CN107235487B - The preparation method of graphene - Google Patents
The preparation method of graphene Download PDFInfo
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- CN107235487B CN107235487B CN201610169825.5A CN201610169825A CN107235487B CN 107235487 B CN107235487 B CN 107235487B CN 201610169825 A CN201610169825 A CN 201610169825A CN 107235487 B CN107235487 B CN 107235487B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The following steps are included: a) using graphite material as the material of anode, the mixed solution of oxalic acid and hydrogen peroxide carries out cell reaction and realizes electrochemical stripping to anode material as electrolyte for the preparation method of graphene；B) electrolyte after reacting in step a is separated by solid-liquid separation, to extract the graphene presoma of dispersion in the electrolytic solution, then graphene presoma is subjected to drying and processing and makes remaining electrolyte decomposition thereon, obtains graphene sample；C) graphene sample dried in step b is dissolved in organic solvent, then the organic solvent dissolved with graphene sample is ultrasonically treated, obtain graphene solution.The present invention provides a kind of preparation method of graphene; the electrolyte mixed by using oxalic acid and hydrogen peroxide realizes the electrochemical stripping to graphite material under electric field action; inexpensive, pollution-free, free from admixture and prepare with scale graphene may be implemented; convenient for removal of impurities; environmental protection and energy saving improve yield.
Description
Technical field
The present invention relates to grapheme material preparation technical fields, and in particular to a kind of preparation method of graphene.
Background technique
Since obtaining high-quality graphene using the removing of micromechanics stripping means, uniqueness possessed by graphene is conductive
Thermally conductive and mechanical performance attracts always scientific research circle and the great interest of industrial circle.Due to excellent properties, the market of graphene
Demand is also increasing, this require grapheme material preparation constantly improve and can be realized the technology of preparing of green non-pollution with
Obtain the graphene of high-volume high quality.However in face of industrial application, there is also very big challenges for current preparation.Firstly, can
There are low yield, high energy consumption and transfer difficulties etc. to ask for the chemical vapour deposition technique and epitaxial growth method for obtaining high-quality graphene
Topic；In addition, although large scale preparation graphene may be implemented in chemistry redox method, but there are a large amount of oxygen-containing groups to be connected to stone
On black alkene lamella, the electrical and thermal conductivity performance of graphene is caused to be greatly lowered.Moreover, ultrasonic stripping method and liquid phase shear stripping method
The grapheme material of high quality can be obtained, does not also use strong acid or strong oxidizer, and do not have metal ion, but obtained
Graphene lateral dimension is less than normal, it is most important that yield is very low, and often yield is lower than 5%, and needs to be separated by filtration, economy
Difference, total cost performance be not still high.
For existing graphene preparation technology or the high cost of high quality or at low cost of poor quality, graphene industry
Development need it is a kind of can be mass-produced, the technology of preparing of high quality, low cost and green non-pollution, to break through grapheme material
Bottleneck.It is one of possible approach that electrochemistry, which prepares graphene,.Compared to oxidation-reduction method, electrochemical process does not need Strong oxdiative
Agent instead electric field oxidation removing；Compared to chemical vapour deposition technique, the yield of electrochemistry preparation is far longer than gas
Phase deposition technique；Compared to the yield that ultrasound or liquid phase shearing are lower than 5%, electrochemical process can obtain the yield close to 100%.
However existing electrochemistry technology of preparing not enough or is not enough to the grapheme material for large scale preparation high quality.
