CN107352532A - Graphene oxide and its preparation method and application - Google Patents
Graphene oxide and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to grapheme material technical field, it is related to graphene oxide and its preparation method and application.The preparation method of graphene oxide provided by the invention, graphite is well mixed with oxidisability salt, then crushing stripping and oxidation processes are carried out by way of mechanical force and chemical, obtain intermediate；By intermediate washing, dry, produce graphene oxide.On the one hand graphite raw material of the present invention is oxidized the shearing of property salt particle and peeled off, on the one hand realize that functionalization aoxidizes, obtain graphene oxide under conditions of mechanism；On the basis of mechanical force and chemical, improve the technique that graphene oxide is prepared under the harsh conditions such as traditional strong acid, strong oxidizer, not only reduce cost, shorten the time for preparing graphene oxide, control using and discharging for poisonous and harmful substance, and obtained graphene oxide more meets the concept of graphene " presoma ", graphene is above closer in performance and application；Meanwhile yield is high, simple and easy, green.
Description
Technical field
The invention belongs to grapheme material technical field, and in particular to graphene oxide and its preparation method and application.
Background technology
Graphene oxide has its unique advantage and spy as the important presoma for preparing graphene in structure and performance
Point, these excellent properties make it be had broad application prospects in numerous areas such as energy environment, microelectronics, composites.
At present, the method for preparing graphene oxide mainly has：Brodie methods, Staudenmaier methods and Hummers methods.
Wherein, Brodie methods are added potassium chlorate in the mixed liquor of graphite and fuming nitric aicd, due to using potassium chlorate as oxidant,
It is dangerous larger, and more toxic gas (ClO can be produced in course of reaction2).Staudenmaier rules are in the concentrated sulfuric acid
Under system, using potassium chlorate and fuming nitric aicd as oxidant, reaction required time is longer, and poison gas has equally been had in course of reaction
Body (Cl2、ClO2) produce.And although Hummers methods instead of potassium chlorate with potassium permanganate, reduce the discharge of toxic gas,
Need the technological factor that controls more in its course of reaction, and equally have certain risk in experimentation.Sum it up, mesh
More or less it can all be related to the raw materials such as potassium permanganate, the concentrated sulfuric acid, preparation flow in the preceding main stream approach for preparing graphene oxide
Relative complex, there is also environmental protection and the hidden danger of secure context；In addition, the graphene oxide obtained in such method contains largely not
Recoverable defect, although dispersive property is lifted in a solvent, electric conductivity is often very poor.
In recent years, the theory of this emerging cross discipline of mechanical force and chemical and the research of application receive many researchers'
Concern.For example, Dai Liming et al. (Proc.Natl.Acad.Sci.U.S.A., 2012,109,5588-5593) are by machinery
Power chemistry is incorporated into the system for preparing modified graphene, by handling graphite powder and dry ice in planetary ball mill, is obtained
Carboxylation graphene, the dispersive property of the modified graphene in a solvent are improved significantly.But this method reaction condition
Harshness, can not scale of mass production.Publication No. CN103288078 A patent of invention discloses a kind of preparation of graphene oxide
Method, mechanochemistry processing is carried out using the oxidants such as benzoyl peroxide and Peracetic acid and graphite powder, obtains graphite oxide
Alkene.For the yield of graphene oxide obtained by this method close to 30%, yield is relatively low, needs further to be improved；And this method use has
Machine peroxide, often there is very high reactivity explosion accident easily occurs under the conditions of mechanical force and chemical, be raw safely
One big hidden danger of production.
In consideration of it, special propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of graphene oxide, using graphite and oxidisability salt as original
Material, carry out crushing stripping in the presence of mechanical force and chemical after the two mixing and oxidation processes are carried out to graphite flake, and then
To graphene oxide；This method novel and unique, simple and easy, high-efficiency environment friendly, and security is good, high income, it is easy to accomplish work
Industry large-scale production.
The second object of the present invention is to provide a kind of graphene oxide, and obtained oxidation stone is prepared by the method for the present invention
Black alkene, there is higher electric conductivity and preferable dispersive property, have in water, in part organic solvent and macromolecule resin
Good dispersiveness and stability.
The third object of the present invention is to provide a kind of application of graphene oxide, and graphene oxide of the invention has good
Good electric conductivity and dispersiveness, it is thus possible in the field such as composite, conductive electrode and energy conversion and memory device
Using.
