CN107235486A - The preparation method of water-soluble graphene - Google Patents
The preparation method of water-soluble graphene Download PDFInfo
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- CN107235486A CN107235486A CN201610169746.4A CN201610169746A CN107235486A CN 107235486 A CN107235486 A CN 107235486A CN 201610169746 A CN201610169746 A CN 201610169746A CN 107235486 A CN107235486 A CN 107235486A
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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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- 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
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Abstract
The preparation method of water-soluble graphene comprises the following steps：A) using graphite material as anode material, the aqueous solution of persulfate carries out electrochemical stripping of the cell reaction realization to anode material, obtains tentatively scattered water soluble disperse thing as electrolyte；B) dispersion obtained in step a is subjected to ultrasonically treated, filtration washing and drying and processing successively, obtains water-soluble graphene powder, then water-soluble graphene powder is dispersed in water, obtain the dispersion liquid of graphene.The present invention provides a kind of preparation method of water-soluble graphene, the electrochemical stripping to graphite material is realized under electric field action for electrolyte by using the aqueous solution of persulfate, the characteristics of with safety, low, pollution-free cost, weak oxide, overcome graphene poorly water-soluble and the problem of water-soluble and electric conductivity can not be taken into account, post processing is easy, and product has water miscible while the good conductive capability of holding and mechanical strength, free from admixture, efficiency and yield are high, and technological process is simple.
Description
Technical field
The present invention relates to grapheme material preparing technical field, and in particular to a kind of preparation of water-soluble graphene
Method.
Background technology
Graphene is very big with industrial circle because its unique conductive and heat-conductive and mechanical performance attract scientific research circle always
Interest.For graphene self character, the graphene of structural integrity is by without any labile bond
The two dimensional crystal that benzene hexatomic ring is combined, the inert state in surface, the phase with other media (such as solvent)
Interaction is weaker, and has stronger Van der Waals force between the piece and piece of graphene, easily produces back folded and poly-
Collection, makes it be insoluble in water and conventional organic solvent, and this is to the effectively scattered of graphene and extensively using causing
Great difficulty.And with the development of the industry, grapheme material is in electronics, information, the energy, material
Wide application prospect is shown with the field such as biological medicine, this requires that grapheme material has high-quality, nothing
With good dispersibility to meet different application field while impurity, high conductivity.In addition, facing
The increasing market demand, the extensive preparation of graphene also requires that nontoxic, pollution-free, inexpensive, work
The features such as skill is simple, and also there is very big challenge in these areas in existing grapheme material.In order to abundant
Its advantageous property is played, improves its molding processibility (such as improving dissolubility, dispersiveness in the base),
Effective functionalization must be carried out to graphene.It is chemical oxidation to study most commonly used functional method at present
Reducing process, graphene oxide soluble in water can be prepared on a large scale, but oxy radical and defect are a lot,
Electrical and thermal conductivity performance is caused to be greatly lowered, and preparation process is complicated and introduces substantial amounts of acid and strong oxidizer,
It is difficult to completely cleared.Exist in the prior art makes graphite functionalization using sulfuric acid and potassium permanganate, and adds ten
Dialkyl benzene sulfonic acids sodium obtains water miscible graphene, and gained graphene is uniformly dispersed and prepared in water
The conductance of conductive film is up to 1300S/m, but preparation process has used strong acid, strong oxidizer, technique
Complexity, seriously polluted, removal of impurities is difficult, destroys big to graphene assertive evidence structure, defect is more.In the prior art
There is also a kind of technology of preparing of water at normal temperature dissolubility graphene, pass through the concentrated sulfuric acid and potassium permanganate oxidation graphite
Material, has similarly used that to face preparation technology not environmentally friendly enough, and cost is high, the problems such as product is not pure enough.
In addition, also exist in the prior art using concentrated sulfuric acid oxidation, the method for hydrazine hydrate reduction prepares water-soluble stone
Black alkene, this technology is relative to the use of strong acid strong oxidizer, and security improves, and technique is also relatively easy,
But during introduce too many chemical substance, gained sample is not pure enough, and defect is more, and raw material hydrazine hydrate has
Malicious explosive, seriously polluted, cost is high.