In the document and patent that the electrochemistry having disclosed prepares graphene, used electrolyte can be divided into ion
Liquid, strong acid and some salting liquids.Wherein, it exists in the prior art and ionic liquid is used to insert as electrolyte progress cathode
Layer removing can get with a thickness of 2~3 layers, the graphene that oxygen content is 2.5%, but when using ionic liquid as electrolyte,
The common problem encountered is that the expensive and complicated zwitterion impurity removal of ionic liquid is highly difficult etc., thus is difficult to industry
Change and uses.There is also a kind of technologies of similar il electrolyte mechanism in the prior art, particular by high-temperature heating chlorine
To change the salt such as potassium, sodium chloride, melts it as electrolyte, resulting graphene defect is few, and it is low for equipment requirements, but high temperature item
Part energy consumption is higher, containing cleared ion such as chloride ion, potassium ion and sodium ion etc. is largely difficult in obtained product, greatly
The use of ground influence graphene.In addition, there is also use a large amount of sulfuric acid and glycine as electrolyte, although stripping in the prior art
Quickly from speed, the graphene that can be completed, and be can get with a thickness of 2~5 layers in 5 minutes, but equally exist and be difficult to remove completely
Net sulfate radical and glycine ion.In addition, relatively environment-friendly and easy method is using some salting liquids as electrolyte, example
Such as, the electrolyte that solvation is made of lithium salts and propene carbonate exists in the prior art, makes lithium ion in electrolytic process
It is inserted into graphite layers and carries out removing acquisition graphene, but there are complicated for operation, electrolyte and foreign ion after removing removals
The problem of cost that is very troublesome and increasing industrialization.In addition, there is also also use similar electrolysis in the prior art
Liquid K2SO4Salting liquid is removed, and voltage needed for this technology is lower, and required time is also shorter, but the product reacted can draw
Enter and be difficult to completely cleared metal ion, and sulfate ion equally understands partial oxidation of graphite alkene lamella, remaining sulfate radical
Compare and is difficult to remove.Moreover, there is also using ammonium sulfate, as electrolyte, the yield that this method obtains is up in the prior art
85%, the reaction time is short, but this method similarly faces the problem that sulfate ion can not be cleared, while sulfate ion
SO is also had in electrolytic process2Toxic gas generates, not enough environmental protection and safety.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, it is high to provide a kind of environmental protection and energy saving, low cost and yield
The preparation method of graphene.
To achieve the above object, present invention employs following technical solutions:
A kind of preparation method of graphene, comprising the following steps:
A) using graphite material as the material of anode, the mixed solution of oxalic acid and hydrogen peroxide is electrolysed as electrolyte
The electrochemical stripping to anode material is realized in reaction；
B) electrolyte after reacting in step a is separated by solid-liquid separation, to extract the graphene of dispersion in the electrolytic solution
Presoma, then graphene presoma progress drying and processing is made into remaining electrolyte decomposition thereon, obtain graphene sample；
C) graphene sample dried in step b is dissolved in organic solvent, then to dissolved with graphene sample
Organic solvent be ultrasonically treated, obtain graphene solution.
Preferably, it is stirred during the progress of the cell reaction of step a along with magneton, the magneton stirring
Revolving speed is 50~500r/min.
Preferably, the molar concentration rate of the electrolyte mesoxalic acid of step a and hydrogen peroxide is 1: 0.5~1: 50.
Preferably, the constant voltage of cell reaction described in step a is 3~30V, and the temperature of electrolyte is 5~30 DEG C.
Preferably, the cathode of cell reaction described in step a is platinized platinum, and the distance of anode and cathode is 1~10cm, electrolysis
The time of reaction is 1~180 minute.
Preferably, the temperature of drying and processing described in step b is 60~200 DEG C, and the time is 10~90 minutes.
Preferably, the temperature of the drying and processing is 190 DEG C, and the time is 30 minutes.
Preferably, the time of ultrasonic treatment described in step c is 10~60 minutes.
Preferably, the graphite material is in graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite
Any one or more block graphite material being process.
Preferably, organic solvent described in step c is that n,N-Dimethylformamide, N-Methyl pyrrolidone and dimethyl are sub-
Any one or more in sulfone.
The preparation method of graphene of the invention, the electrolyte mixed by using oxalic acid and hydrogen peroxide are made in electric field
It is realized with lower to the electrochemical stripping of graphite material, inexpensive, pollution-free, free from admixture and prepare with scale graphite may be implemented
Alkene；During the reaction with it, due to not having strong acid and metal ion, obtained electrolysate does not need clearly electrolyte itself
It washes, directly progress drying and processing, the oxalic acid remained on electrolysate and hydrogen peroxide can be completely removed, environmental protection and energy saving mention
High product purity and yield simplify production technology, are easy to implement large-scale production, and cell reaction process is main happens is that grass
Acid is reacted with hydrogen peroxide, generates water and carbon dioxide, nontoxic and pollution-free, in addition to electrolyte in entire process flow, will not be produced
Raw other pollutants expect process flow from former material, then arrive final product, and complete green non-pollution realizes production process environment
It is friendly；Electrolyte is oxalic acid and hydrogen peroxide, itself is nontoxic, pollution-free, soluble easily in water, so electrolyte may be selected to be water
Phase, more environmentally-friendly cleaning reduce production cost.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of the graphene obtained of embodiment one；
Fig. 2 is the scanning electron microscope diagram of the graphene obtained of embodiment one；
Fig. 3 is the transmission electron microscope figure of the graphene obtained of embodiment one；
Fig. 4 is the transmission electron microscope figure of the graphene obtained of embodiment one；
Fig. 5 is selective electron diffraction figure under the transmission electron microscope of the graphene obtained of embodiment one；
Fig. 6 is the Raman spectrogram for the graphene that one electrochemical stripping of embodiment obtains.
