CN107235487A - The preparation method of graphene - Google Patents
The preparation method of graphene Download PDFInfo
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- CN107235487A CN107235487A CN201610169825.5A CN201610169825A CN107235487A CN 107235487 A CN107235487 A CN 107235487A CN 201610169825 A CN201610169825 A CN 201610169825A CN 107235487 A CN107235487 A CN 107235487A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- 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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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The preparation method of graphene comprises the following steps：A) using graphite material as the material of anode, the mixed solution of oxalic acid and hydrogen peroxide is used as electrolyte, carries out cell reaction and realizes electrochemical stripping to anode material；B) reacted electrolyte in step a is subjected to separation of solid and liquid, to extract scattered graphene presoma in the electrolytic solution, then the electrolyte decomposition that graphene presoma progress drying and processing to remain thereon, obtains graphene sample；C) obtained graphene sample will be dried in step b to be dissolved in organic solvent, then the organic solvent for being dissolved with graphene sample is carried out 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 can be realized; it is easy to removal of impurities; environmental protection and energy saving, improve yield.
Description
Technical field
The present invention relates to grapheme material preparing technical field, and in particular to a kind of preparation method of graphene.
Background technology
Since acquisition high-quality graphene is peeled off using micromechanics stripping means, it is only that graphene has
High electric conductivity heat conduction and mechanical performance attract scientific research circle and the great interest of industrial circle always.Due to superiority
Can, the market demand of graphene is also increasing, and this requires the preparation constantly improvement of grapheme material and can
The technology of preparing of green non-pollution is realized to obtain the high-quality graphene of high-volume.But current preparation face
Also there is very big challenge to commercial application.First, the chemical vapor deposition of high-quality graphene can be obtained
There is low yield, high energy consumption and transfer in technology and epitaxial growth method；In addition, chemical oxidation is also
Although former method can be realized prepares graphene on a large scale, there are a large amount of oxy radicals and be connected to graphene sheet layer
On, cause the electrical and thermal conductivity performance of graphene to be greatly lowered.Moreover, ultrasonic stripping method and liquid phase shearing stripping
High-quality grapheme material can be obtained from method, also without using strong acid or strong oxidizer, and without metal
Ion, but the graphene lateral dimension obtained is less than normal, it is most important that and yield is very low, and often yield is less than
5%, and need to be separated by filtration, less economical, total cost performance is not still high.
For existing graphene preparation technology, otherwise high-quality high cost, otherwise cost low quality is poor, stone
Black alkene industry development need badly it is a kind of can be mass-produced, high-quality, inexpensive and green non-pollution preparation skill
Art, to break through grapheme material bottleneck.It is one of possible approach that electrochemistry, which prepares graphene,.Compared to oxygen
Change reducing process, electrochemical process does not need strong oxidizer, the substitute is electric field oxidation stripping；Compared to change
Gas phase deposition technology is learned, yield prepared by electrochemistry is far longer than gas phase deposition technology；Compared to ultrasound or liquid
Mutually shearing is less than 5% yield, and electrochemical process can obtain the yield close to 100%.But existing electrochemistry
Technology of preparing not enough or be not enough to be used for prepare high-quality grapheme material on a large scale.
In disclosed electrochemistry prepares the document and patent of graphene, used electrolyte can divide
For ionic liquid, strong acid, and some salting liquids.Wherein, exist in the prior art and made using ionic liquid
Negative electrode intercalation stripping is carried out for electrolyte, the graphene that thickness is 2~3 layers, oxygen content is 2.5% can be obtained,
But when using ionic liquid as electrolyte, the common problem encountered is that ionic liquid is expensive and complexity
Zwitterion impurity remove highly difficult etc., thus be difficult to industrialization and use.Also there is one kind in the prior art
The technology of similar il electrolyte mechanism, particular by salt such as high-temperature heating potassium chloride, sodium chloride,
It is set to melt as electrolyte, the graphene defect of gained is few, low for equipment requirements, but hot conditions energy
Consumption is higher, containing largely it is difficult to cleared ion such as chlorion, potassium ion and sodium ion in obtained product
Deng the greatly use of influence graphene.A large amount of sulfuric acid and sweet ammonia are used in addition, also existing in the prior art
Acid is used as electrolyte, although peeling rate quickly, can be completed in 5 minutes, and it is 2~5 that can obtain thickness
The graphene of layer, but equally exist and be difficult to cleared sulfate radical and glycine ion completely.In addition, relative ring
Protect and easy method is, as electrolyte, lithium to be used for example, existing in the prior art using some salting liquids
The electrolyte of solvation is made in salt and propene carbonate, lithium ion is inserted into graphite layers in electrolytic process
Peel off and obtain graphene, but there is the removal of electrolyte and foreign ion after complex operation, stripping very
The problem of bothering and add the cost of industrialization.In addition, also similar in the presence of also using in the prior art
Electrolyte K2SO4Salting liquid is peeled off, and the voltage needed for this technology is relatively low, and required time is also shorter,
But the product of reaction can introduce and be difficult to completely cleared metal ion, and sulfate ion equally understands part oxygen
Graphite alkene lamella, remaining sulfate radical is also relatively difficult to remove.Used moreover, also existing in the prior art
Ammonium sulfate is as electrolyte, and the yield that this method is obtained is up to 85%, and the reaction time is short, but this method
The problem of sulfate ion can not be cleared is similarly faced, while sulfate ion also has in electrolytic process
SO2Toxic gas is produced, not enough environmental protection and safety.