Existing chemical oxidation techniques prepare water-soluble graphene mainly by strong acid, strong oxidizer and scattered
Agent is obtained, the problems such as prepare with scale faces high seriously polluted, cost, complex process, not high security,
The graphene defect of acquisition is more, and impurity content is high.Therefore, a kind of extensive, low cost is needed badly, without miscellaneous
Matter, while the water-soluble graphene technology of preparing of green safety.Electrochemistry is to prepare having for graphene on a large scale
One of effect means, its principle is by electric field-assisted intercalation and stripping, compared to chemical oxidation intercalation, electrification
Method does not need strong oxidizer and strong acid, the substitute is electric field oxidation stripping, time high with yield
It is short, environmental protection, the advantages of yield is high.But graphene prepared by existing electrochemical techniques is essentially all molten
Solution can not be dissolved in the water in organic solvent.Graphene prepared by electrochemistry is difficult to be dissolved in the main of water
Reason is under electric field action, although graphite is in anode, there is the process that electric field-assisted is aoxidized, but due to electricity
Quick stripping, independent graphene is formed departing from electrode surface once being stripped, would not be by
Electric field is aoxidized, and the oxidation benefit of electrolyte in itself is extremely weak.Exist in the prior art with cetyl trimethyl
Ammonium bromide solution peels off the method that graphite prepares graphene oxide as electrolyte, and obtaining graphene oxide has
Good functionalization, its carbon-to-oxygen ratio can reach 5.5.It is inefficient but this method reaction time is longer,
And electrolyte is complicated, removal of impurities is difficult so that the extensive pure grapheme material of acquisition is relatively difficult,
Cost is also of a relatively high, is difficult to apply to the extensive preparation of high-quality water soluble graphene.One article report
Road has obtained the graphene of 7,7,8,8- tetracyano-p-quinodimethane functionalizations, and its oxygen content reaches 20.62%,
There is good dispersibility in water, but this technical matters is complicated, electrolyte preparation procedure is more, cost
Height, and electrolyte and graphene product interaction are strong, it is difficult to remove, it is difficult to prepared by extensive industrialization
Water miscible grapheme material.Therefore, a kind of technique is invented simple, low cost, free of contamination water-soluble stone
Black alkene technology of preparing has very big meaning.
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 low-cost and pollution-less, operation letter
The preparation method of single and easily removal of impurities water-soluble graphene.
To achieve the above object, present invention employs following technical scheme：
A kind of preparation method of water-soluble graphene, comprises the following steps：
A) using graphite material as anode material, the aqueous solution of persulfate is as electrolyte, and progress is electrolysed anti-
The electrochemical stripping to anode material should be realized, tentatively scattered water soluble disperse thing is obtained；
B) dispersion obtained in step a is subjected to ultrasonically treated, filtration washing and drying and processing successively,
Water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, point of graphene is obtained
Dispersion liquid.
Preferably, the constant voltage of cell reaction described in step a is 30~80V.
Preferably, the constant voltage is 50V-60V.
Preferably, stirred during the progress of the step a cell reaction along with magneton, magneton is stirred
The rotating speed mixed is 50~500r/min.
Preferably, the molar concentration of persulfate is 0.01~0.5M in electrolyte described in step a.
Preferably, the negative electrode of cell reaction described in step a is platinized platinum, the distance of anode and negative electrode for 0.5~
5cm, the time of cell reaction is 1~120 minute, and the temperature of electrolyte is 5~30 DEG C.
Preferably, the time ultrasonically treated described in step b is 10~60 minutes.
Preferably, the time of drying and processing described in step b is 40~60 DEG C.
Preferably, persulfate described in step a is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, over cure
In sour hydrogen sodium, hydrogen persulfate ammonium and ammonium persulfate-sodium bisulfate any one or it is a variety of.
Preferably, the graphite material is graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly directional heat
Solve any one or more in graphite.