Specific embodiment
Below in conjunction with the embodiment that attached drawing 1 to 6 provides, the specific of the preparation method of graphene of the invention is further illustrated
Embodiment.The preparation method of graphene of the invention is not limited to the following description.
The preparation method of graphene of the invention the following steps are included:
A) using graphite material as anode material, the mixed solution of oxalic acid and hydrogen peroxide be electrolysed anti-as electrolyte
It should realize the electrochemical stripping to anode material.
B) electrolyte after reacting in step a is separated by solid-liquid separation, to extract the graphene of dispersion in the electrolytic solution
Presoma, then graphene presoma progress drying and processing is made into remaining electrolyte decomposition thereon, obtain graphene sample.
C) graphene sample dried in step b is dissolved in organic solvent, then to dissolved with graphene sample
Organic solvent be ultrasonically treated, obtain graphene solution.
Wherein, graphite material can be using in graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite
Any one or more block graphite material being process；Organic solvent in step c can use N, N- dimethyl methyl
Any one or more in amide, N-Methyl pyrrolidone and dimethyl sulfoxide.It can be using conduction materials such as graphite or platinized platinums
Expect the cathode as cell reaction in step a.
The preparation method of graphene of the invention, the electrolyte mixed by using oxalic acid and hydrogen peroxide are made in electric field
It is realized with lower to the electrochemical stripping of graphite material, inexpensive, pollution-free, free from admixture and prepare with scale graphite may be implemented
Alkene；During the reaction with it, due to not having strong acid and metal ion, obtained electrolysate does not need clearly electrolyte itself
It washes, directly progress drying and processing, the oxalic acid remained on electrolysate and hydrogen peroxide can be completely removed, environmental protection and energy saving mention
High product purity and yield simplify production technology, are easy to implement large-scale production, and cell reaction process is main happens is that grass
Acid is reacted with hydrogen peroxide, generates water and carbon dioxide, nontoxic and pollution-free, in addition to electrolyte in entire process flow, will not be produced
Raw other pollutants expect process flow from former material, then arrive final product, and complete green non-pollution realizes production process environment
It is friendly；Electrolyte is oxalic acid and hydrogen peroxide, itself is nontoxic, pollution-free, soluble easily in water, so electrolyte may be selected to be water
Phase, more environmentally-friendly cleaning reduce production cost.
The principle of preparing graphene by electrochemical stripping of the invention: under the action of electric field, oxalic acid occurs ionization and forms grass
Acid group and oxalic acid hydrogen radical anion, and the oxalate and oxalic acid hydrogen radical ion that ionize out are mobile simultaneously to the graphite material as anode
It is equably inserted into the lamellar spacing of graphite material；Then oxalate and oxalic acid hydrogen radical are carried out with the hydrogen peroxide in solution anti-again
It answers, generates a large amount of carbon dioxide gas, these carbon dioxide gas in the lamellar spacing of graphite material constantly gather by expansion,
Finally graphene is equably stripped out from graphite material.Judgement based on a large amount of electron micrographs and Raman data,
The number of plies of obtained graphene is 1-10 layers, yield >=93%, and defect is less.
The specific embodiment of the preparation method of graphene of the invention.
Embodiment one
The present embodiment successively uses following steps to prepare graphene.
