862254A - A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene - Google Patents
A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene Download PDFInfo
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Abstract
A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene, selection H-type electrolytic cell are equipment, and centre separates anode and cathode tank house with ion diaphragm；Anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber；DC power supply is connected with graphite yin, yang electrode, opens DC power supply, electrolysis is until obtain removing graphene；Graphene solution after cathode chamber and anode chamber's removing is poured into container, and DMF is added, washing obtains graphene solution after ultrasound.Under the action of electric field, the anode chamber and the cathode chamber distinguishes the process of peeling-off graphite, anion insertion anode graphite removing generates anode graphite alkene in anode chamber, cathodic disbonding graphite is generated in cation insertion graphite linings in cathode chamber, the stripping process of two electrodes can occur simultaneously, realize the purpose that the removing simultaneously of yin-yang bipolar electrode prepares graphene.
Description
Technical field
The content of present invention is related to a kind of preparation method of graphene, and in particular to a kind of electrochemistry yin-yang bipolar electrode removing system
The method of standby graphene, is realized in cathode and anode using electrochemical techniques while preparing graphene.
Background technique
It is in the electrolytic solution, under the action of electric field, to pass through cathodic reduction or anode that electrochemical method, which prepares graphene,
Graphite oxide source electrode drives the ion in solution to be embedded into and expands the structure of working electrode graphite and produce
Raw removing.Stripping process only needs power supply, electrolyte, graphite electrode and to electrode, simple equipment and lower cost,
And environmentally friendly and preparation graphene defect is few, and controllability is strong, and the period is short, so that electrochemical method becomes extensive raw
Produce the potential method of graphene.
It is under the action of electric field that Anodic removing, which prepares graphene, and anion, which is embedded into graphite linings, produces graphite
The booster action for the gas that the raw decomposition for expanding electrolyte in addition generates generates removing, and the electrolyte used is mainly aqueous solution
And ionic liquid.Parvez et al. (ACS Nano 2013,7, (4), 3598-3606.) is with ammonium sulfate, sodium sulphate and potassium sulfate
Aqueous solution be electrolyte, natural graphite flakes are electrode, constant pressure 10V sulfate ion insertion graphite linings removing generate graphite
Alkene can quickly and efficiently generate graphene in these solution, but since the electrochemical window of water is relatively narrow, in the process of removing
In, the electrolysis of water makes the graphene of removing be easy to produce oxidation.Researchers have used the broader ionic liquid of electrochemical window
Body is electrolyte, and Na Liu et al. people (Advanced Functional Materials 2008,18, (10), 1518-1525) makes
It is electrolyte with 1- octyl -3- methylimidazole hexafluorophosphate plasma liquid, electrochemical stripping is carried out at constant pressure 15V, compared with
Big PF6 -It can be embedded into generate in graphite linings and expand and remove generation graphene.Xunyu Lu
(Phys.Chem.Chem.Phys., 2013,15,20005) carries out anode removing in acetyl nitrate ammonium ion liquid and prepares stone
Black alkene, nitrate ion have planar structure, can be well embedded in graphite linings, and TEM structure shows that graphene has 3-4 layers
Thickness.The content of oxide group can be reduced using ionic liquid as the graphene that electrolyte electrochemical is removed, but after removing
Graphene still contains more oxide group.
It is under the action of electric field that electrochemical cathode removing, which prepares graphene, and the cation of cation either solvation is embedding
Enter to make into graphite linings graphite to generate expansion subsequent ultrasonic treatment or the auxiliary for decomposing the gas generated of solvent in addition
Effect generates removing, and cathodic reduction can generate oxidation to avoid the graphite of removing.The solvent that cathodic disbonding generates graphene is main
There are propene carbonate, dimethyl sulfoxide and NMP, solute includes lithium salts and alkylammonium salt.Wang et al. (Journal of the
American Chemical Society, 2011,133, (23), 8888-8891.) it is with lithium perchlorate propene carbonate (PC)
The solvated ion that electrolyte, lithium ion and PC are formed is embedded into cathode graphite linings under electric field action, in addition subsequent super
Several layers of graphenes of the available high quality of sonication, the graphene of 70% removing is all within 5 layers in product.This method
The high graphene of the yield of high quality can be prepared, but the time that preparation process is spent is long, and subsequent ultrasound in addition
Processing effect is so that the lamella size of graphene is smaller.In addition dimethyl sulfoxide (DMSO) also has wider electrochemical window, and
It is also a kind of solvent of good dispersed graphite alkene.Abdelkader et al. (ACS Applied Materials&
Interfaces 2014,6, (3), 1632-1639) utilize DMSO/Li+The solvated ion of formation can under electric field action
It is embedded among graphite linings, DMSO, which is decomposed, among graphite linings generates SO2Equal gases, promote graphene layer to take off from graphite electrode
It falls and is dispersed in electrolyte.Graphite can be rapidly removed in the DMSO electrolyte of lithium salts, but is mostly graphite flake, graphite
Alkene yield is not high.Cooper et al. (Carbon 2014,66,340-350) research shows that the NMP with alkylammonium salt is organic
Solution is removing electrolyte, and alkylammonium salt cation is embedded into the highly directional cracking graphite layers of cathode, removing system at constant pressure
The number of plies of standby graphene out is between 2-5 layers, and oxygen content very little, but there is still a need for use highly directional cracking stone for this method
Ink is that graphitic source just can effectively generate removing.