To achieve the above object, the technical solution adopted by the present invention is：
According to an aspect of the present invention, the present invention provides a kind of preparation method of graphene oxide, and methods described includes
Following steps：
Graphite is well mixed with oxidisability salt, then carries out crushing at stripping and oxidation by way of mechanical force and chemical
Reason, obtains intermediate；
Gained intermediate is washed and dried, produces graphene oxide.
As further preferred technical scheme, the graphite be crystalline flake graphite, expanded graphite, intercalated graphite, graphite powder or
One or more of mixtures in graphene powder；
And/or the particle diameter of the graphite is 40~15000 mesh.
As further preferred technical scheme, the oxidisability salt is persulfate, preferably potassium peroxydisulfate, persulfuric acid
One or more of mixtures in sodium, potassium hydrogen persulfate or hydrogen persulfate sodium.
As further preferred technical scheme, the mass ratio of the graphite and oxidisability salt is 1：(1~100).
As further preferred technical scheme, the mode of action of the mechanical force and chemical is abrasive action, compression, punching
One or more of combinations in the effect of hitting, rubbing action, shear action or progradation；
And/or the processing equipment of the mechanical force and chemical is horizontal ball mill, vibrator, planetary ball mill, stirred
Mix one or more of combinations in grinding machine, ultrasonic machine, roller mill or sand mill.
As further preferred technical scheme, the processing time of the mechanical force and chemical is 1~24 hour.
As further preferred technical scheme, the washing includes washing, pickling and the washing carried out successively；
And/or the drying is freeze-drying, is dried in vacuo, is in forced air drying or spray drying one or more of
Combination, the dry time is preferably 24~60 hours.
According to another aspect of the present invention, the present invention also provides a kind of graphene oxide, by weighing above-described oxidation
The preparation method of graphene is made.
According to another aspect of the present invention, the present invention also provides a kind of graphene oxide in composite, conductive electrode
Or energy conversion and the application in memory device.
As further preferred technical scheme, the composite includes graphene nanometer conductive compound material and graphene
At least one of nano anti-corrosive composite.
Compared with prior art, the beneficial effects of the present invention are：
1st, the method that the present invention uses mechanical force and chemical, with reference to mechanical stripping and oxidation reaction, not only instead of tradition side
The hazardous chemical such as the conventional concentrated sulfuric acid, potassium permanganate in method, and method is simple and easy, environment-friendly, safe and efficient, yield
Height, cost are low, it is easy to accomplish extensive, industrialization promotion production.
2nd, the oxidisability salt that the present invention uses is both to peel off auxiliary agent and oxidant, and stripping is played in the presence of mechanical force
The effect of graphite is crushed, and carries out oxidation processes to graphite flake under conditions of mechanical activation, the oxidisability salt is more stable
And safety, and such salt is widely used in water process and soil remediation process, to environmental hazard very little, has good economy
Benefit and environmental benefit.
3rd, the graphene oxide layer as made from the inventive method is at 1~10 layer, in water, organic solvent, macromolecule resin
There are excellent dispersiveness and stability in；Meanwhile described graphene oxide has good electric conductivity, particularly passes through
After heat treatment, electrical conductivity is close to ordinary graphite alkene, thus in terms of the fields such as composite, electronic device, biologic medical
Have a wide range of applications.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the figure after the dispersion liquid of graphene oxide made from the embodiment of the present invention 1 is stood one month；
Fig. 2 is that the HRTEM of graphene oxide made from the embodiment of the present invention 2 schemes；
Fig. 3 is the infrared analysis figure of graphene oxide made from the embodiment of the present invention 2；
Fig. 4 is that the HRTEM of graphene oxide made from the embodiment of the present invention 3 schemes.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment and embodiment, but this area skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and be not construed as the model of the limitation present invention
Enclose.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.Actual conditions person is indicated, is suggested according to normal condition or manufacturer
Condition carry out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional products that can be obtained by commercially available purchase.
In a first aspect, present embodiment provides a kind of preparation method of graphene oxide, the described method comprises the following steps：
(a) graphite is well mixed with oxidisability salt, then carries out crushing stripping and oxygen by way of mechanical force and chemical
Change is handled, and obtains intermediate；
(b) gained intermediate is washed, dried, produce graphene oxide.