The content of the invention
It is an object of the invention to the defect for overcoming prior art, there is provided a kind of environmental protection and energy saving, low cost and production
The preparation method of the high graphene of rate.
To achieve the above object, present invention employs following technical scheme：
A kind of preparation method of graphene, comprises the following steps：
A) using graphite material as the material of anode, the mixed solution of oxalic acid and hydrogen peroxide enters as electrolyte
The electrochemical stripping to anode material is realized in row cell reaction；
B) reacted electrolyte in step a is subjected to separation of solid and liquid, disperseed in the electrolytic solution with extracting
Graphene presoma, then graphene presoma is subjected to the electrolyte decomposition that drying and processing to remain thereon,
Obtain graphene sample；
C) obtained graphene sample will be dried in step b to be dissolved in organic solvent, then to being dissolved with graphite
The organic solvent of alkene sample carries out ultrasonically treated, acquisition graphene solution.
Preferably, stirred during the progress of the step a cell reaction along with magneton, the magnetic
The rotating speed of son stirring is 50~500r/min.
Preferably, the molar concentration rate of the step a electrolyte mesoxalic acid and hydrogen peroxide be 1: 0.5~
1∶50。
Preferably, the constant voltage of cell reaction described in step a is 3~30V, the temperature of electrolyte for 5~
30℃。
Preferably, the negative electrode of cell reaction described in step a is platinized platinum, and the distance of anode and negative electrode is 1~10cm,
The time of cell 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 ultrasonically treated described in step c is 10~60 minutes.
Preferably, the graphite material is graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly directional heat
Solve any one or more block graphite material processed in graphite.
Preferably, organic solvent described in step c be DMF, 1-METHYLPYRROLIDONE and
Any one or more in dimethyl sulfoxide (DMSO).
The preparation method of the graphene of the present invention, the electrolyte mixed by using oxalic acid and hydrogen peroxide exists
The electrochemical stripping to graphite material is realized under electric field action, it is possible to achieve inexpensive, pollution-free, free from admixture
With prepare with scale graphene；Electrolyte in itself with it during the course of the reaction, due to no strong acid and metal from
Son, resulting electrolysate need not be cleaned, and directly carry out drying and processing, you can will remain in electrolysis production
Oxalic acid and hydrogen peroxide on thing are thoroughly removed, environmental protection and energy saving, improve product purity and yield, simplify production work
Skill, is easy to implement large-scale production, and cell reaction process mainly happens is that the reaction of oxalic acid and hydrogen peroxide,
Water and carbon dioxide, nontoxic pollution-free are produced, except electrolyte in whole technological process, will not be produced other
Pollutant, technological process is expected from former material, then to final product, complete green non-pollution, realization was produced
Journey is environment-friendly；Electrolyte is oxalic acid and hydrogen peroxide, and itself is nontoxic, pollution-free, soluble in water, institute
Aqueous phase may be selected to be with electrolyte, more environmentally-friendly cleaning reduces production cost.
Brief description of the drawings
The scanning electron microscope diagram for the graphene that Fig. 1 is obtained by embodiment one；
The scanning electron microscope diagram for the graphene that Fig. 2 is obtained by embodiment one；
The transmission electron microscope figure for the graphene that Fig. 3 is obtained by embodiment one；
The transmission electron microscope figure for the graphene that Fig. 4 is obtained by embodiment one；
SEAD figure under the transmission electron microscope for the graphene that Fig. 5 is obtained by embodiment one；
Fig. 6 is the Raman spectrogram for the graphene that the electrochemical stripping of embodiment one is obtained.