Existing is all to realize independent anode/cathode to remove graphene using electrochemical method, be will lead to so another
An outer electrode has only served the effect to electrode, and resulting in electrode cannot make full use of.Electrochemical stripping graphene is in yin-yang
Pole generates simultaneously will improve energy utilization rate when preparing graphene, so that the extensive efficient production of graphene may be at
For reality.
To sum up, electrochemistry is prepared in the method for graphene and is had the following disadvantages at present：Removing can only be when preparing graphene
Cathode or anode generate single electrode removing, another electrode could not make full use of, and result in the waste of the energy.
Summary of the invention
To overcome the problems of the prior art, the purpose of the present invention is to provide a kind of removings of electrochemistry yin-yang bipolar electrode to make
The method of standby graphene, this method can more effectively utilize power supply, so that cathode, anode removing simultaneously prepares graphene, lead to
Design H electrode structure is crossed, so that anode and cathode tank house separates, and separates the electrolyte of the anode chamber and the cathode chamber using ion diaphragm.In yin
Pole and anode, which are separately added into, can remove the electrolyte for generating graphene, so that it may realize that yin-yang bipolar electrode removing prepares graphene
Purpose.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene, includes the following steps：
(1) selecting H-type electrolytic cell is equipment, and centre separates anode and cathode tank house with ion diaphragm；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber；
(4) DC power supply is connected with graphite yin, yang electrode, opens DC power supply, electrolysis is until obtain removing graphene；
(5) graphene solution after cathode chamber and anode chamber's removing is poured into container, and DMF is added, washed after ultrasound
It washs to obtain graphene solution.
A further improvement of the present invention lies in that ion diaphragm is cation membrane or anion membrane.
A further improvement of the present invention lies in that the concentration of anolyte is 0.01mol/L~10mol/L.
A further improvement of the present invention lies in that anolyte is salts solution, the aqueous solution of surfactant, ion
The acetonitrile solution of liquid, the acetonitrile solution of normal temperature molten salts or NaClO4Acetonitrile solution.
A further improvement of the present invention lies in that salts solution is sulfate solution or nitrate aqueous solution；Surface is living
Property agent aqueous solution be SDS, SDBS or PSS aqueous solution；Ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborate, 1-
Butyl -3- methylimidazole hexafluorophosphate, 1- butyl -3- methylimidazole perchlorate, 1- butyl -3- methyl ammonium tetrafluoro boric acid
Salt, 1- butyl -3- methyl ammonium perchlorate, 1- butyl -3- methyl ammonium hexafluorophosphate, 1- butyl -1- methyi-pyrrofidinium tetrafluoro
Borate, 1- butyl -1- methyi-pyrrofidinium perchlorate, 1- butyl -1- methyi-pyrrofidinium hexafluorophosphate；Normal temperature molten salts are pressed
Mass percent meter, including 50%~57% acetamide, 30%~38% urea and 5%~20% metal salt.
A further improvement of the present invention lies in that sulfate is potassium sulfate or sodium sulphate；Nitrate is potassium nitrate or sodium nitrate；
Metal salt is lithium salts, sodium salt, sylvite, ammonium salt, zinc salt, magnesium salts or nickel salt.