Mechanical force and chemical is a branch of chemistry, is the relatively more extensive emerging skill of current more concerned, research field
Art, the application prospect in many fields are extensive.It studies emphatically the change that condensed state matter occurs when by mechanical force
Learn or physical chemistry changes.Specifically, mechano-chemical reation is the different modes of action by mechanical force, such as grinding, pressure
Contracting, impact, friction, shearing, extension etc., introduce the accumulation of mechanical energy, so that the physicochemical properties and knot of stress object
Structure changes, activated interfaces, reactivity is improved, so as to excite and accelerate caused chemical reaction.It is anti-with general chemistry
Should be different, mechano-chemical reation is not related with temperature, and mechano-chemical reation is considered as mainly by the phase of powder particle
Caused by interaction, this is one of main feature of mechano-chemical reation.Powder granule is locally born in crushing process
Larger stress or the alternate stress zone of action can produce the decomposition reaction of mechanical force and chemical, redox reaction, dissolving reaction,
Hydration reaction, solutionizing and solid phase reaction, the polymerisation of organic compound etc., these cause mechano-chemical reation and general
There is obvious difference for chemical reaction.
The characteristics of by means of mechanical force and chemical, field of graphene is introduced into, is stone for preparing or grapheme modified
The large-scale production and application of black alkene provide opportunity.However, at present on preparing oxidation by the method for mechanical force and chemical
Graphene research is relatively weak.In view of this, in the present invention, by means of moment excitation caused by mechanical force, utilize
Oxidant serves as stripping/oxidant, realizes the preparation of graphene oxide, for graphene oxide application study provide it is strong
Technical support.
The present invention is using graphite as raw material, with being both to peel off auxiliary agent and the oxidisability salt of oxidant to mix, in mechanical force
In the presence of, peel off and crush graphite and oxidation processes are carried out to graphite flake, then carry out washing drying again, obtain aoxidizing stone
Black alkene.On the one hand, it is of the invention with it is existing the main stream approach of graphene oxide is prepared using the concentrated sulfuric acid, potassium permanganate etc. compared with,
Flow is simple, easily operated control, and efficiency high is environment-friendly, effectively alleviates the hidden danger of its existing environmental protection and secure context,
And the graphene oxide being prepared, electric conductivity and dispersive property are more preferable.On the other hand, the present invention is with using benzoyl peroxide
The mode of the oxidants such as formyl and Peracetic acid is compared, yield and more efficient, and more stable and safety, environmental benefit is more preferable,
The potential safety hazard easily to be caused an explosion accident existing for it can effectively be alleviated.To sum up, method of the invention is simple and easy, green
Environmental protection, efficiency high, effect is good, cost is cheap, it is easier to realizes industrial-scale production.
In a kind of optional embodiment, in step (a), the graphite is crystalline flake graphite, expanded graphite, intercalation stone
One or more of mixtures in ink, graphite powder or graphene powder；
And/or the particle diameter of the graphite is 40~15000 mesh, preferably 50~1000 mesh, more preferably 100~
500 mesh.
Optionally, the particle diameter of graphite is typical but non-limiting is：40 mesh, 50 mesh, 60 mesh, 80 mesh, 100 mesh, 120 mesh,
150 mesh, 180 mesh, 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 600 mesh, 800 mesh, 1000 mesh, 1500
Mesh, 10000 mesh or 15000 mesh.
In a kind of optional embodiment, in step (a), the oxidisability salt is persulfate, preferably persulfuric acid
One or more of mixtures in potassium, sodium peroxydisulfate, potassium hydrogen persulfate or hydrogen persulfate sodium.
In a kind of optional embodiment, in step (a), the mass ratio of the graphite and oxidisability salt is 1：(1~
100), preferably 1：(1~50), more preferably 1：(5~20).
Optionally, the mass ratio of graphite and oxidisability salt is typical but non-limiting is：1：1、1；2、1：3、1：4、1：5、
1：6、1：8、1：10、1：12、1：15、1：18、1：20、1：25、1：30、1：40、1：50、1：60、1：70、1：80、1：90 or 1：
100。
Optionally, in step (a), first by the way of stirring graphite is well mixed with oxidisability salt, then will mixing
Sample afterwards is carried out crushing stripping by the way of mechanical force and chemical and carries out oxidation processes to graphite flake, obtains intermediate.
Before automatic reaction, first graphite is well mixed with oxidisability salt so that two kinds of raw materials can be contacted fully, so
Carry out mechanical force and chemical processing again afterwards, by the mixing of early stage, intercalation/stripping can be made to be carried out with oxidation more thorough,
It is more homogeneous.
