CN107235486B - The preparation method of water-soluble graphene - Google Patents
The preparation method of water-soluble graphene Download PDFInfo
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- CN107235486B CN107235486B CN201610169746.4A CN201610169746A CN107235486B CN 107235486 B CN107235486 B CN 107235486B CN 201610169746 A CN201610169746 A CN 201610169746A CN 107235486 B CN107235486 B CN 107235486B
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Abstract
The preparation method of water-soluble graphene is the following steps are included: a) using graphite material as anode material, the aqueous solution of persulfate carries out cell reaction realization to the electrochemical stripping of anode material, obtain the water soluble disperse object tentatively dispersed as electrolyte；B) dispersion obtained in step a is successively ultrasonically treated, filtration washing and drying and processing, obtains water-soluble graphene powder, then water-soluble graphene powder is dispersed in water, obtains the dispersion liquid of graphene.The present invention provides a kind of preparation method of water-soluble graphene, aqueous solution by using persulfate is that electrolyte realizes the electrochemical stripping to graphite material under electric field action, has the characteristics that safe, at low cost, pollution-free, weak oxide, it overcomes graphene poorly water-soluble and cannot be considered in terms of water-soluble and electric conductivity problem, post-processing is easy, and product has conductive capability and mechanical strength water-soluble while kept, free from admixture, efficiency and yield are high, and process flow is simple.
Description
Technical field
The present invention relates to grapheme material preparation technical fields, and in particular to a kind of preparation method of water-soluble graphene.
Background technique
Graphene is greatly emerging with industrial circle because its unique conductive and heat-conductive and mechanical performance attract always scientific research circle
Interest.For graphene self character, the graphene of structural integrity be by without any labile bond benzene hexatomic ring combine and
At two dimensional crystal, the inert state in surface is weaker with the interaction of other media (such as solvent), and the piece of graphene
There is stronger Van der Waals force between piece, be easy to produce back folded and aggregation, make that it is insoluble in water and there are commonly solvents, this gives
The effective dispersion and extensive use of graphene have caused great difficulties.And with the development of the industry, grapheme material is in electricity
The fields such as son, information, the energy, material and biological medicine show wide application prospect, this requires grapheme material to have height
Have good dispersibility to meet different application field while quality, free from admixture, high conductivity.In addition, in face of more next
The features such as bigger market demand, the large scale preparation of graphene also requires nontoxic, pollution-free, inexpensive, simple process, and show
There is also very big challenges in these areas for some grapheme materials.In order to give full play to its advantageous property, improves its molding and add
Work (such as raising dissolubility, dispersibility in the base), it is necessary to which effective functionalization is carried out to graphene.Research at present is most
It is chemistry redox method for extensive functional method, can be contained with large scale preparation graphene oxide soluble in water
There are many oxygen groups and defect, and electrical and thermal conductivity performance is caused to be greatly lowered, and preparation process it is complicated and introduce a large amount of acid and
Strong oxidizer, it is difficult to completely cleared.Existing in the prior art is functionalized graphite using sulfuric acid and potassium permanganate, and is added 12
Sodium alkyl benzene sulfonate obtains water-soluble graphene, and gained graphene is uniformly dispersed in water and prepared conductive film is led
Electric rate is up to 1300S/m, but preparation process has used strong acid, and strong oxidizer, complex process is seriously polluted, and removal of impurities is difficult, right
Graphene assertive evidence structure is destroyed greatly, and defect is more.In the prior art there is also a kind of technology of preparing of water-soluble graphene under room temperature,
By the concentrated sulfuric acid and potassium permanganate oxidation graphite material, not environmentally friendly enough, at high cost, the product that faces preparation process has similarly been used
The problems such as not pure enough.In addition, the method for hydrazine hydrate reduction is water-soluble to prepare in the prior art there is also being aoxidized using the concentrated sulfuric acid
Property graphene, use of this technology relative to strong acid strong oxidizer, the safety is improved, and technique is also relatively easy, but process
Middle to introduce too many chemical substance, gained sample is not pure enough, and defect is more, the toxic explosive of raw material hydrazine hydrate, seriously polluted, at
This height.