Embodiment
The embodiment provided below in conjunction with accompanying drawing 1 to 6, further illustrates the preparation side of the graphene of the present invention
The embodiment of method.The preparation method of the graphene of the present invention is not limited to the following description.
The preparation method of the graphene of the present invention comprises the following steps：
A) using graphite material as anode material, the mixed solution of oxalic acid and hydrogen peroxide is used as electrolyte, carries out
The electrochemical stripping to anode material is realized in cell reaction.
B) reacted electrolyte in step a is subjected to separation of solid and liquid, disperseed in the electrolytic solution with extracting
Graphene presoma, then graphene presoma is subjected to the electrolyte decomposition that drying and processing to remain thereon,
Obtain graphene sample.
C) obtained graphene sample will be dried in step b to be dissolved in organic solvent, then to being dissolved with graphite
The organic solvent of alkene sample carries out ultrasonically treated, acquisition graphene solution.
Wherein, graphite material can use graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly directional heat
Solve any one or more block graphite material processed in graphite；Organic solvent in step c can
With using any one or more in DMF, 1-METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO).
Can be using negative electrode of the conductive materials such as graphite or platinized platinum as cell reaction in step a.
The preparation method of the graphene of the present invention, the electrolyte mixed by using oxalic acid and hydrogen peroxide exists
The electrochemical stripping to graphite material is realized under electric field action, it is possible to achieve inexpensive, pollution-free, free from admixture
With prepare with scale graphene；Electrolyte in itself with it during the course of the reaction, due to no strong acid and metal from
Son, resulting electrolysate need not be cleaned, and directly carry out drying and processing, you can will remain in electrolysis production
Oxalic acid and hydrogen peroxide on thing are thoroughly removed, environmental protection and energy saving, improve product purity and yield, simplify production work
Skill, is easy to implement large-scale production, and cell reaction process mainly happens is that the reaction of oxalic acid and hydrogen peroxide,
Water and carbon dioxide, nontoxic pollution-free are produced, except electrolyte in whole technological process, will not be produced other
Pollutant, technological process is expected from former material, then to final product, complete green non-pollution, realization was produced
Journey is environment-friendly；Electrolyte is oxalic acid and hydrogen peroxide, and itself is nontoxic, pollution-free, soluble in water, institute
Aqueous phase may be selected to be with electrolyte, more environmentally-friendly cleaning reduces production cost.
The principle of the preparing graphene by electrochemical stripping of the present invention：In the presence of electric field, oxalic acid is ionized
Oxalate and oxalic acid hydrogen radical anion are formed, and the oxalate and oxalic acid hydrogen radical ion that ionize out are to as anode
Graphite material move and be equably inserted into the lamellar spacing of graphite material；Then oxalate and oxalic acid hydrogen radical
Reacted again with the hydrogen peroxide in solution, produce substantial amounts of carbon dioxide, these carbon dioxides
Constantly expansion is gathered in the lamellar spacing of graphite material, and most graphene is equably shelled from graphite material at last
Separate out and.Judgement based on a large amount of electron micrographs and Raman data, the number of plies of resulting graphene is
1-10 layers, yield >=93%, defect is less.
The specific embodiment of the preparation method of the graphene of the present invention.
Embodiment one
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, graphite flake that thickness is 1mm as anode, 10cm*10cm platinized platinum as negative electrode,
200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemical stripping as electrolyte to graphite flake.Its
In, hydrogen peroxide is the aqueous solution of hydrogen peroxide, and hydrogen peroxide can use 30% commercially available hydrogen peroxide, at this
The molar concentration of electrolyte mesoxalic acid is 1M, and the molar concentration of hydrogen peroxide is 5M, i.e. oxalic acid and hydrogen peroxide
Molar concentration rate be 1: 5；The distance of anode and negative electrode is 2cm, and voltage constant is in 10V, and along with magnetic
Son stirring, the rotating speed of magneton stirring is 50r/min, and electrolyte is constant by temperature by cycle refrigeration system
At 25 DEG C, electrochemical stripping is carried out 30 minutes to graphite flake, graphene presoma is obtained.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 30 minutes directly at 190 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses N- first
Base pyrrolidones, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 30 minutes, you can obtain
Obtain graphene solution.
