CN105692599B - A kind of preparation method without fragment super large piece graphene oxide - Google Patents
A kind of preparation method without fragment super large piece graphene oxide Download PDFInfo
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- CN105692599B CN105692599B CN201610046898.5A CN201610046898A CN105692599B CN 105692599 B CN105692599 B CN 105692599B CN 201610046898 A CN201610046898 A CN 201610046898A CN 105692599 B CN105692599 B CN 105692599B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of preparation method of the super large piece without fragment graphene oxide.Before the washing of this method graphite oxide crystal, the method separated using mesh screen is gone out chip separation.And using 10 times to be diluted with the frozen water of upper volume so that its chip will not be destroyed because of the heat of solution of sulfuric acid.Washing is further shaken using shaking table so that graphene oxide layer avoids the broken of mechanical force when peeling off.Preparation process of the present invention is simple and safe controllable, and time consumption and energy consumption is few, by simply before product the step of lock out operation one obtain the graphene oxide of no fragment super large.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly a kind of preparation method without fragment super large piece graphene oxide.
Background technology
2004, Univ Manchester UK A.K.Geim professors seminar successfully prepared graphite with mechanical stripping method
Alkene, has overthrown this judgement that perfect two dimensional crystal structure can not be stabilized under non-absolute zero.Then graphene is excellent
Mechanical property, electrical properties, thermal property, optical property found in succession.Graphene has the theoretical specific surface area of super large,
In addition the excellent properties that monolithic Rotating fields have, the carbon-based material using graphene as source material has obtained significant progress
And application.It is considered as that most probable realizes important method prepared by graphene industrialization that oxidation-reduction method, which prepares graphene,.And its
Intermediate oxidation graphene is then the important presoma of graphene, is that grapheme material realizes macroscopic view assembling and modified most important
Intermediate.Macroscopical assembled material fiber, film, aeroge for having been carried out at present etc. are all to rely on graphene oxide to make
Standby.
The existing method for preparing graphene oxide mainly has Brodie, Staudenmaier, Hofmann, Hummers
And modified Hummers.However, during oxidation and ultrasound are peeled off, graphene oxide inevitably part
It is broken into many small pieces.The graphene oxide fragment of these small pieces significantly reduces the conduction of the macroscopical assembled material of graphene
Heat conductivility, limits the application of graphene oxide.Therefore, a kind of method for preparing no fragment super large piece graphene oxide needs
Propose.
Hereafter, it is thus proposed that Density ultracentrifugation (DGU) technology separates graphene oxide, but due to its separation
Time cost it is higher, it is difficult to realize large-scale production.2011, Tsing-Hua University Shi Gaoquan professors seminar was worked out with pH points
Level method can isolate large stretch of graphene oxide with small pieces, greatly improve graphene oxide assembled material when pH is 4.0
Mechanical performance and electrical property., the method that teacher Shi Gaoquan is found that suction filtration classification again in 2015.But these methods are all
It is completely exfoliated after graphene oxide and goes classification again, effect is not good and inefficient, can only be used as scientific research purposes, it is impossible to work
Industry is amplified.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of easy without fragment super large piece graphene oxide
Preparation method, the area of graphene oxide sheet prepared by this method is big and without fragment；The process operation is simple, quickly, and
Pollution problem is alleviated to a certain extent.
The purpose of the present invention is achieved through the following technical solutions：A kind of preparation without fragment super large piece graphene oxide
Method, it the step of it is as follows：
（1）After the reaction solution dilution for the oxidized graphite flake that Modified-Hummer methods are obtained, enter in the mesh screen of 140 mesh
Row filtering, obtains filtration product；
（2）The filtration product that step 1 is obtained is in frozen water according to volume ratio 1：After 10 is well mixed, 2h is stood, is added dropwise
Enter hydrogen peroxide（H2O2Mass fraction be 30%）, until the color of mixed liquor no longer changes（Potassium permanganate i.e. in mixed liquor is
Remove completely）；
（3）Concentrated hydrochloric acid is added dropwise in mixed liquor after being handled to step 2（Concentration is 12mol/L）, until cotton-shaped oxygen
Graphite disappears, then goes out graphite oxide chip with the screen filtration of 140 mesh；
（4）The graphite oxide chip that step 3 is obtained is placed in shaking table, 20 ~ 80 turns/min, concussion washing so that oxidation
Graphite wafer is peeled off, and obtains the graphene oxide of no fragment super large piece, and average-size is more than 87 um, and breadth coefficient is in 0.2-0.5
Between.