A further improvement of the present invention lies in that catholyte is that the organic electrolyte of alkali metal salt, alkylammonium salt have
The acetonitrile solution of machine electrolyte or ionic liquid；
The concentration of the organic electrolyte of the organic electrolyte and alkylammonium salt of alkali metal salt is 0.01mol/L~10mol/
L；The acetonitrile solution intermediate ion liquid solubility of ionic liquid is 0.01mol/L~1mol/L.
A further improvement of the present invention lies in that the organic electrolyte of alkali metal salt and the organic electrolyte of alkylammonium salt are logical
It crosses for alkali metal salt or alkylammonium salt to be added in organic solvent and be made；
Alkali metal salt is lithium chloride, sodium chloride, potassium chloride, lithium carbonate, sodium carbonate, potassium carbonate, lithium sulfate, sodium sulphate, sulphur
Sour potassium, lithium perchlorate, sodium perchlorate, potassium hyperchlorate, lithium nitrate, sodium nitrate, potassium nitrate, lithium phosphate, sodium phosphate or potassium phosphate；
Alkylammonium salt is etamon chloride, tetraethylammonium bromide, tetraethyl ammonium perchlorate, tetraethyl ammonium hexafluorophosphate,
Tetraethyl ammonium tetrafluoroborate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium perchlorate, tetrabutyl ammonium hexafluorophosphate, four
Butyl ammonium tetrafluoroborate, tetramethyl ammonium chloride, 4 bromide, tetramethyl ammonium perchlorate, tetramethyl ammonium hexafluorophosphate or four
Methyl ammonium tetrafluoroborate.
A further improvement of the present invention lies in that organic solvent is n,N-Dimethylformamide, N, N- dimethyl trifluoroacetyl
Amine, dimethyl sulfoxide, N-Methyl pyrrolidone, N- ethyl pyrrolidone, propene carbonate, ethylene carbonate, dimethyl carbonate,
Dibutyl carbonate, methyl ethyl carbonate, carbonic acid first butyl ester, butylene, dipropyl carbonate, 1,4-butyrolactone, methyl esters, acetic acid first
Ester, methyl formate, methyl propionate, 1,2- dimethoxy-ethane, 1,3- dioxolanes, 4- methyl-1,3-dioxy also pentane, four
Hydrogen furans, dimethyl-tetrahydrofuran, acetonitrile, haloflex, cyclohexyl benzene, glycol sulfite, ethyl sulfate, sulfurous acid
Acrylic ester, vinylene carbonate, vinylethylene carbonate, sulfuric acid acrylic ester, 1,4- butane sultones, in 1,3- propane sulfonic acid
Ester, 4- potassium sulfate ethyl ester, 4- methyl glycol sulfite, methane-disulfonic acid ethyl, butylene sulfite, 4- methyl sulfurous acid
(trimethyl silane) phosphite ester of vinyl acetate three or three (trimethyl silane) borates.
A further improvement of the present invention lies in that graphite electrode is graphite rod, graphite foil, natural graphite powder tabletting, natural stone
Ink sheet or highly directional cracking graphite；
The spacing of two graphite electrodes is 0.5~2cm, and the depth that electrode immerses electrolyte is 2~5cm；
The revolving speed of centrifugation is 100~3000r/min；
Ultrasonic time is 20min~120min.
Compared with prior art, the device have the advantages that being：
The present invention is device using H-type electrolytic cell, so that the anode chamber and the cathode chamber separates, it is intermediate to separate anode and cathode electricity with ion diaphragm
Liquid is solved, only ion passes through between the anode chamber and the cathode chamber, and solvent cannot pass through, and thus can make the anode chamber and the cathode chamber relatively independently
Carry out electrochemical stripping process.The anode chamber and the cathode chamber can use different types of cathode and anolyte respectively, by adjusting electricity
Position can make cathode and anode electrolysis room while reach the current potential of electrolyte removing graphene, without as in common electrolysis
It can only achieve the current potential of cathode/anode single electrode removing graphene in liquid.In the anode compartment, the graphite electrode of anode is in electric field
Under effect, the anion of solvation be can be plugged into the graphite of stratiform, so that expansion is generated between graphite linings, in higher positive electricity
Under the effect of position, the ion dissociation of insertion simultaneously generates gas, so that graphite split layer removing graphite be promoted to form anode graphite alkene.?