Scanning electron microscope test result such as Fig. 1 and Fig. 2 of graphene obtained by the embodiment of the present invention one
It is shown, the macro surface pattern and microcosmic edge pattern of graphene are disclosed respectively, can be with by Fig. 1 and Fig. 2
Find out the lamellar structure of graphene than more complete；The transmission electron microscope of graphene obtained by embodiment one
As a result as shown in Figure 3 and Figure 4, graphene sheet layer size and the number of plies of graphene are presented respectively, by right
Fig. 3 and Fig. 4 observation and analysis understands that the piece number of plies of obtained graphene is 1~3 layer；Embodiment one
SEAD figure is as shown in Figure 5 under the transmission electron microscope of obtained graphene, it is shown that graphite
The complete lattice structure of alkene；Raman results show graphene as shown in fig. 6, give G peaks one low
Defect it is very low；In addition, the yield of the graphene obtained by embodiment one is 98.7%.
Embodiment two
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, crystalline flake graphite that thickness is 1mm as anode, 10cm*10cm platinized platinum is used as the moon
Pole, 200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemistry stripping as electrolyte to crystalline flake graphite
From.Wherein, hydrogen peroxide is the aqueous solution of hydrogen peroxide, is 1M in the molar concentration of the electrolyte mesoxalic acid,
The molar concentration of hydrogen peroxide is that the molar concentration rate of 5M, i.e. oxalic acid and hydrogen peroxide is 1: 5；Anode and the moon
The distance of pole is 10cm, and voltage constant is stirred in 30V, and along with magneton, and the rotating speed of magneton stirring is 100
R/min, and electrolyte is constant at 30 DEG C by temperature by cycle refrigeration system, and electrochemistry is carried out to crystalline flake graphite
Peel off 3 minutes, obtain graphene presoma.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 80 minutes directly at 60 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses N- first
Base pyrrolidones, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 30 minutes, you can obtain
Obtain graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention two be 1~5 layer, yield is 98%, defect compared with
It is few.
Embodiment three
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, graphite foil that thickness is 1mm as anode, 10cm*10cm platinized platinum as negative electrode,
200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemical stripping as electrolyte to graphite foil.Its
In, hydrogen peroxide is the aqueous solution of hydrogen peroxide, is 1M, peroxidating in the molar concentration of the electrolyte mesoxalic acid
The molar concentration of hydrogen is that the molar concentration rate of 1M, i.e. oxalic acid and hydrogen peroxide is 1: 1；Anode and negative electrode away from
From for 4cm, voltage constant is stirred in 20V, and along with magneton, and the rotating speed of magneton stirring is 180r/min,
And electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, 50 points of electrochemical stripping is carried out to graphite foil
Clock, obtains graphene presoma.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 35 minutes directly at 120 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses N- first
Base pyrrolidones, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 30 minutes, you can obtain
Obtain graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention three be 2~5 layers, yield is 93%, defect compared with
It is few.
Example IV
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, graphite rod that thickness is 1mm as anode, 10cm*10cm platinized platinum as negative electrode,
200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemical stripping as electrolyte to graphite rod.Its
In, hydrogen peroxide is the aqueous solution of hydrogen peroxide, is 1M, peroxidating in the molar concentration of the electrolyte mesoxalic acid
The molar concentration of hydrogen is that the molar concentration rate of 2M, i.e. oxalic acid and hydrogen peroxide is 1: 2；Anode and negative electrode away from
From for 3cm, voltage constant is stirred in 15V, and along with magneton, and the rotating speed of magneton stirring is 250r/min,
And electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, 60 points of electrochemical stripping is carried out to graphite rod
Clock, obtains graphene presoma.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 45 minutes directly at 100 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses N- first
Base pyrrolidones, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 10 minutes, you can obtain
Obtain graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention four is 3~6 layers, and yield is 98.4%, defect
It is less.