Step a:
Be 5 grams using weight, with a thickness of 1mm graphite flake as anode, the platinized platinum of 10cm*10cm as cathode, 200mL's
The mixed solution of oxalic acid and hydrogen peroxide carries out electrochemical stripping as electrolyte, to graphite flake.Wherein, hydrogen peroxide is hydrogen peroxide
Aqueous solution, commercially available 30% hydrogen peroxide can be used in hydrogen peroxide, is 1M, peroxide in the molar concentration of the electrolyte mesoxalic acid
The molar concentration for changing hydrogen is 5M, i.e., the molar concentration rate of oxalic acid and hydrogen peroxide is 1: 5；The distance of anode and cathode is 2cm, electricity
It presses constant in 10V, and is stirred along with magneton, the revolving speed of magneton stirring is 50r/min, and electrolyte passes through cycle refrigeration system
Temperature is constant at 25 DEG C, graphite flake is carried out electrochemical stripping 30 minutes, graphene presoma is obtained.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 30 minutes at 190 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses N- methylpyrrole
Alkanone, then ultrasonic treatment is carried out 30 minutes to the organic solvent dissolved with graphene sample, it can be obtained graphene solution.
The scanning electron microscope test result of graphene obtained by the embodiment of the present invention one is as depicted in figs. 1 and 2, point
The macro surface pattern and microcosmic edge pattern of graphene are not disclosed, can be seen that the lamellar structure of graphene by Fig. 1 and Fig. 2
Than more complete；The transmission electron microscope result of graphene obtained by embodiment one is as shown in Figure 3 and Figure 4, presents respectively
The number of plies of graphene sheet layer size and graphene, by the observation and analysis to Fig. 3 and Fig. 4 it is found that obtained graphene
The piece number of plies is 1~3 layer；Selective electron diffraction figure such as Fig. 5 institute under the transmission electron microscope of graphene obtained by embodiment one
Show, it is shown that the complete lattice structure of graphene；Raman results show graphene as shown in fig. 6, give the low peak G
Defect it is very low；In addition, the yield of graphene obtained by embodiment one is 98.7%.
Embodiment two
The present embodiment successively uses following steps to prepare graphene.
Step a:
Using weight be 5 grams, with a thickness of 1mm crystalline flake graphite as anode, the platinized platinum of 10cm*10cm is as cathode, 200mL
Oxalic acid and hydrogen peroxide mixed solution as electrolyte, electrochemical stripping is carried out to crystalline flake graphite.Wherein, hydrogen peroxide is peroxide
The aqueous solution for changing hydrogen is 1M in the molar concentration of the electrolyte mesoxalic acid, and the molar concentration of hydrogen peroxide is 5M, i.e. oxalic acid and mistake
The molar concentration rate of hydrogen oxide is 1: 5；The distance of anode and cathode is 10cm, and voltage is constant in 30V, and stirs along with magneton
It mixes, the revolving speed of magneton stirring is 100r/min, and electrolyte is constant at 30 DEG C by temperature by cycle refrigeration system, to scale stone
Ink carries out electrochemical stripping 3 minutes, obtains graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 80 minutes at 60 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses N- methylpyrrole
Alkanone, then ultrasonic treatment is carried out 30 minutes to the organic solvent dissolved with graphene sample, it can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention two is 1~5 layer, and yield 98%, defect is less.
Embodiment three
The present embodiment successively uses following steps to prepare graphene.
Step a:
Be 5 grams using weight, with a thickness of 1mm graphite foil as anode, the platinized platinum of 10cm*10cm as cathode, 200mL's
The mixed solution of oxalic acid and hydrogen peroxide carries out electrochemical stripping as electrolyte, to graphite foil.Wherein, hydrogen peroxide is hydrogen peroxide
Aqueous solution, be 1M in the molar concentration of the electrolyte mesoxalic acid, the molar concentration of hydrogen peroxide is 1M, i.e. oxalic acid and peroxidating
The molar concentration rate of hydrogen is 1: 1；The distance of anode and cathode is 4cm, and voltage is constant in 20V, and stirs along with magneton, magneton
The revolving speed of stirring is 180r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, carries out electricity to graphite foil
Chemical stripping 50 minutes, obtain graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 35 minutes at 120 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses N- methylpyrrole
Alkanone, then ultrasonic treatment is carried out 30 minutes to the organic solvent dissolved with graphene sample, it can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention three is 2~5 layers, and yield 93%, defect is less.
Example IV
The present embodiment successively uses following steps to prepare graphene.