Further, the Modified-Hummer methods in the step 1 are specially：- 10oUnder C, potassium permanganate is filled
Divide and be dissolved in the concentrated sulfuric acid that mass fraction is 98%, stop stirring after adding graphite, 60 revs/min of stirring 2h, in low temperature（-
10-20oC）Lower reaction 6-48h, obtains the oxidized graphite flake reaction solution of wide distribution；Described graphite, potassium permanganate and the concentrated sulfuric acid
Mass volume ratio is：1 g：2-4g：30-40ml, the granularity of graphite is more than 150 μm.
Further, the mesh screen is the acidproof mesh screens such as titanium alloy.
Further, in the step 1, the reaction solution of oxidized graphite flake is diluted by diluents such as the concentrated sulfuric acids, dilute
The volume for releasing agent is 1-10 times of reaction solution volume.
Preparation process of the present invention is simple and safe controllable, and time consumption and energy consumption is few, is directly converted into graphite greatly by a kind of method
Piece and the graphene oxide without fragment, are that the research and development of High-performance graphene material and application are laid a good foundation.Secondly, in this method
During preparing graphene oxide, without using the halogen of contaminative, manganese ion can also be recycled, and produce pollution small.
Brief description of the drawings
Fig. 1 is the graphite oxide crystal before filtering（It is left）, the graphite oxide crystal after filtering（It is right）.
Fig. 2 is the graphene oxide before filtering（It is left）, the graphene oxide after filtering（It is right）.
Fig. 3 is 50 degree and reacts obtained graphene oxide down.
Fig. 4 is 50 degree and reacts obtained graphene oxide Size Distribution down（It is left）, 20 degree are reacted obtained graphite oxide down
Alkene Size Distribution（It is right）.
Embodiment
Normal graphite flake layer is all irregular, its surface and many defects of marginal existence or has been loaded a lot
Graphite scrap, in oxidizing process, fragment can come off and big bulk oxidation graphite wafer departs from, after oxidation reaction is completed
These defects or fragment become to be present in graphene oxide for the fragment of graphene oxide.Because fragment graphene oxide
It is similar with large stretch of graphene oxide property, it is difficult to be separated with simple method.
The present invention is before the washing of graphite oxide crystal, and the method separated using mesh screen is gone out chip separation.And use 10
It is diluted again with the frozen water of upper volume so that its chip will not be destroyed because of the heat of solution of sulfuric acid.Further use and shake
Bed concussion washing so that graphene oxide layer avoids the broken of mechanical force when peeling off.Further, the present invention is gone back
Graphene film is prepared by cryogenic conditions, at low temperature, potassium permanganate oxidation is weaker, its selfdecomposition produces the speed of oxygen
It is slow, therefore gas is just very weak to the fragmentation of graphite oxide crystal so that the graphene oxide of big lamella is preserved.
And there is no violent stirring and ultrasonic procedure in course of reaction and cleaning process, therefore lamella there is no it is broken.It is comprehensive
What time close the above, we have obtained the graphene oxide without fragment of super large piece, average-size is more than 87 um, and breadth coefficient exists
Between 0.2-0.5, shive content is less than 1%.
With reference to embodiment, the invention will be further described.
Embodiment 1
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, 20oC、50 o6h is reacted under C respectively, the oxidation of wide distribution is respectively obtained
Graphite crystal；As shown in figure 1, there is more fragment in the graphite oxide chip obtained at a temperature of two kinds, this causes its right
The graphene oxide answered equally has many fragments（Fig. 2）.