The preparation method of the water-soluble graphene of the present invention, is electrolyte by using the aqueous solution of persulfate
The electrochemical stripping to graphite material is realized under electric field action, it is low, pollution-free, weak with safety, cost
The characteristics of oxidation, overcome graphene poorly water-soluble and the problem of water-soluble and electric conductivity can not be taken into account, fit
Large-scale industrialized production is closed, with extensive prospects for commercial application；Electrolyte is the salt with oxidisability,
The effect of strong acid it is not related to, so electrolyte may be selected to be aqueous phase, post processing is easy；Required electrolyte is dense
Degree is relatively low, and cost is low, and production efficiency is high, pollution-free；Electrolytic process is without strong oxidation, to graphene film
The destructiveness of the intrinsic structure of layer is relatively low so that sample with water miscible while keeping good conductive energy
Power and mechanical strength；Over cure acid group is decomposed in the reaction, and metal ion can also be in suction filtration cleaning process
Remove, obtain product free from admixture；The process time of reaction is short, efficiency high, and yield is high, and technological process is simple,
Cost is low, can be mass-produced.
Brief description of the drawings
The graphene transmission electron microscope figure that Fig. 1 is obtained by embodiment one；
The graphene SEAD microscope figure that Fig. 2 is obtained by embodiment one；
The graphene scanning electron microscope diagram that Fig. 3 is obtained by embodiment one；
The graphene that Fig. 4 is obtained by embodiment one is dissolved in the displaying figure of water；
The graphene X-ray photoelectron spectroscopic analysis figure that Fig. 5 is obtained by embodiment one.
Embodiment
The embodiment provided below in conjunction with accompanying drawing 1 to 5, further illustrates the water-soluble graphene of the present invention
The embodiment of preparation method.The preparation method of the water-soluble graphene of the present invention is not limited to following implementation
The description of example.
The preparation method of the water-soluble graphene of the present invention comprises the following steps：
A) using graphite material as anode material, the aqueous solution of persulfate is as electrolyte, and progress is electrolysed anti-
The electrochemical stripping to anode material should be realized, tentatively scattered water soluble disperse thing is obtained；
B) dispersion obtained in step a is subjected to ultrasonically treated, filtration washing and drying and processing successively,
Water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, point of graphene is obtained
Dispersion liquid.Stirred described in step a while cell reaction along with magneton, the rotating speed of magneton stirring for 50~
500r/min。
Wherein, persulfate described in step a is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, persulfuric acid
Any one in hydrogen sodium and ammonium persulfate-sodium bisulfate or a variety of, preferably persulfuric acid complex salt.It is described
Graphite material is any one in graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite
Plant or a variety of.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 water-soluble graphene of the present invention, is electrolyte by using the aqueous solution of persulfate
The electrochemical stripping to graphite material is realized under electric field action, it is low, pollution-free, weak with safety, cost
The features such as oxidation, overcome graphene poorly water-soluble and take into account the problem of water-soluble and electric conductivity, be adapted to big
Scale industrialization is produced, with extensive prospects for commercial application；Electrolyte is the salt with oxidisability, no
It is related to the effect of strong acid, so electrolyte may be selected to be aqueous phase, post processing is easy；Required concentration of electrolyte
Relatively low, cost is low, and production efficiency is high, pollution-free；Electrolytic process is without strong oxidation, to graphene sheet layer
Intrinsic structure destructiveness it is relatively low so that sample with water miscible while keeping good conductive capability
And mechanical strength；Over cure acid group is decomposed in the reaction, and metal ion can also be removed in suction filtration cleaning process,
Obtain product free from admixture；The process time of reaction is short, efficiency high, and yield is high, and technological process is simple, cost
It is low, it can be mass-produced.