In cathode chamber, the cation of solvation is embedded among graphite linings, so that expansion is generated between graphite linings, in lower negative potential
Under effect, the solvated ion of insertion decomposes and generates gas, so that graphite split layer removing graphite be promoted to form cathode graphite
Alkene.Anode and cathode thus may be implemented while generating the graphene of electrochemical stripping, improve the utilization rate of electric energy.This method is only
D.C. regulated power supply, H-type electrolytic cell, ion diaphragm and anode and cathode electrolyte are needed, equipment cost is lower, obtains graphene
Process is simple and easy, cheap, environment is relatively friendly, and process is easily controllable, is convenient for industrial application.
Detailed description of the invention
Fig. 1 is the SEM figure that the removing simultaneously of yin-yang bipolar electrode prepares graphene.Wherein, (a) is anode, (b) is cathode.
Specific embodiment
The present invention will be described in detail in the following with reference to the drawings and specific embodiments.
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre separates anode and cathode tank house with ion diaphragm；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 0.5~2cm, the depth for immersing electrolyte is 2~5cm.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, is electrolysed time enough under constant pressure or constant current,
Until the removing graphene needed for obtaining.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and ultrasound 20min~120min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, passes through low-speed centrifugal (100~3000r/
Min unstripped graphite) is removed, extracts upper liquid, so that it may obtain graphene solution.
Graphite electrode is other than using graphite rod in the present invention, graphite foil, tabletting natural graphite powder, natural graphite flakes,
And highly directional cracking graphite (HOPG) can be used as graphite electrode.
Ion diaphragm includes：The cation membrane and anion membrane of various models.
Anode chamber's electrolyte includes：Sulfate solution, the various salts solutions such as nitrate aqueous solution,
The aqueous solution of the various surfactants such as SDS, SDBS or PSS and the ionic liquid that can produce anode electrochemical removing graphene
Body, normal temperature molten salts or NaClO4Acetonitrile solution etc..
Wherein, ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- butyl -3- methylimidazole hexafluorophosphoric acid
Salt, 1- butyl -3- methylimidazole perchlorate, 1- butyl -3- methyl ammonium tetrafluoroborate, 1- butyl -3- methyl ammonium perchloric acid
Salt, 1- butyl -3- methyl ammonium hexafluorophosphate, 1- butyl -1- methyi-pyrrofidinium tetrafluoroborate, 1- butyl -1- methyl-pyrrole
Cough up alkane perchlorate, 1- butyl -1- methyi-pyrrofidinium hexafluorophosphate；
Normal temperature molten salts by mass percentage, including 50%~57% acetamide, 30%~38% urea and 5%~
20% metal salt, wherein metal salt is lithium salts, sodium salt, sylvite, ammonium salt, zinc salt, magnesium salts or nickel salt.
Catholyte is：The organic electrolyte of alkali metal salt or alkylammonium salt can produce cathodic disbonding graphene
The acetonitrile solution of ionic liquid or ionic liquid.
The organic electrolyte of alkali metal salt and the organic electrolyte of alkylammonium salt are by by alkali metal salt or alkylammonium salt
It is added in organic solvent and is made；
Wherein, organic solvent is：N,N-dimethylformamide, N, N- dimethyl trifluoroacetamide, dimethyl sulfoxide, N- first
Base pyrrolidones, N- ethyl pyrrolidone, propene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, carbonic acid first
Ethyl ester, carbonic acid first butyl ester, butylene, dipropyl carbonate, 1,4-butyrolactone, methyl esters, methyl acetate, methyl formate, propionic acid
Methyl esters, 1,2- dimethoxy-ethane, 1,3- dioxolanes, 4- methyl-1,3-dioxy also pentane, tetrahydrofuran, dimethyl four
Hydrogen furans, acetonitrile, haloflex, cyclohexyl benzene, glycol sulfite, ethyl sulfate, propylene sulfite, carbonic acid Asia second
Enester, vinylethylene carbonate, sulfuric acid acrylic ester, 1,4- butane sultones, 1,3- propane sultone, 4- potassium sulfate second
Ester, 4- methyl glycol sulfite, methane-disulfonic acid ethyl, butylene sulfite, three (front three of 4- methyl ethylene sulfite
Base silane) phosphite ester or three (trimethyl silane) borates etc..
Alkali metal salt includes：Lithium chloride, sodium chloride, potassium chloride, lithium carbonate, sodium carbonate, potassium carbonate, lithium sulfate, sodium sulphate,
Potassium sulfate, lithium perchlorate, sodium perchlorate, potassium hyperchlorate, lithium nitrate, sodium nitrate, potassium nitrate, lithium phosphate, sodium phosphate or potassium phosphate
Deng.