Existing chemical oxidation techniques prepare water-soluble graphene and mainly pass through strong acid, strong oxidizer and dispersing agent to obtain
, the problems such as prepare with scale faces seriously polluted, at high cost, complex process, not high safety, the graphene defect of acquisition compared with
More, impurity content is high.Therefore, a kind of extensive, low cost, free from admixture, while green safe water-soluble graphene system are needed
Standby technology.Electrochemistry is one of the effective means of large scale preparation graphene, principle be by electric field-assisted intercalation and removing,
Compared to chemical oxidation intercalation, electrochemical process does not need strong oxidizer and strong acid instead electric field oxidation removing, has
The advantages that yield is high, and the time is short, environmentally protective, and yield is high.But the graphene of existing electrochemical techniques preparation is essentially all molten
Solution can not be dissolved in the water in organic solvent.It is in electricity that the graphene of electrochemistry preparation, which is difficult to the main reason for being dissolved in water,
Under field action, although graphite is in anode, the process for thering is electric field-assisted to aoxidize, due to the quick removing of electric field, once by shelling
From independent graphene is formed departing from electrode surface, would not be aoxidized by electric field, and the oxidation benefit of electrolyte itself
It is extremely weak.The removing graphite using cetyl trimethylammonium bromide solution as electrolyte exists in the prior art and prepares graphene oxide
Method, obtaining graphene oxide has good functionalization, and carbon-to-oxygen ratio can achieve 5.5.But this method reaction time
It is longer, it is inefficient, and structure is complicated for electrolyte, removal of impurities is difficult, compares so that obtaining extensive pure grapheme material
Difficulty, cost is also relatively high, is difficult to apply to the large scale preparation of high-quality water soluble graphene.One article reports
To 7,7,8, the 8- functionalized graphenes of tetracyano-p-quinodimethane, oxygen content reaches 20.62%, has in water well
Dispersibility, but this technical matters is complicated, electrolyte preparation procedure is more, and it is at high cost, and electrolyte and graphene product
Interaction is strong, is difficult to remove, it is difficult to which extensive industrialization prepares water-soluble grapheme material.Therefore, a kind of technique is invented
Simply, inexpensive, free of contamination water-soluble graphene technology of preparing has very big meaning.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of low-cost and pollution-less, easy to operate and easy is provided
The preparation method of the water-soluble graphene of removal of impurities.
To achieve the above object, present invention employs following technical solutions:
A kind of preparation method of water-soluble graphene, comprising the following steps:
A) using graphite material as anode material, the aqueous solution of persulfate carries out cell reaction realization as electrolyte
To the electrochemical stripping of anode material, the water soluble disperse object tentatively dispersed is obtained；
B) dispersion obtained in step a is successively ultrasonically treated, filtration washing and drying and processing, is obtained water-soluble
Property graphene powder, then water-soluble graphene powder is dispersed in water, obtain the dispersion liquid of graphene.
Preferably, the constant voltage of cell reaction described in step a is 30~80V.
Preferably, the constant voltage is 50V-60V.
Preferably, it is stirred during the progress of the cell reaction of step a along with magneton, the revolving speed of magneton stirring
For 50~500r/min.
Preferably, the molar concentration of persulfate is 0.01~0.5M in electrolyte described in step a.
Preferably, the cathode of cell reaction described in step a is platinized platinum, and the distance of anode and cathode is 0.5~5cm, electricity
The time of solution reaction is 1~120 minute, and the temperature of electrolyte is 5~30 DEG C.
Preferably, the time of ultrasonic treatment 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, hydrogen persulfate sodium, mistake
In ammonium hydrogen sulfate and ammonium persulfate-sodium bisulfate any one or it is a variety of.
Preferably, the graphite material is in graphite flake, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite
Any one or more.