Further, in mechanical force and chemical processing procedure, powder shaped oxidisability salt as remover by graphite particle by
Layer peels off, and in the process, using moment excitation energy caused by mechanical force, the effect of oxidisability is played, to graphite particle/stone
Ink sheet layer is aoxidized, and the two complements each other, and individual layer/few Rotating fields are presented in obtained graphene oxide, and edge/interior is oxygen-containing
Functional group is modified.
In a kind of optional embodiment, in step (a), the mode of action of the mechanical force and chemical is abrasive action,
One or more of combinations in compression, percussion, rubbing action, shear action or progradation；
And/or the processing equipment of the mechanical force and chemical is horizontal ball mill, vibrator, planetary ball mill, stirred
Mix one or more of combinations in grinding machine, ultrasonic machine, roller mill or sand mill.
It is understood that the mechanical force and chemical processing equipment employed in the present invention, preferably above-mentioned several, but not
It is limited to above-mentioned several, can also is centrifugal grinding mills, basket-type grinder or colloid mill etc., in protection scope of the present invention
It is interior.
In a kind of optional embodiment, in step (a), the processing time of the mechanical force and chemical is 1~24 hour.
Optionally, the processing time of mechanical force and chemical typical but non-limiting is：1 hour, 2 hours, 3 hours, it is 4 small
When, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 14 hours, 15 hours, 16 hours, 18
Hour, 20 hours, 22 hours or 24 hours.
The present invention step (a) can be：By graphite and potassium peroxydisulfate, sodium peroxydisulfate, potassium hydrogen persulfate or hydrogen persulfate
One or more of mixtures in the persulfates such as sodium be stirred mixing it is well mixed after, using horizontal ball mill, vibration
The equipment such as ball mill, planetary ball mill or agitator mill carry out mechano-chemical reation, react under room temperature condition carry out 1~
24 hours, intermediate is made；
Wherein, graphite used is crystalline flake graphite, expanded graphite, intercalated graphite, graphite powder or graphene powder, the grain of graphite
Footpath is 40~15000 mesh, and the mass ratio of graphite and oxidisability salt is 1：(1~100).
The oxidisability salt such as the potassium peroxydisulfate used compared to organic peroxide, the present invention are more stable and safe, and this
Class salt is widely used in water process and soil remediation process, to environmental hazard very little.The present invention uses oxidisability salt bonding machine
Tool power chemical process prepares graphene oxide, so as to the use of reduce or forgo dangerous and toxic chemical, improves oxidation
Graphene yield, the preparation cost of graphene oxide is reduced, to realize scale of mass production graphene oxide, and its industrial applications
Lay the foundation.
In a kind of optional embodiment, in step (b), the washing includes washing, pickling and the water carried out successively
Wash；
And/or the drying is freeze-drying, is dried in vacuo, is in forced air drying or spray drying one or more of
Combination, the dry time is preferably 24~60 hours.
Optionally, dry to be freeze-dried, the time of freeze-drying is 24~60 hours, preferably 30~50 hours, is entered
One step is preferably 38~48 hours.
The present invention step (b) can be：Obtained intermediate is washed, the purification process of pickling etc., after separation,
The processing that the product of gained is dried in vacuo or is freeze-dried etc., wherein the dry time is 24~60 hours, so as to
To purity is higher, graphene oxide of excellent performance.
Optionally, the advanced water-filling of the intermediate of gained is washed, then carries out pickling, then washed again.Wherein, the first step
Washing be in order to remove the graphite powder particle of remaining oxidisability salt in course of reaction and unstripped/oxidation, pickling be in order to
Remove reaction in metal impurities that may be present, last water-washing process be by remnants acid and impurity remove, by this three
Product purity is high obtained by after step, excellent performance.
Second aspect, present embodiment provides a kind of graphene oxide, by the preparation side of above-described graphene oxide
Method is made.
The third aspect, present embodiment provide a kind of graphene oxide in composite, conductive electrode and energy conversion
With the application in memory device.
Further, the composite includes graphene nanometer conductive compound material and graphene nano anti-corrosion composite wood
At least one of material.
It is 500nm or so as the piece footpath size of the graphene oxide obtained by the preparation method of the present invention；Piece footpath thickness is 1
~5nm, wherein individual layer or few layer graphene oxide sheet be present.