Alkylammonium salt is etamon chloride, tetraethylammonium bromide, tetraethyl ammonium perchlorate, tetraethyl ammonium hexafluorophosphate,
Tetraethyl ammonium tetrafluoroborate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium perchlorate, tetrabutyl ammonium hexafluorophosphate, four
Butyl ammonium tetrafluoroborate, tetramethyl ammonium chloride, 4 bromide, tetramethyl ammonium perchlorate, tetramethyl ammonium hexafluorophosphate or four
Methyl ammonium tetrafluoroborate.
The concentration range of electrolyte is：
Anode aqueous electrolyte：0.01mol/L~10mol/L；
Catholyte：1. alkali metal and alkylammonium salt organic electrolyte：0.01mol/L~10mol/L.
2. pure ionic liquid
3. the acetonitrile solution intermediate ion liquid solubility of ionic liquid is：0.01mol/L~1mol/L.
Voltage between anodic-cathodic is 5~100V.Electrolysis time is generally：1~200h.
Sulfate is potassium sulfate or sodium sulphate；Nitrate is potassium nitrate or sodium nitrate.
Embodiment 1
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The potassium sulfate solution of 0.01mol/L, catholyte are the n,N-Dimethylformamide solution of the lithium chloride of 0.01mol/L；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 0.5cm, the depth for immersing electrolyte is 2cm.Wherein, graphite electrode is graphite rod.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 10V, permanent
Pressure/constant-current electrolysis 180h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 20min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (100r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 2
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The sodium nitrate aqueous solution of 0.06mol/L, catholyte are the dimethyl sulfoxide of the sodium carbonate of 0.06mol/L；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 1cm, the depth for immersing electrolyte is 3cm.Wherein, graphite electrode is graphite foil.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 20V, permanent
Pressure/constant-current electrolysis 150h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 50min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (500r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 3
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion yin diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The SDBS aqueous solution of 0.1mol/L, catholyte are the carbonic allyl ester solution of the potassium sulfate of 0.1mol/L；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 1.5cm, the depth for immersing electrolyte is 4cm.Wherein, graphite electrode is tabletting natural graphite
Powder.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 30V, permanent
Pressure/constant-current electrolysis 130h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 60min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (1000r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 4
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion yin diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The acetonitrile solution of the normal temperature molten salts of 0.5mol/L, normal temperature molten salts by mass percentage, including 50% acetamide, 38% urea with
And 12% lithium salts.Catholyte is the 1,4-butyrolactone solution of the sodium perchlorate of 0.5mol/L；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 2cm, the depth for immersing electrolyte is 5cm.Wherein, graphite electrode is natural graphite flakes.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 40V, permanent
Pressure/constant-current electrolysis 70h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 80min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (3000r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 5
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
1- butyl -1- methyi-pyrrofidinium perchlorate, catholyte are the 4- methyl-1 of the tetraethyl ammonium hexafluorophosphate of 1mol/L,
3- dioxy also pentane solution；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 2cm, the depth for immersing electrolyte is 5cm.Wherein, graphite electrode is highly directional cracking graphite
(HOPG)。
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 50V, permanent
Pressure/constant-current electrolysis 50h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 100min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (2000r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 6
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The NaClO of 3mol/L4Acetonitrile solution, catholyte are the ionic liquid of the 1- butyl -3- methyl ammonium perchlorate of 1mol/L
Acetonitrile solution；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 1cm, the depth for immersing electrolyte is 4cm.Wherein, graphite electrode is graphite rod.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 60V, permanent
Pressure/constant-current electrolysis 40h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 120min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (800r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 7
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The PSS aqueous solution of 5mol/L, catholyte are the ionic liquid of 1- butyl -1- methyi-pyrrofidinium perchlorate；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 2cm, the depth for immersing electrolyte is 3cm.Wherein, graphite electrode is graphite rod.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 70V, permanent
Pressure/constant-current electrolysis 20h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 30min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (700r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 8
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The aqueous sodium persulfate solution of 10mol/L, catholyte are the 4- methyl ethylene sulfite three of the tetramethyl ammonium chloride of 10mol/L
The solution of (trimethyl silane) phosphite ester；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 1cm, the depth for immersing electrolyte is 2cm.Wherein, graphite electrode is graphite rod.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 5V, permanent
Pressure/constant-current electrolysis 200h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 40min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (100r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 9
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The potassium sulfate solution of 8mol/L, catholyte are three (trimethyl silane) acid ester solutions of the potassium phosphate of 8mol/L；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 2cm, the depth for immersing electrolyte is 2cm.Wherein, graphite electrode is graphite rod.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 80V, permanent
Pressure/constant-current electrolysis 10h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 110min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (3000r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
Embodiment 10
The step of yin-yang the two poles of the earth of the invention prepare graphene simultaneously is as follows：
(1) selecting H-type electrolytic cell is equipment, and centre ion sun diaphragm separates anode and cathode tank house；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；Wherein anolyte is
The ionic liquid of 1- butyl -3- methylimidazole perchlorate, catholyte are 1- butyl -3- methylimidazole hexafluorophosphate
Ionic liquid；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber, two
For a graphite electrode spacing between 1cm, the depth for immersing electrolyte is 3cm.Wherein, graphite electrode is graphite rod.