The preparation method of water-soluble graphene of the invention, the aqueous solution by using persulfate are electrolyte in electric field
Effect is lower to realize to the electrochemical stripping of graphite material have the characteristics that safe, at low cost, pollution-free, weak oxide, overcome stone
Black alkene poorly water-soluble and the problem that cannot be considered in terms of water solubility and electric conductivity are suitble to large-scale industrialized production, have extensive
Prospects for commercial application；Electrolyte is the salt with oxidisability, is not related to the effect of strong acid, so electrolyte may be selected to be water
Phase, post-processing are easy；Required concentration of electrolyte is lower, at low cost, and high production efficiency is pollution-free；Electrolytic process is without Strong oxdiative
Effect, it is to the extent of the destruction of the intrinsic structure of graphene sheet layer lower, so that sample is with water-soluble while having kept
Conductive capability and mechanical strength；Over cure acid group decomposes in the reaction, and metal ion can also remove in filtering cleaning process, obtains
Obtain product free from admixture；The process time of reaction is short, high-efficient, and yield is high, and process flow is simple, at low cost, can be mass-produced.
Detailed description of the invention
Fig. 1 is the graphene transmission electron microscope figure obtained of embodiment one；
Fig. 2 is the graphene selective electron diffraction microscope figure obtained of embodiment one；
Fig. 3 is the graphene scanning electron microscope diagram obtained of embodiment one；
Fig. 4 is the display diagram that the graphene obtained of embodiment one is dissolved in water；
Fig. 5 is the graphene X-ray photoelectron spectroscopic analysis figure obtained of embodiment one.
Specific embodiment
Below in conjunction with the embodiment that attached drawing 1 to 5 provides, the preparation method of water-soluble graphene of the invention is further illustrated
Specific embodiment.The preparation method of water-soluble graphene of the invention is not limited to the following description.
The preparation method of water-soluble graphene of the invention the following steps are included:
A) using graphite material as anode material, the aqueous solution of persulfate carries out cell reaction realization as electrolyte
To the electrochemical stripping of anode material, the water soluble disperse object tentatively dispersed is obtained；
B) dispersion obtained in step a is successively ultrasonically treated, filtration washing and drying and processing, is obtained water-soluble
Property graphene powder, then water-soluble graphene powder is dispersed in water, obtain the dispersion liquid of graphene.Electricity described in step a
It is stirred while solution reaction along with magneton, the revolving speed of magneton stirring is 50~500r/min.
Wherein, persulfate described in step a is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen persulfate sodium and over cure
Any one in potassium hydrogen phthalate complex salt or a variety of, preferably persulfuric acid complex salt.The graphite material is graphite flake, scale
Any one or more in graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite.It can be using conductions such as graphite or platinized platinums
Cathode of the material as cell reaction in step a.
The preparation method of water-soluble graphene of the invention, the aqueous solution by using persulfate are electrolyte in electric field
Effect is lower to realize to the electrochemical stripping of graphite material have the characteristics that safe, at low cost, pollution-free, weak oxide, overcome stone
Black alkene poorly water-soluble and the problem for taking into account water solubility and electric conductivity are suitble to large-scale industrialized production, have extensive industrial
Application prospect；Electrolyte is the salt with oxidisability, is not related to the effect of strong acid, so electrolyte may be selected to be water phase, after
Processing is easy；Required concentration of electrolyte is lower, at low cost, and high production efficiency is pollution-free；Electrolytic process without strong oxidation,
It is lower to the extent of the destruction of the intrinsic structure of graphene sheet layer, so that sample is with conductive energy that is water-soluble while having kept
Power and mechanical strength；Over cure acid group decomposes in the reaction, and metal ion can also remove in filtering cleaning process, obtains product
Free from admixture；The process time of reaction is short, high-efficient, and yield is high, and process flow is simple, at low cost, can be mass-produced.