Embodiment five
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, the highly oriented pyrolytic graphite that thickness is 1mm be used as anode, 10cm*10cm platinized platinum
As negative electrode, 200mL oxalic acid and the mixed solution of hydrogen peroxide are as electrolyte, to highly oriented pyrolytic graphite
Carry out electrochemical stripping.Wherein, hydrogen peroxide is the aqueous solution of hydrogen peroxide, in rubbing for the electrolyte mesoxalic acid
Your concentration is 0.1M, and the molar concentration of hydrogen peroxide is for the molar concentration rate of 5M, i.e. oxalic acid and hydrogen peroxide
1∶50；The distance of anode and negative electrode is 2cm, and voltage constant is stirred in 10V, and along with magneton, magneton
The rotating speed of stirring is 320r/min, and electrolyte is constant at 30 DEG C by temperature by cycle refrigeration system, right
Highly oriented pyrolytic graphite carries out electrochemical stripping 120 minutes, obtains graphene presoma.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 60 minutes directly at 200 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses N- first
Base pyrrolidones, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 10 minutes, you can obtain
Obtain graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention five be 1~5 layer, yield is 98%, defect compared with
It is few.
Embodiment six
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, the graphite flake that thickness is 1mm be used as anode, 10cm*10cm*0.3mm graphite is made
For negative electrode, 200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemistry as electrolyte to graphite flake
Peel off.Wherein, hydrogen peroxide is the aqueous solution of hydrogen peroxide, is 0.5M in the molar concentration of the electrolyte mesoxalic acid,
The molar concentration of hydrogen peroxide is that the molar concentration rate of 5M, i.e. oxalic acid and hydrogen peroxide is 1: 10；Anode and the moon
The distance of pole is 1cm, and voltage constant is stirred in 3V, and along with magneton, and the rotating speed of magneton stirring is 400
R/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, and electrochemistry stripping is carried out to graphite flake
From 180 minutes, graphene presoma is obtained.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 90 minutes directly at 60 DEG C.
Step c：
By dried in step b obtain graphene sample dissolving organic solvent in, organic solvent uses N, N- bis-
NMF, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 60 minutes, you can obtain
Obtain graphene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention six be 1~7 layer, yield is 94%, defect compared with
It is few.
Embodiment seven
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, graphite flake that thickness is 1mm as anode, 10cm*10cm platinized platinum as negative electrode,
200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemical stripping as electrolyte to graphite flake.Its
In, hydrogen peroxide is the aqueous solution of hydrogen peroxide, is 1M, peroxidating in the molar concentration of the electrolyte mesoxalic acid
The molar concentration of hydrogen is that the molar concentration rate of 0.5M, i.e. oxalic acid and hydrogen peroxide is 1: 0.5；Anode and negative electrode
Distance be 4cm, voltage constant stirs in 30V, and along with magneton, and the rotating speed of magneton stirring is 500r/min,
And electrolyte is constant at 10 DEG C by temperature by cycle refrigeration system, electrochemical stripping 150 is carried out to graphite flake
Minute, obtain graphene presoma.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 10 minutes directly at 200 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses diformazan
Base sulfoxide, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 15 minutes, you can obtain stone
Black alkene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention seven is 3~7 layers, and yield is 95.8%, defect
It is less.
Embodiment eight
The present embodiment prepares graphene using following steps successively.
Step a：
Be 5 grams using weight, graphite flake that thickness is 1mm as anode, 10cm*10cm platinized platinum as negative electrode,
200mL oxalic acid and the mixed solution of hydrogen peroxide carry out electrochemical stripping as electrolyte to graphite flake.Its
In, hydrogen peroxide is the aqueous solution of hydrogen peroxide, is 0.1M, peroxide in the molar concentration of the electrolyte mesoxalic acid
The molar concentration for changing hydrogen is that the molar concentration rate of 5M, i.e. oxalic acid and hydrogen peroxide is 1: 50；Anode and negative electrode
Distance is 4cm, and voltage constant is stirred in 3V, and along with magneton, and the rotating speed of magneton stirring is 450r/min,
And electrolyte is constant at 5 DEG C by temperature by cycle refrigeration system, electrochemical stripping is carried out 1 minute to graphite flake,
Obtain graphene presoma.
Step b：
Separation of solid and liquid is realized by filtering to reacted electrolyte in step a, electrolysis is dispersed in extract
Graphene presoma in liquid, the electrolyte after recyclable filtering, the graphene presoma being filtrated to get can not
Cleaning treatment is carried out, drying obtains pure graphene sample for 90 minutes directly at 180 DEG C.
Step c：
Obtained graphene sample will be dried in step b to be dissolved in organic solvent, organic solvent uses diformazan
Base sulfoxide, then the organic solvent for being dissolved with graphene sample is carried out ultrasonically treated 50 minutes, you can obtain stone
Black alkene solution.