(4) DC power supply is connected with graphite yin, yang electrode, opens power supply, the voltage between anodic-cathodic is 100V, permanent
Pressure/constant-current electrolysis 1h obtains required removing graphene.
(5) graphene solution after cathode chamber and anode chamber's removing is poured into conical flask respectively, and be added a certain amount of
DMF (n,N-Dimethylformamide), and the ultrasound 70min in Ultrasound Instrument.
(6) by filtering washing, ethyl alcohol cleaning repeatedly, removes ion and the electrolyte etc. in graphene.
(7) obtained filter cake will be filtered to be dispersed in DMF again, after ultrasound, is removed by low-speed centrifugal (2000r/min)
Unstripped graphite is removed, upper liquid is extracted, obtains graphene solution.
From (a) in Fig. 1 and (b) as can be seen that it can be seen from stereoscan photograph electrochemical bipolar removing graphite yin,
The graphene that anode obtains all show it is nearly transparent, crimp laminate structure, and the piece diameter of graphene it is larger (>10um), it demonstrate,proves
Bright method of the invention has obtained the graphene of large stretch of diameter, in addition quality height, the few (Id/Ig of defect of graphene<0.08), oxygen contains
Measure low (C/O>20), and conductivity is excellent, in 30000Sm-1More than.
It is only illustrated in the present invention with part material, the raw material for the similar performance for including in the present invention can be realized this
The purpose of invention.When the present invention prepares graphene primarily directed to existing electrochemical method, either anodic oxidation removing is gone back
It is cathodic reduction removing, can only be removed using an electrode in existing method, another electrode is to act as pair
The effect of electrode, this has resulted in cannot making full use of for electric energy.It, can be more effectively in order to during preparing graphene
Using power supply, so that cathode, anode removing simultaneously prepares graphene, and the present invention is by design H electrode structure, so that anode and cathode is electric
It solves room to separate, and separates the electrolyte of the anode chamber and the cathode chamber using ion diaphragm.Generation can be removed by being separately added into cathode and anode
The electrolyte of graphene, so that it may realize that yin-yang bipolar electrode removing prepares the purpose of graphene.
Claims (10)
1. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene, which is characterized in that include the following steps：
(1) selecting H-type electrolytic cell is equipment, and centre separates anode and cathode tank house with ion diaphragm；
(2) anolyte is added in anode chamber, the catholyte of equivalent is added in cathode chamber；
(3) two root graphite electrodes are taken, one is used as anode, and in addition one is used as cathode, is respectively put into the anode chamber and the cathode chamber；
(4) DC power supply is connected with graphite yin, yang electrode, opens DC power supply, electrolysis is until obtain removing graphene；
(5) graphene solution after cathode chamber and anode chamber's removing is poured into container, and DMF is added, washed after ultrasound
To graphene solution.
2. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 1, which is characterized in that
Ion diaphragm is cation membrane or anion membrane.
3. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 1, which is characterized in that
The concentration of anolyte is 0.01mol/L~10mol/L.
4. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 1 or 3, feature exist
In anolyte is the second of salts solution, the aqueous solution of surfactant, the acetonitrile solution of ionic liquid, normal temperature molten salts
Nitrile solution or NaClO4Acetonitrile solution.
5. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 4, which is characterized in that
Salts solution is sulfate solution or nitrate aqueous solution；The aqueous solution of surfactant is the water of SDS, SDBS or PSS
Solution；Ionic liquid is 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- butyl -3- methylimidazole hexafluorophosphate, 1- fourth
Base -3- methylimidazole perchlorate, 1- butyl -3- methyl ammonium tetrafluoroborate, 1- butyl -3- methyl ammonium perchlorate, 1- fourth
Base -3- methyl ammonium hexafluorophosphate, 1- butyl -1- methyi-pyrrofidinium tetrafluoroborate, the high chlorine of 1- butyl -1- methyi-pyrrofidinium
Hydrochlorate, 1- butyl -1- methyi-pyrrofidinium hexafluorophosphate；Normal temperature molten salts by mass percentage, including 50%~57% acetyl
Amine, 30%~38% urea and 5%~20% metal salt.
6. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 5, which is characterized in that
Sulfate is potassium sulfate or sodium sulphate；Nitrate is potassium nitrate or sodium nitrate；Metal salt is lithium salts, sodium salt, sylvite, ammonium salt, zinc
Salt, magnesium salts or nickel salt.
7. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 1, which is characterized in that
Catholyte is organic electrolyte, the organic electrolyte of alkylammonium salt or the acetonitrile solution of ionic liquid of alkali metal salt；
The concentration of the organic electrolyte of the organic electrolyte and alkylammonium salt of alkali metal salt is 0.01mol/L~10mol/L；From
The acetonitrile solution intermediate ion liquid solubility of sub- liquid is 0.01mol/L~1mol/L.
8. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 7, which is characterized in that
The organic electrolyte of alkali metal salt and the organic electrolyte of alkylammonium salt are by the way that alkali metal salt or alkylammonium salt to be added to
It is made in solvent；
Alkali metal salt be lithium chloride, sodium chloride, potassium chloride, lithium carbonate, sodium carbonate, potassium carbonate, lithium sulfate, sodium sulphate, potassium sulfate,
Lithium perchlorate, sodium perchlorate, potassium hyperchlorate, lithium nitrate, sodium nitrate, potassium nitrate, lithium phosphate, sodium phosphate or potassium phosphate；
Alkylammonium salt is etamon chloride, tetraethylammonium bromide, tetraethyl ammonium perchlorate, tetraethyl ammonium hexafluorophosphate, tetrem
Base ammonium tetrafluoroborate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium perchlorate, tetrabutyl ammonium hexafluorophosphate, the tetrabutyl
Ammonium tetrafluoroborate, tetramethyl ammonium chloride, 4 bromide, tetramethyl ammonium perchlorate, tetramethyl ammonium hexafluorophosphate or tetramethyl
Ammonium tetrafluoroborate.
9. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 8, which is characterized in that
Organic solvent is N,N-dimethylformamide, N, N- dimethyl trifluoroacetamide, dimethyl sulfoxide, N-Methyl pyrrolidone, N-
Ethyl pyrrolidone, propene carbonate, ethylene carbonate, dimethyl carbonate, dibutyl carbonate, methyl ethyl carbonate, carbonic acid first fourth
Ester, butylene, dipropyl carbonate, 1,4-butyrolactone, methyl esters, methyl acetate, methyl formate, methyl propionate, 1,2- diformazan
Oxygroup ethane, 1,3- dioxolanes, 4- methyl-1,3-dioxy also pentane, tetrahydrofuran, dimethyl-tetrahydrofuran, acetonitrile, chlorine
Change polyethylene, cyclohexyl benzene, glycol sulfite, ethyl sulfate, propylene sulfite, vinylene carbonate, ethylene carbonate
Ethyl, sulfuric acid acrylic ester, 1,4- butane sultones, 1,3- propane sultone, 4- potassium sulfate ethyl ester, 4- methyl sulfurous acid
Ethyl, methane-disulfonic acid ethyl, butylene sulfite, 4- methyl ethylene sulfite three (trimethyl silane) phosphite ester
Or three (trimethyl silane) borate.
10. a kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene according to claim 1, feature exist
In graphite electrode is graphite rod, graphite foil, natural graphite powder tabletting, natural graphite flakes or highly directional cracking graphite；
The spacing of two graphite electrodes is 0.5~2cm, and the depth that electrode immerses electrolyte is 2~5cm；
The revolving speed of centrifugation is 100~3000r/min；
Ultrasonic time is 20min~120min.
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