The present invention prepares the principle of graphene: selecting oxidant persulfate as electrolyte, in the effect of higher electric field
Under, over cure acid radical anion and persulfuric acid hydrogen radical anion transport in electrolyte to anode and are gradually equably intercalation into stone
In the lamellar spacing of ink, then under the action of Anodic, graphite flake layer is aoxidized and it is made to fall off it is dissolved in electrolyte
In.Relative to other inorganic salts persulfates as electrolyte, oxidisability is stronger, it is easier to obtain having hydrophilic graphite
Alkene；High electric field accelerates electron transfer rate simultaneously but also the quickening of over cure acid group hydrogen persulfate radical ion free radicalization, mentions
High reaction efficiency；In electrochemical process, anode happens is that oxidation reaction, the process of anodization i.e. electrochemical oxidation
Process.Therefore water solubility of the invention is embodied in functionalized graphene, since persulfate is under electrochemical action, so that stone
Many oxygen-containing groups are connected on black alkene lamella, improve the polarity of graphene, graphene is enable to have dissolution in water
Power, while also there is good electric conductivity.Wherein, the oxidisability of persulfate is weak with respect to potassium permanganate very much, to graphite-structure
Destructiveness it is lower, and relative to strong acid, non-corrosive, sylvite, sodium salt or ammonium salt after reaction can be by simple
Washing completely removes.In addition, the stripping process of the migration and graphite of ion can be accelerated using high voltage (30~80V), relatively
Production efficiency and yield are improved in other electrochemical methods, while a high electric field also can promote oxidation process, so that
The persulfate of graphite oxide is not enough under usual conditions under high electric field by graphite oxidation.
The specific embodiment of the preparation method of water-soluble graphene of the invention.
Embodiment one
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of potassium hydrogen phthalate complex salt carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein electrolysis
The molar concentration of ammonium persulfate-sodium bisulfate is 0.05M in liquid；In cell reaction, the distance of anode and cathode is 1.5cm, electricity
It presses constant in 50V, and is stirred along with magneton, the revolving speed of magneton stirring is 300r/min, and electrolyte passes through circularly cooling system
It unites temperature is constant at 25 DEG C, graphite flake is carried out electrochemical stripping 5 minutes, obtain the water soluble disperse object tentatively dispersed.
Step b:
Dispersion obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 50 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 4mg mL in the dispersion liquid-1。
Transmission electron microscope test result such as Fig. 1 and Fig. 2 of the resulting graphene of the embodiment of the present invention one, take off respectively
The size and crystal property for having shown the lamella of graphene, by the observation and analysis to Fig. 1 and Fig. 2 it is found that resulting stone
The piece number of plies of black alkene is 3-5 layers；Scanning electron microscope result as shown in figure 3, illustrate the microscopic appearance of water-soluble graphene,
The lamellar structure of graphene is than more complete as seen from Figure 3；Picture such as Fig. 4 institute of resulting water-soluble graphene dispersion liquid
Show, illustrates the dispersibility of water-soluble graphene in water；Resulting graphene X-ray photoelectron spectroscopic analysis result such as Fig. 5
It is shown, it is shown that the oxygen-containing functional group of the graphene graphene.In addition, in resulting graphene dispersing solution graphene oxygen content
For 19.85at.%.
Embodiment two
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the graphite of 10cm*10cm*0.3mm is as cathode, 200mL
Ammonium persulfate-sodium bisulfate aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake,
In, the molar concentration of ammonium persulfate-sodium bisulfate is 0.01M in electrolyte；In cell reaction, the distance of anode and cathode is
1cm, voltage are constant in 40V, and stir along with magneton, and the revolving speed of magneton stirring is 50r/min, and electrolyte passes through circulation system
Cooling system is constant at 25 DEG C by temperature, carries out electrochemical stripping 40 minutes to graphite flake, obtains the water soluble disperse tentatively dispersed
Object.
Step b:
Dispersion obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 40 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 3.5mg mL in the dispersion liquid-1。
The number of plies of the resulting water-soluble graphene of the embodiment of the present invention two is 3-8 layers, oxygen content 15.63at.%.
Embodiment three
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of sour sodium carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein over cure in electrolyte
The molar concentration of sour sodium is 0.1M；In cell reaction, the distance of anode and cathode is 1.5cm, and voltage is constant in 30V, and companion
As magneton stirs, the revolving speed of magneton stirring is 500r/min, and electrolyte is constant 5 by temperature by cycle refrigeration system
DEG C, graphite flake is carried out electrochemical stripping 60 minutes, the water soluble disperse object tentatively dispersed is obtained.
Step b:
Dispersion obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 45 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 1mg mL in the dispersion liquid-1。
The number of plies of the resulting water-soluble graphene of the embodiment of the present invention three is 1-5 layers, oxygen content 20.01at.%.