The present invention prepares the principle of graphene：From oxidant persulfate as electrolyte, in higher electric field
In the presence of, over cure acid radical anion and persulfuric acid hydrogen radical anion transport in electrolyte to anode and by
Gradually equably it is intercalation into the lamellar spacing of graphite, then in the presence of Anodic, by graphite flake layer
Aoxidize and it is come off and be dissolved in electrolyte.Relative to other inorganic salts persulfates as electrolyte, its
Oxidisability is stronger, it is easier to obtain possessing hydrophilic graphene；High electric field accelerates electron transfer rate
Also over cure acid group hydrogen persulfate radical ion free radicalization is accelerated simultaneously, improve reaction efficiency；In electrochemistry
During, anode happens is that oxidation reaction, i.e. the process electrochemical oxidation of anodization process.Cause
This water solubility of the invention is embodied in the graphene of functionalization, because persulfate is under electrochemical action, makes
Obtain and be connected to many oxy radicals on graphene sheet layer, improve the polarity of graphene, possess graphene
Solvability in water, while also having good electric conductivity.Wherein, the oxidisability of persulfate is relative
Potassium permanganate is weak a lot, to the destructive relatively low of graphite-structure, and relative to strong acid, non-corrosiveness, instead
Sylvite, sodium salt or ammonium salt after answering can be by simply washing complete removal.In addition, utilizing high electricity
Pressure (30~80V) can accelerate the migration of ion and the stripping process of graphite, be carried relative to other electrochemical methods
High production efficiency and yield, while a high electric field can also promote oxidizing process so that in usual conditions
Under be not enough to the persulfate of graphite oxide under high electric field by graphite oxidation.
The specific embodiment of the preparation method of the water-soluble graphene of the present invention.
Embodiment one
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Ammonium persulfate-sodium bisulfate the aqueous solution as electrolyte, cell reaction is carried out to carry out electrification to graphite flake
Learn and peel off, wherein, the molar concentration of ammonium persulfate-sodium bisulfate is 0.05M in electrolyte；In cell reaction,
The distance of anode and negative electrode is 1.5cm, and voltage constant is stirred in 50V, and along with magneton, magneton stirring
Rotating speed be 300r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, to graphite flake
Carry out electrochemical stripping 5 minutes, obtain tentatively scattered water soluble disperse thing.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 50 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 4mg in the dispersion liquid
mL-1。
Transmission electron microscope test result such as Fig. 1 and Fig. 2 of the graphene of the gained of embodiments of the invention one,
Disclose the size and crystal property of the lamella of graphene respectively, by the observation to Fig. 1 and Fig. 2 and
Analysis understands that the piece number of plies of the graphene of gained is 3-5 layers；SEM result as shown in figure 3,
The microscopic appearance of water-soluble graphene is illustrated, the lamellar structure of graphene is than more complete as seen from Figure 3；
The picture of the water-soluble graphene dispersion liquid of gained is as shown in figure 4, illustrate point of the water-soluble graphene in water
The ability of dissipating；The graphene X-ray photoelectron spectroscopic analysis result of gained is as shown in Figure 5, it is shown that graphene
The oxygen-containing functional group of the graphene.In addition, the oxygen content of graphene is 19.85 in the graphene dispersing solution of gained
At.%.
Embodiment two
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm*0.3mm graphite is used as the moon
Pole, the aqueous solution of 200mL ammonium persulfate-sodium bisulfate carries out cell reaction with to graphite flake as electrolyte
Electrochemical stripping is carried out, wherein, the molar concentration of ammonium persulfate-sodium bisulfate is 0.01M in electrolyte；In electricity
In solution reaction, the distance of anode and negative electrode is 1cm, and voltage constant is stirred in 40V, and along with magneton,
The rotating speed of magneton stirring is 50r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system,
Electrochemical stripping is carried out 40 minutes to graphite flake, tentatively scattered water soluble disperse thing is obtained.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 40 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 3.5mg in the dispersion liquid
mL-1。
The number of plies of the water-soluble graphene of the gained of embodiments of the invention two is 3-8 layers, and oxygen content is 15.63
At.%.
Embodiment three
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Sodium peroxydisulfate the aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake,
Wherein, the molar concentration of sodium peroxydisulfate is 0.1M in electrolyte；In cell reaction, anode and negative electrode away from
From for 1.5cm, voltage constant is stirred in 30V, and along with magneton, and the rotating speed of magneton stirring is 500r/min,
And electrolyte is constant at 5 DEG C by temperature by cycle refrigeration system, 60 points of electrochemical stripping is carried out to graphite flake
Clock, obtains tentatively scattered water soluble disperse thing.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 45 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 1mg mL in the dispersion liquid-1。
The number of plies of the water-soluble graphene of the gained of embodiments of the invention three is 1-5 layers, and oxygen content is 20.01
At.%.