Step a:
Be 5 grams using weight, with a thickness of 1mm graphite rod as anode, the platinized platinum of 10cm*10cm as cathode, 200mL's
The mixed solution of oxalic acid and hydrogen peroxide carries out electrochemical stripping as electrolyte, to graphite rod.Wherein, hydrogen peroxide is hydrogen peroxide
Aqueous solution, be 1M in the molar concentration of the electrolyte mesoxalic acid, the molar concentration of hydrogen peroxide is 2M, i.e. oxalic acid and peroxidating
The molar concentration rate of hydrogen is 1: 2；The distance of anode and cathode is 3cm, and voltage is constant in 15V, and stirs along with magneton, magneton
The revolving speed of stirring is 250r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, carries out electricity to graphite rod
Chemical stripping 60 minutes, obtain graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 45 minutes at 100 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses N- methylpyrrole
Alkanone, then ultrasonic treatment is carried out 10 minutes to the organic solvent dissolved with graphene sample, it can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention four is 3~6 layers, and yield 98.4%, defect is less.
Embodiment five
The present embodiment successively uses following steps to prepare graphene.
Step a:
It is 5 grams using weight, is used as anode with a thickness of the highly oriented pyrolytic graphite of 1mm, the platinized platinum of 10cm*10cm is as negative
Pole, the oxalic acid of 200mL and the mixed solution of hydrogen peroxide carry out electrochemical stripping to highly oriented pyrolytic graphite as electrolyte.Its
In, it is 0.1M in the molar concentration of the electrolyte mesoxalic acid that hydrogen peroxide, which is the aqueous solution of hydrogen peroxide, hydrogen peroxide it is mole dense
Degree is 5M, i.e., the molar concentration rate of oxalic acid and hydrogen peroxide is 1: 50；The distance of anode and cathode be 2cm, voltage it is constant
10V, and stirred along with magneton, the revolving speed of magneton stirring is 320r/min, and electrolyte passes through cycle refrigeration system for temperature
It is constant that highly oriented pyrolytic graphite is carried out electrochemical stripping 120 minutes at 30 DEG C, obtain graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 60 minutes at 200 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses N- methylpyrrole
Alkanone, then ultrasonic treatment is carried out 10 minutes to the organic solvent dissolved with graphene sample, it can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention five is 1~5 layer, and yield 98%, defect is less.
Embodiment six
The present embodiment successively uses following steps to prepare graphene.
Step a:
Be 5 grams using weight, with a thickness of 1mm graphite flake as anode, the graphite of 10cm*10cm*0.3mm as cathode,
The oxalic acid of 200mL and the mixed solution of hydrogen peroxide carry out electrochemical stripping to graphite flake as electrolyte.Wherein, hydrogen peroxide is
The aqueous solution of hydrogen peroxide is 0.5M in the molar concentration of the electrolyte mesoxalic acid, and the molar concentration of hydrogen peroxide is 5M, i.e., careless
The molar concentration rate of acid and hydrogen peroxide is 1: 10；The distance of anode and cathode is 1cm, and voltage is constant in 3V, and along with magnetic
Son stirring, the revolving speed of magneton stirring is 400r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, to stone
Ink sheet carries out electrochemical stripping 180 minutes, obtains graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 90 minutes at 60 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses N, N- dimethyl methyl
Amide, then ultrasonic treatment is carried out 60 minutes to the organic solvent dissolved with graphene sample, it can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention six is 1~7 layer, and yield 94%, defect is less.
Embodiment seven
The present embodiment successively uses following steps to prepare graphene.
Step a:
Be 5 grams using weight, with a thickness of 1mm graphite flake as anode, the platinized platinum of 10cm*10cm as cathode, 200mL's
The mixed solution of oxalic acid and hydrogen peroxide carries out electrochemical stripping as electrolyte, to graphite flake.Wherein, hydrogen peroxide is hydrogen peroxide
Aqueous solution, be 1M in the molar concentration of the electrolyte mesoxalic acid, the molar concentration of hydrogen peroxide is 0.5M, i.e. oxalic acid and peroxide
The molar concentration rate for changing hydrogen is 1: 0.5；The distance of anode and cathode is 4cm, and voltage is constant in 30V, and stirs along with magneton,
Magneton stirring revolving speed be 500r/min, and electrolyte by cycle refrigeration system temperature is constant at 10 DEG C, to graphite flake into
Row electrochemical stripping 150 minutes, obtain graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 10 minutes at 200 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses dimethyl sulfoxide,
Ultrasonic treatment is carried out 15 minutes to the organic solvent dissolved with graphene sample again, can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention seven is 3~7 layers, and yield 95.8%, defect is less.
Embodiment eight
The present embodiment successively uses following steps to prepare graphene.