Example IV
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of potassium hydrogen phthalate carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein mistake in electrolyte
The molar concentration of potassium acid sulfate is 0.05M；In cell reaction, the distance of anode and cathode is 5cm, and voltage is constant in 80V, and
Stirred along with magneton, magneton stirring revolving speed be 300r/min, and electrolyte by cycle refrigeration system by temperature it is constant
30 DEG C, graphite flake is carried out electrochemical stripping 8 minutes, obtains the water soluble disperse object tentatively dispersed.
Step b:
Dispersion obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 60 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 2mg mL in the dispersion liquid-1。
The number of plies of the resulting water-soluble graphene of the embodiment of the present invention four is 1-6 layers, oxygen content 18.95at.%.
Embodiment five
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of potassium hydrogen phthalate carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein mistake in electrolyte
The molar concentration of potassium acid sulfate is 0.5M；In cell reaction, the distance of anode and cathode is 2cm, and voltage is constant in 50V, and
Stirred along with magneton, magneton stirring revolving speed be 500r/min, and electrolyte by cycle refrigeration system by temperature it is constant
25 DEG C, graphite flake is carried out electrochemical stripping 1 minute, obtains the water soluble disperse object tentatively dispersed.
Step b:
Dispersion obtained in step a is first ultrasonically treated 30 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 50 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 4.6mg mL in the dispersion liquid-1。
The number of plies of the resulting water-soluble graphene of the embodiment of the present invention five is layer 1-7, oxygen content 21.3at.%.
Embodiment six
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of sour hydrogen ammonium carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein mistake in electrolyte
The molar concentration of ammonium hydrogen sulfate is 0.1M；In cell reaction, the distance of anode and cathode is 0.5cm, and voltage is constant in 60V,
And stirred along with magneton, magneton stirring revolving speed be 50r/min, and electrolyte by cycle refrigeration system by temperature it is constant
25 DEG C, graphite flake is carried out electrochemical stripping 5 minutes, obtains the water soluble disperse object tentatively dispersed.
Step b:
Dispersion obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 45 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 4.7mg mL in the dispersion liquid-1。
The number of plies of the resulting water-soluble graphene of the embodiment of the present invention six is 2-6 layers, oxygen content 19.98at.%.
Embodiment seven
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of sour potassium carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein over cure in electrolyte
The molar concentration of sour potassium is 0.5M；In cell reaction, the distance of anode and cathode is 2cm, and voltage is constant in 70V, and adjoint
Magneton stirring, magneton stirring revolving speed be 300r/min, and electrolyte by cycle refrigeration system temperature is constant at 30 DEG C,
Graphite flake is carried out electrochemical stripping 120 minutes, the water soluble disperse object tentatively dispersed is obtained.
Step b:
Dispersion obtained in step a is first ultrasonically treated 60 minutes, then filters and washs, filtered electricity can be recycled
Liquid is solved, is then dried at 60 DEG C, water-soluble graphene powder is obtained, then water-soluble graphene powder is dispersed in water, obtains
To the dispersion liquid of graphene, the concentration of graphene is 3.6mg mL in the dispersion liquid-1。
The number of plies of the resulting water-soluble graphene of the embodiment of the present invention seven is 2-7 layers, oxygen content 20.56at.%.
It is realized in the step b for preparing graphene process of the invention using suction filtration and extracts the dispersion being dispersed in electrolyte
Object, naturally it is also possible to be realized using other filter types or centrifugal separation technology.
The comparative example of the preparation method of water-soluble graphene of the invention.
Comparative example one
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the sulfuric acid of 200mL
Aqueous solution as electrolyte, carry out cell reaction to carry out electrochemical stripping to graphite flake, wherein sulfuric acid rubs in electrolyte
Your concentration is 0.05M；In cell reaction, the distance of anode and cathode is 1.5cm, and voltage is constant in 50V, and along with magneton
Stirring, the revolving speed of magneton stirring is 300r/min, and electrolyte is constant at 25 DEG C by temperature by cycle refrigeration system, to graphite
Piece carries out electrochemical stripping 90 minutes, obtains the graphite floatation object removed on a small quantity.