The piece number of plies of graphene obtained by the embodiment of the present invention eight is 2~4 layers, and yield is 95.1%, defect
It is less.
Certainly, the separation of solid and liquid in the step b of graphene preparation process of the invention can also be using centrifugation point
From technology.
Above content is to combine specific preferred embodiment further description made for the present invention, no
It can assert that the specific implementation of the present invention is confined to these explanations.For the common of the technical field of the invention
For technical staff, without departing from the inventive concept of the premise, some simple deductions can also be made or replaced
Change, should all be considered as belonging to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of graphene, it is characterised in that comprise the following steps：
A) using graphite material as the material of anode, the mixed solution of oxalic acid and hydrogen peroxide enters as electrolyte
The electrochemical stripping to anode material is realized in row cell reaction；
B) reacted electrolyte in step a is subjected to separation of solid and liquid, disperseed in the electrolytic solution with extracting
Graphene presoma, then graphene presoma is subjected to the electrolyte decomposition that drying and processing to remain thereon,
Obtain graphene sample；
C) obtained graphene sample will be dried in step b to be dissolved in organic solvent, then to being dissolved with graphite
The organic solvent of alkene sample carries out ultrasonically treated, acquisition graphene solution.
2. the preparation method of graphene according to claim 1, it is characterised in that in step a institute
Stirred during the progress for stating cell reaction along with magneton, the rotating speed of the magneton stirring is 50~500
r/min。
3. the preparation method of graphene according to claim 1, it is characterised in that step a's is described
The molar concentration rate of electrolyte mesoxalic acid and hydrogen peroxide is 1: 0.5~1: 50.
4. the preparation method of graphene according to claim 1, it is characterised in that described in step a
The constant voltage of cell reaction is 3~30V, and the temperature of electrolyte is 5~30 DEG C.
5. the preparation method of graphene according to claim 1, it is characterised in that described in step a
The negative electrode of cell reaction is platinized platinum, and the distance of anode and negative electrode is 1~10cm, time of cell reaction for 1~
180 minutes.
6. the preparation method of graphene according to claim 1, it is characterised in that described in step b
The temperature of drying and processing is 60~200 DEG C, and the time is 10~90 minutes.
7. the preparation method of graphene according to claim 6, it is characterised in that the drying and processing
Temperature be 190 DEG C, the time be 30 minutes.
8. the preparation method of graphene according to claim 1, it is characterised in that described in step c
The ultrasonically treated time is 10~60 minutes.
9. the preparation method of graphene according to claim 1, it is characterised in that the graphite material
For any one or more in graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite
The block graphite material processed.
10. the preparation method of graphene according to claim 1, it is characterised in that described in step c
Organic solvent be DMF, 1-METHYLPYRROLIDONE and dimethyl sulfoxide (DMSO) in any one or
It is a variety of.
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| CN107879318A (en) * | 2017-11-01 | 2018-04-06 | 太原理工大学 | A kind of method that bubble stripping method prepares class graphite phase carbon nitride nanometer sheet |
| CN112479203A (en) * | 2020-12-14 | 2021-03-12 | 南京航空航天大学 | Method and product for generating antifriction graphene film on diamond surface in situ |
| CN114314570A (en) * | 2022-01-14 | 2022-04-12 | 曲靖华金雨林科技有限责任公司 | Method for preparing graphene |
| CN114759182A (en) * | 2022-05-25 | 2022-07-15 | 昆明理工大学 | Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107879318A (en) * | 2017-11-01 | 2018-04-06 | 太原理工大学 | A kind of method that bubble stripping method prepares class graphite phase carbon nitride nanometer sheet |
| CN107879318B (en) * | 2017-11-01 | 2020-11-06 | 太原理工大学 | Method for preparing graphite-like phase carbon nitride nanosheets by bubble stripping method |
| CN112479203A (en) * | 2020-12-14 | 2021-03-12 | 南京航空航天大学 | Method and product for generating antifriction graphene film on diamond surface in situ |
| CN112479203B (en) * | 2020-12-14 | 2022-03-04 | 南京航空航天大学 | Method and product for generating antifriction graphene film on diamond surface in situ |
| CN114314570A (en) * | 2022-01-14 | 2022-04-12 | 曲靖华金雨林科技有限责任公司 | Method for preparing graphene |
| CN114759182A (en) * | 2022-05-25 | 2022-07-15 | 昆明理工大学 | Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery |
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