Meanwhile the graphene oxide has higher electrical conductivity, the electrical conductivity after high-temperature process has quantity
Lifting in level.
In addition, the graphene oxide has in water, ethanol, ethylene glycol, NMP, DMF, butyl equal solvent
Excellent dispersiveness, and the stability of dispersion liquid is very good, standing for several weeks is not in sedimentation.
As can be seen here, graphene oxide produced by the present invention has good dispersiveness, stability, electric conductivity and can added
Work performance, therefore there is preferable application prospect in the field such as composite, conductive electrode and energy conversion and memory device.
For example, can be using graphene oxide provided by the invention as in anode material for lithium-ion batteries or negative material
Functional material uses；Or used described graphene oxide as main material in composite or functional material.
With reference to specific embodiment, comparative example and accompanying drawing, the invention will be further described.
Embodiment 1
A kind of preparation method of graphene oxide, comprises the following steps：
(a) the mesh crystalline flake graphites of 2g 325 are uniformly mixed with 40g ammonium persulfate-sodium bisulfates, are 10 in ratio of grinding media to material：
1st, under conditions of rotational speed of ball-mill is 240rpm/min, ball milling 8 hours, obtain intermediate in planetary ball mill；
(b) intermediate of gained is washed with deionized unreacted persulfate, slow-speed of revolution centrifugation remove it is unstripped/
The graphite powder of oxidation, then with mass concentration be about 5% hydrochloric acid washed product present in metal impurities, finally use deionized water
Centrifuge washing product is freeze-dried 48 hours to neutrality, that is, obtains graphene oxide powder.
Picture after the water of obtained graphene oxide, ethanol, NMP, DMF dispersion liquid stand one month in embodiment 1, such as
Shown in Fig. 1, its dispersion liquid concentration is 0.5mg/ml.
From figure 1 it appears that dispersion stabilization of the gained graphene oxide in water, ethanol, NMP, DMF common solvent
It is very good.
The yield of graphene oxide is 78% in embodiment 1, predominantly individual layer/few layer graphene oxide, gained oxidation stone
Black alkene can be stabilized under 10000rpm/min centrifugal conditions.Elementary analysis test is carried out to gained graphene oxide, surveyed
Test result shows that the oxygen content in graphene oxide is 8.6wt%, phosphorus content 87wt%.
The graphene oxide powder 190mg obtained in embodiment 1 is weighed, uniform disk is pressed into tablet press machine, is tested
Its electrical conductivity, the electrical conductivity measured are 2380S/m；It is handled to 30min, mass excess 168mg under 800 DEG C of nitrogen atmospheres,
It is 20350S/m to measure electrical conductivity.
Embodiment 2
A kind of preparation method of graphene oxide, comprises the following steps：
(a) the mesh graphite powders of 2g 15000 are uniformly mixed with 40g potassium hydrogen persulfates, are 10 in ratio of grinding media to material：1st, ball milling
Under conditions of rotating speed is 240rpm/min, ball milling 8 hours, obtain intermediate in planetary ball mill；
(b) intermediate of gained is washed with deionized unreacted persulfate, slow-speed of revolution centrifugation remove it is unstripped/
The graphite powder of oxidation, then with mass concentration be about 5% hydrochloric acid washed product present in metal impurities, finally use deionized water
Centrifuge washing product is freeze-dried 48 hours to neutrality, that is, obtains graphene oxide powder.
The HRTEM figures and infrared analysis collection of illustrative plates of obtained graphene oxide in embodiment 2, respectively as shown in Figures 2 and 3.
As can be seen that the piece footpath size of gained graphene oxide is 500nm from Fig. 2 and Fig. 3, the piece number of plies is about 5
Layer；For oxygen-containing functional group based on epoxy, carboxyl, hydroxyl, the graphene oxide prepared with chemical reduction method is similar.
The yield of graphene oxide is 84% in embodiment 2, and gained graphene oxide can centrifuge in 10000rpm/min
Under the conditions of be stabilized.Elementary analysis test is carried out to gained graphene oxide, test result shows containing in graphene oxide
Oxygen amount is 11wt%, phosphorus content 86wt%.
The graphene oxide powder 194mg obtained in embodiment 2 is weighed, uniform disk is pressed into tablet press machine, is tested
Its electrical conductivity, the electrical conductivity measured are 1587S/m；It is handled to 30min, mass excess 172mg under 800 DEG C of nitrogen atmospheres,
It is 23809S/m to measure electrical conductivity.