Step b:
Graphite floatation object obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, can be recycled after filtering
Electrolyte, then dried at 50 DEG C, obtain intermediate product, then intermediate product is dispersed in water, not obtaining can stablize point
Scattered graphene solution.
The number of plies of the resulting graphene of comparative example one of the invention is 3-9 layers, oxygen content 12.34at.%.
Comparative example two
The present embodiment successively uses following steps to prepare graphene.
Step a:
By 5 grams of weight, the graphite flake of thickness 1mm is as anode, and the platinized platinum of 10cm*10cm is as cathode, the over cure of 200mL
The aqueous solution of potassium hydrogen phthalate complex salt carries out cell reaction as electrolyte to carry out electrochemical stripping to graphite flake, wherein electrolysis
The molar concentration of ammonium persulfate-sodium bisulfate is 0.05M in liquid；In cell reaction, the distance of anode and cathode is 1.5cm, electricity
It presses constant in 10V, and is stirred along with magneton, the revolving speed of magneton stirring is 300r/min, and electrolyte passes through circularly cooling system
It unites temperature is constant at 25 DEG C, graphite flake is carried out electrochemical stripping 120 minutes, obtain the graphite floatation object removed on a small quantity.
Step b:
Graphite floatation object obtained in step a is first ultrasonically treated 10 minutes, then filters and washs, can be recycled after filtering
Electrolyte, then dried at 50 DEG C, obtain intermediate product, then intermediate product is dispersed in water, not obtaining can stablize point
Scattered graphene solution.
The number of plies of the resulting graphene of comparative example two of the invention is 2-10 layers, oxygen content 13.75at.%.
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.
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, In
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 (9)
1. a kind of preparation method of water-soluble graphene, which comprises the following steps:
A) using graphite material as anode material, the aqueous solution of persulfate carries out cell reaction and realizes to sun as electrolyte
The electrochemical stripping of pole material, obtains the water soluble disperse object that tentatively disperses, and the constant voltage of the cell reaction is 30~
80V；
B) dispersion obtained in step a is successively ultrasonically treated, filtration washing and drying and processing, obtains water-soluble stone
Black alkene powder, then water-soluble graphene powder is dispersed in water, obtain the dispersion liquid of graphene.
2. the preparation method of water-soluble graphene according to claim 1, which is characterized in that the cell reaction it is constant
Voltage is 50V-60V.
3. the preparation method of water-soluble graphene according to claim 1, which is characterized in that in the electrolysis of step a
It is stirred during the progress of reaction along with magneton, the revolving speed of magneton stirring is 50~500r/min.
4. the preparation method of water-soluble graphene according to claim 1, which is characterized in that electrolyte described in step a
The molar concentration of middle persulfate is 0.01~0.5M.
5. the preparation method of water-soluble graphene according to claim 1, which is characterized in that electrolysis described in step a is anti-
The cathode answered is platinized platinum, and the distance of anode and cathode is 0.5~5cm, and the time of cell reaction is 1~120 minute, electrolyte
Temperature is 5~30 DEG C.
6. the preparation method of water-soluble graphene according to claim 1, which is characterized in that at ultrasound described in step b
The time of reason is 10~60 minutes.
7. the preparation method of water-soluble graphene according to claim 1, which is characterized in that at drying described in step b
The time of reason is 40~60 DEG C.
8. the preparation method of water-soluble graphene according to claim 1, which is characterized in that persulfuric acid described in step a
Salt is appointing in potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, hydrogen persulfate sodium, hydrogen persulfate ammonium and ammonium persulfate-sodium bisulfate
Meaning is one or more kinds of.
9. the preparation method of water-soluble graphene according to claim 1, which is characterized in that the graphite material is graphite
Any one or more in piece, crystalline flake graphite, graphite foil, graphite rod and highly oriented pyrolytic graphite.
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| CN113666366A (en) * | 2020-05-13 | 2021-11-19 | 中国科学技术大学 | Method for preparing graphene through electrochemical anode stripping |
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