Step a:
Be 5 grams using weight, with a thickness of 1mm graphite flake as anode, the platinized platinum of 10cm*10cm as cathode, 200mL's
The mixed solution of oxalic acid and hydrogen peroxide carries out electrochemical stripping as electrolyte, to graphite flake.Wherein, hydrogen peroxide is hydrogen peroxide
Aqueous solution, be 0.1M in the molar concentration of the electrolyte mesoxalic acid, the molar concentration of hydrogen peroxide is 5M, i.e. oxalic acid and peroxide
The molar concentration rate for changing hydrogen is 1: 50；The distance of anode and cathode is 4cm, and voltage is constant in 3V, and stirs along with magneton, magnetic
The revolving speed of son stirring is 450r/min, and electrolyte is constant at 5 DEG C by temperature by cycle refrigeration system, carries out electricity to graphite flake
Chemical stripping 1 minute, obtain graphene presoma.
Step b:
Electrolyte after reaction in step a is realized by filtering and is separated by solid-liquid separation, is dispersed in the electrolytic solution with extracting
Filtered electrolyte can be recycled in graphene presoma, and the graphene presoma being obtained by filtration can be without cleaning treatment, directly
It is dried 90 minutes at 180 DEG C and obtains pure graphene sample.
Step c:
The graphene sample dried in step b is dissolved in organic solvent, organic solvent uses dimethyl sulfoxide,
Ultrasonic treatment is carried out 50 minutes to the organic solvent dissolved with graphene sample again, can be obtained graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention eight is 2~4 layers, and yield 95.1%, defect is less.
Certainly, the separation of solid and liquid in the step b of graphene preparation process of the invention can also use centrifugal separation technology.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention
Protection scope.
Claims (10)
1. a kind of preparation method of graphene, which comprises the following steps:
A) using graphite material as the material of anode, the mixed solution of oxalic acid and hydrogen peroxide carries out cell reaction as electrolyte
Realize the electrochemical stripping to anode material；
B) electrolyte after reacting in step a is separated by solid-liquid separation, to extract the graphene forerunner of dispersion in the electrolytic solution
Body, then graphene presoma progress drying and processing is made into remaining electrolyte decomposition thereon, obtain graphene sample；
C) graphene sample dried in step b is dissolved in organic solvent, then had to dissolved with graphene sample
Solvent is ultrasonically treated, and graphene solution is obtained.
2. the preparation method of graphene according to claim 1, which is characterized in that in the cell reaction of step a
It is stirred during progress along with magneton, the revolving speed of the magneton stirring is 50~500r/min.
3. the preparation method of graphene according to claim 1, which is characterized in that the electrolyte mesoxalic acid of step a
Molar concentration rate with hydrogen peroxide is 1: 0.5~1: 50.
4. the preparation method of graphene according to claim 1, which is characterized in that the perseverance of cell reaction described in step a
Constant voltage is 3~30V, and the temperature of electrolyte is 5~30 DEG C.
5. the preparation method of graphene according to claim 1, which is characterized in that the yin of cell reaction described in step a
Extremely platinized platinum, the distance of anode and cathode are 1~10cm, and the time of cell reaction is 1~180 minute.
6. the preparation method of graphene according to claim 1, which is characterized in that the temperature of drying and processing described in step b
Degree is 60~200 DEG C, and the time is 10~90 minutes.
7. the preparation method of graphene according to claim 6, which is characterized in that the temperature of the drying and processing is 190
DEG C, the time is 30 minutes.
8. the preparation method of graphene according to claim 1, which is characterized in that ultrasonic treatment described in step c when
Between be 10~60 minutes.
9. the preparation method of graphene according to claim 1, which is characterized in that the graphite material is graphite flake, squama
Any one or more block graphite material being process in piece graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite.
10. the preparation method of graphene according to claim 1, which is characterized in that organic solvent described in step c is N,
Any one or more in dinethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN104803380A (en) * | 2015-05-12 | 2015-07-29 | 中国科学院上海微系统与信息技术研究所 | Preparation method of graphene |
| CN104860300A (en) * | 2015-04-20 | 2015-08-26 | 德阳烯碳科技有限公司 | Graphene preparation method |
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| CN104773730A (en) * | 2015-04-29 | 2015-07-15 | 中国科学院深圳先进技术研究院 | Method for preparing graphene |
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