Example IV
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Potassium hydrogen persulfate the aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake,
Wherein, the molar concentration of potassium hydrogen persulfate is 0.05M in electrolyte；In cell reaction, anode and negative electrode
Distance is 5cm, and voltage constant is stirred in 80V, and along with magneton, and the rotating speed of magneton stirring is 300r/min,
And electrolyte is constant at 30 DEG C by temperature by cycle refrigeration system, 8 points of electrochemical stripping is carried out to graphite flake
Clock, obtains tentatively scattered water soluble disperse thing.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 60 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 2mg in the dispersion liquid
mL-1。
The number of plies of the water-soluble graphene of the gained of embodiments of the invention four is 1-6 layers, and oxygen content is 18.95
At.%.
Embodiment five
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Potassium hydrogen persulfate the aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake,
Wherein, the molar concentration of potassium hydrogen persulfate is 0.5M in electrolyte；In cell reaction, anode and negative electrode
Distance is 2cm, and voltage constant is stirred in 50V, and along with magneton, and the rotating speed of magneton stirring is 500r/min,
And electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, 1 point of electrochemical stripping is carried out to graphite flake
Clock, obtains tentatively scattered water soluble disperse thing.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 30 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 50 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 4.6mg in the dispersion liquid
mL-1。
The number of plies of the water-soluble graphene of the gained of embodiments of the invention five is layer 1-7, and oxygen content is 21.3
At.%.
Embodiment six
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Hydrogen persulfate ammonium the aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake,
Wherein, the molar concentration of hydrogen persulfate ammonium is 0.1M in electrolyte；In cell reaction, anode and negative electrode
Distance is 0.5cm, and voltage constant is stirred in 60V, and along with magneton, and the rotating speed of magneton stirring is 50r/min,
And electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, 5 points of electrochemical stripping is carried out to graphite flake
Clock, obtains tentatively scattered water soluble disperse thing.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 45 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 4.7mg in the dispersion liquid
mL-1。
The number of plies of the water-soluble graphene of the gained of embodiments of the invention six is 2-6 layers, and oxygen content is 19.98
At.%.
Embodiment seven
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Potassium peroxydisulfate the aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake,
Wherein, the molar concentration of potassium peroxydisulfate is 0.5M in electrolyte；In cell reaction, anode and negative electrode away from
From for 2cm, voltage constant is stirred in 70V, and along with magneton, and the rotating speed of magneton stirring is 300r/min,
And electrolyte is constant at 30 DEG C by temperature by cycle refrigeration system, electrochemical stripping 120 is carried out to graphite flake
Minute, obtain tentatively scattered water soluble disperse thing.
Step b：
It is recyclable to take out by the dispersion obtained in step a first ultrasonically treated 60 minutes, then suction filtration and washing
Electrolyte after filter, is then dried at 60 DEG C, obtains water-soluble graphene powder, then by water-soluble graphite
Alkene powder is dispersed in water, and obtains the dispersion liquid of graphene, and the concentration of graphene is 3.6mg in the dispersion liquid
mL-1。
The number of plies of the water-soluble graphene of the gained of embodiments of the invention seven is 2-7 layers, and oxygen content is 20.56
At.%.
Realize to extract using suction filtration in the step b for preparing graphene process of the present invention and be dispersed in electrolyte
Dispersion, naturally it is also possible to realized using other filter types or centrifugal separation technology.
The comparative example of the preparation method of the water-soluble graphene of the present invention.
Comparative example one
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Sulfuric acid the aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake, wherein,
The molar concentration of sulfuric acid is 0.05M in electrolyte；In cell reaction, the distance of anode and negative electrode is 1.5cm,
Voltage constant is stirred in 50V, and along with magneton, and the rotating speed of magneton stirring is 300r/min, and electrolyte
It is by cycle refrigeration system that temperature is constant at 25 DEG C, electrochemical stripping is carried out 90 minutes to graphite flake, obtained
The graphite floatation thing peeled off on a small quantity.