Embodiment 3
A kind of preparation method of graphene oxide, comprises the following steps：
(a) the mesh graphite powders of 2g 325 are uniformly mixed with 40g potassium hydrogen persulfates, are 10 in ratio of grinding media to material：1st, ball milling turns
Under conditions of speed is 240rpm/min, ball milling 12 hours, obtain intermediate in planetary ball mill；
(b) intermediate of gained is washed with deionized unreacted persulfate, slow-speed of revolution centrifugation remove it is unstripped/
The graphite powder of oxidation, then with mass concentration be 5% hydrochloric acid washed product present in metal impurities, finally with deionized water from
Heart washed product is freeze-dried 48 hours to neutrality, that is, obtains graphene oxide powder.
The HRTEM figures of obtained graphene oxide in embodiment 3, as shown in Figure 4.
Figure 4, it is seen that the piece footpath size of gained graphene oxide is more than 500nm, the piece number of plies is about 10 layers.
The yield of graphene oxide is 71% in embodiment 3, and gained graphene oxide can centrifuge in 10000rpm/min
Under the conditions of be stabilized.
Embodiment 4
A kind of preparation method of graphene oxide, comprises the following steps：
(a) the mesh graphite powders of 20g 325 are uniformly mixed with 400g sodium peroxydisulfates, are 20 in ratio of grinding media to material：1st, ball milling turns
Under conditions of speed is 32rpm/min, ball milling 24 hours, obtain intermediate in horizontal ball mill；
(b) intermediate of gained is washed with deionized unreacted persulfate, slow-speed of revolution centrifugation remove it is unstripped/
The graphite powder of oxidation, then with mass concentration be 5% hydrochloric acid washed product present in metal impurities, finally with deionized water from
Heart washed product is freeze-dried 60 hours to neutrality, that is, obtains graphene oxide powder.
The yield of graphene oxide is 60% in embodiment 4, and gained graphene oxide can centrifuge in 10000rpm/min
Under the conditions of be stabilized.
Embodiment 5
A kind of preparation method of graphene oxide, comprises the following steps：
(a) the mesh expanded graphites of 20g 40 are uniformly mixed with 600g potassium peroxydisulfates, are 20 in ratio of grinding media to material：1st, rotating speed is
Under conditions of 50rpm/min, ground 20 hours in agitator mill, obtain intermediate；
Step (b) is same as Example 1.
The yield of graphene oxide is 65% in embodiment 5, and gained graphene oxide can centrifuge in 10000rpm/min
Under the conditions of be stabilized.
Embodiment 6
A kind of preparation method of graphene oxide, comprises the following steps：
(a) the mesh intercalated graphites of 2g 1000 and 100g hydrogen persulfate sodium are uniformly mixed, are 10 in ratio of grinding media to material：1st, ball
Rotating speed is ground under conditions of 500rpm/min, ball milling to be ground in roller mill 5 hours, obtaining intermediate；
Step (b) is same as Example 1.
The yield of graphene oxide is 68% in embodiment 6, and gained graphene oxide can centrifuge in 10000rpm/min
Under the conditions of be stabilized.
Embodiment 7
A kind of preparation method of graphene oxide, comprises the following steps：
By the freeze-drying 48 hours in step (b), vacuum drying 24 hours is replaced with, remaining is same as Example 1.
The yield of graphene oxide is 78% in embodiment 7, and gained graphene oxide can centrifuge in 10000rpm/min
Under the conditions of be stabilized.
Comparative example 1
A kind of preparation method of graphene oxide, using the preparation method of graphene oxide of the prior art；Will
A certain amount of graphite powder and benzoyl peroxide, Peracetic acid/hydrogenperoxide steam generator carry out ball milling 1h, take supernatant liquor and will be upper
Layer clear liquid heating obtains graphene oxide powder after being evaporated.The yield of gained graphene oxide is 22.92%.
Comparative example 2
A kind of preparation method of graphene oxide, using the preparation method of graphene oxide of the prior art；Will
Graphene oxide is prepared using mechanism after the oxidants such as phthalic acid, Peracetic acid, hydrogen peroxide and graphite powder mixing,
A small amount of grinding aid is added, under certain temperature, pressure, ball milling 300min, is then put into water, is stirred, is stood, point
From obtaining graphene oxide.The yield of gained graphene oxide is 32%.