Step b：
By the graphite floatation thing obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing, it can return
Filtered electrolyte is received, is then dried at 50 DEG C, intermediate product is obtained, then intermediate product is dispersed in
In water, do not obtain can stable dispersion graphene solution.
The number of plies of the graphene of the gained of comparative example one of the present invention is 3-9 layers, and oxygen content is 12.34at.%.
Comparative example two
The present embodiment prepares graphene using following steps successively.
Step a：
By 5 grams of weight, thickness 1mm graphite flake is as anode, and 10cm*10cm platinized platinum is used as negative electrode, 200mL
Ammonium persulfate-sodium bisulfate the aqueous solution as electrolyte, cell reaction is carried out to carry out electrification to graphite flake
Learn and peel off, wherein, the molar concentration of ammonium persulfate-sodium bisulfate is 0.05M in electrolyte；In cell reaction,
The distance of anode and negative electrode is 1.5cm, and voltage constant is stirred in 10V, and along with magneton, magneton stirring
Rotating speed is 300r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, and graphite flake is entered
Row electrochemical stripping 120 minutes, obtains the graphite floatation thing peeled off on a small quantity.
Step b：
By the graphite floatation thing obtained in step a first ultrasonically treated 10 minutes, then suction filtration and washing, it can return
Filtered electrolyte is received, is then dried at 50 DEG C, intermediate product is obtained, then intermediate product is dispersed in
In water, do not obtain can stable dispersion graphene solution.
The number of plies of the graphene of the gained of comparative example two of the present invention is 2-10 layers, and oxygen content is 13.75
At.%.
Following table is the part Experiment parameter and experimental result of the embodiment of the present invention one~seven and comparative example one~bis-
List.
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 water-soluble graphene, it is characterised in that comprise the following steps：
A) using graphite material as anode material, the aqueous solution of persulfate is as electrolyte, and progress is electrolysed anti-
The electrochemical stripping to anode material should be realized, tentatively scattered water soluble disperse thing is obtained；
B) dispersion obtained in step a is subjected to ultrasonically treated, filtration washing and drying and processing successively,
Water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, point of graphene is obtained
Dispersion liquid.
2. the preparation method of water-soluble graphene according to claim 1, it is characterised in that step a
Described in cell reaction constant voltage be 30~80V.
3. the preparation method of water-soluble graphene according to claim 2, it is characterised in that the perseverance
Voltage is determined for 50V-60V.
4. the preparation method of water-soluble graphene according to claim 1, it is characterised in that in step a
The cell reaction progress during stirred along with magneton, magneton stirring rotating speed be 50~500
r/min。
5. the preparation method of water-soluble graphene according to claim 1, it is characterised in that step a
Described in electrolyte the molar concentration of persulfate be 0.01~0.5M.
6. the preparation method of water-soluble graphene according to claim 1, it is characterised in that step a
Described in the negative electrode of cell reaction be platinized platinum, the distance of anode and negative electrode is 0.5~5cm, cell reaction when
Between be 1~120 minute, the temperature of electrolyte is 5~30 DEG C.
7. the preparation method of water-soluble graphene according to claim 1, it is characterised in that step b
Described in ultrasonically treated time be 10~60 minutes.
8. the preparation method of water-soluble graphene according to claim 1, it is characterised in that step b
Described in drying and processing time be 40~60 DEG C.
9. the preparation method of water-soluble graphene according to claim 1, it is characterised in that step a
Described in persulfate be potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen persulfate sodium, hydrogen persulfate ammonium
With any one in ammonium persulfate-sodium bisulfate or a variety of.
10. the preparation method of water-soluble graphene according to claim 1, it is characterised in that the stone
Ink material is any one in graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite
Or it is a variety of.
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| CN110357087A (en) * | 2019-08-14 | 2019-10-22 | 中国科学院兰州化学物理研究所 | A method of graphene oxide is prepared based on high concentration inorganic salt solution removing |
| CN111470502A (en) * | 2020-04-14 | 2020-07-31 | 南通强生石墨烯科技有限公司 | Graphene disinfectant and preparation method thereof |
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