The preparation method of graphene oxide provided by the invention, significantly improves graphite oxide it can be seen from more than
The yield of alkene, yield is more than 60%, and gained graphene oxide can stably be deposited under 10000rpm/min centrifugal conditions
；Obtained graphene oxide conducts electricity very well simultaneously, in water, organic solvent it is medium in have it is excellent dispersed and steady
It is qualitative.The method of the present invention has the characteristics of quick, easy, efficient, security is good, green, being capable of mass, industrialization
Preparation with fine dispersion performance, electric conductivity and stability graphene oxide, and then for graphene oxide in composite
Introducing Deng field opens gate.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of graphene oxide, it is characterised in that the described method comprises the following steps：
Graphite is well mixed with oxidisability salt, then carries out crushing stripping and oxidation processes by way of mechanical force and chemical,
Obtain intermediate；
Gained intermediate is washed and dried, produces graphene oxide.
2. the preparation method of graphene oxide according to claim 1, it is characterised in that the graphite be crystalline flake graphite,
One or more of mixtures in expanded graphite, intercalated graphite, graphite powder or graphene powder；
And/or the particle diameter of the graphite is 40~15000 mesh.
3. the preparation method of graphene oxide according to claim 1, it is characterised in that the oxidisability salt is persulfuric acid
One or more of mixtures in salt, preferably potassium peroxydisulfate, sodium peroxydisulfate, potassium hydrogen persulfate or hydrogen persulfate sodium.
4. the preparation method of the graphene oxide according to any one of claims 1 to 3, it is characterised in that the graphite with
The mass ratio of oxidisability salt is 1：(1~100).
5. the preparation method of graphene oxide according to claim 1, it is characterised in that the effect of the mechanical force and chemical
Mode is one or more of in abrasive action, compression, percussion, rubbing action, shear action or progradation
Combination；
And/or the processing equipment of the mechanical force and chemical is horizontal ball mill, vibrator, planetary ball mill, Ball-stirring mill
One or more of combinations in machine, ultrasonic machine, roller mill or sand mill.
6. the preparation method of graphene oxide according to claim 1, it is characterised in that the processing of the mechanical force and chemical
Time is 1~24 hour.
7. the preparation method of the graphene oxide according to claims 1 to 3 or 5~6 any one, it is characterised in that described
Washing includes washing, pickling and the washing carried out successively；
And/or the drying is freeze-drying, is dried in vacuo, one or more of combinations in forced air drying or spray drying,
The dry time is preferably 24~60 hours.
8. a kind of graphene oxide, it is characterised in that as the preparation side of the graphene oxide described in any one of claim 1~7
Method is made.
9. the answering in composite, conductive electrode or energy conversion and memory device of the graphene oxide described in claim 8
With.
10. application according to claim 9, it is characterised in that：It is compound that the composite includes graphene nano conduction
At least one of material and graphene nano antisepsis composite material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607519A (en) * | 2018-05-02 | 2019-04-12 | 华中科技大学 | A kind of preparation method of highly-water-soluble hypoxemia graphene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| CN102757038A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
| CN103288078A (en) * | 2013-07-05 | 2013-09-11 | 何钊 | Process for preparing graphene oxides |
| CN103332670A (en) * | 2013-06-21 | 2013-10-02 | 重庆交通大学 | Method for preparing graphene oxide |
| CN106276857A (en) * | 2016-08-12 | 2017-01-04 | 上海交通大学 | A kind of method preparing functional carbon material |
-
2017
- 2017-09-14 CN CN201710830306.3A patent/CN107352532A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| CN102757038A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院宁波材料技术与工程研究所 | Method for preparing graphene |
| CN103332670A (en) * | 2013-06-21 | 2013-10-02 | 重庆交通大学 | Method for preparing graphene oxide |
| CN103288078A (en) * | 2013-07-05 | 2013-09-11 | 何钊 | Process for preparing graphene oxides |
| CN106276857A (en) * | 2016-08-12 | 2017-01-04 | 上海交通大学 | A kind of method preparing functional carbon material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607519A (en) * | 2018-05-02 | 2019-04-12 | 华中科技大学 | A kind of preparation method of highly-water-soluble hypoxemia graphene |
| CN109607519B (en) * | 2018-05-02 | 2021-09-17 | 华中科技大学 | Preparation method of high-water-solubility low-oxygen graphene |
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