The reaction solution diluting concentrated sulfuric acid that step 1 is obtained（Extension rate can be any multiple, and the present embodiment is diluted
10 times or so）, and use 150um apertures（140 mesh）Titanium alloy mesh screen graphite oxide crystal is filtered out（Reaction solution is reclaimed）,
And be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, H is slowly added to2O2, to remove
Unnecessary potassium permanganate in reaction, the appropriate hydrochloric acid of addition disappears until cotton-shaped graphite oxide, then uses titanium alloy mesh screen（140 mesh）
Filter out graphite oxide chip；Shaking table slowly shakes washing, obtains the graphene oxide of no fragment super large piece（Average-size is 87
Um, breadth coefficient is 0.5）.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1 g：2g：40ml, the granularity of graphite is
200um。
As shown in figure 3, washing obtained oxidation stone after the graphite oxide chip separation isolated after the lower reaction of 50 degree of high temperature
Black alkene equally has many fragments；From fig. 4, it can be seen that under low temperature（20oC）Large stretch of graphene oxide size after Reaction Separation
Distribution more uniform concentration, shive content is few.
Embodiment 2
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, in low temperature（0oC、）Lower reaction 48h, obtains reaction solution；By reaction solution point
It is not diluted with the concentrated sulfuric acid of mass fraction more than 98%, mass fraction for 10% dilute sulfuric acid, then with the titanium in 150um apertures
Alloy mesh screen filters out graphite oxide crystal（Reaction solution is reclaimed）, and be poured slowly into quickly stir relative to filtration product
In the frozen water of 10 times of volumes, 2h is stood, H is slowly added to2O2 , except potassium permanganate unnecessary in dereaction, to add appropriate salt
Acid disappears until cotton-shaped graphite oxide, then filters out graphite oxide chip with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains
Reaction product.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：4g：30ml；The granularity of graphite is 500um.
Using diluting concentrated sulfuric acid, the obtained graphene oxide without fragment super large piece is reacted（Average-size is 98 um, point
Cloth coefficient is 0.4）, and diluted with dilute sulfuric acid, a large amount of fragments are contained in obtained product, Size Distribution coefficient is more than 100%.This
It is highly exothermic in being due to dilute sulfuric acid dilution, destroy graphite oxide crystal.
Embodiment 3
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, in low temperature（20oC）Lower reaction 28h, the graphite oxide for obtaining wide distribution is brilliant
Body；Reaction solution is filtered out graphite oxide crystal with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures（Reaction solution
Reclaim）, and be poured slowly into respectively quickly stir relative in 5 times of volumes of filtration product, 8 times of volumes, the frozen water of 10 times of volumes,
2h is stood, H is slowly added to2O2 , except potassium permanganate unnecessary in dereaction, to add appropriate hydrochloric acid until cotton-shaped graphite oxide
Disappear, then graphite oxide chip is filtered out with titanium alloy reticulated is sieved；Shaking table slowly shakes washing, obtains reaction product；Graphite, Gao Meng
Sour potassium is with concentrated sulfuric acid mass volume ratio：1：5g：34ml, the granularity of graphite is 2mm.
Experimental result shows, the frozen water of 5 times of volumes and 8 times of volumes can not the graphene film for obtaining size uniformity,
The graphene oxide of no fragment super large piece can be just obtained under 10 times of volumes（Average-size is 92 um, and breadth coefficient is 0.2）.By
This understands that the amount of frozen water is too low, and the heat of mixing will be caused to concentrate release, destroys crystal structure.
Embodiment 4
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, in low temperature（10oC）Lower reaction 18h, the graphite oxide for obtaining wide distribution is brilliant
Body；Reaction solution is filtered out graphite oxide crystal with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures（Reaction solution
Reclaim）, and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, H is slowly added to2O2 ,
So that except potassium permanganate unnecessary in dereaction, the appropriate hydrochloric acid of addition disappears until cotton-shaped graphite oxide, then uses titanium alloy mesh screen
Filter out graphite oxide chip；Shaking table slowly shakes washing, obtains the graphene oxide of no fragment super large piece（Average-size is 89
Um, breadth coefficient is 0.5）.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：5g：40ml.The granularity of graphite is
300um。
Embodiment 5
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, in low temperature（15oC）Lower reaction 36h, the graphite oxide for obtaining wide distribution is brilliant
Body；Reaction solution is filtered out graphite oxide crystal with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures（Reaction solution
Reclaim）, and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, H is slowly added to2O2 ,
So that except potassium permanganate unnecessary in dereaction, the appropriate hydrochloric acid of addition disappears until cotton-shaped graphite oxide, then uses titanium alloy mesh screen
Filter out graphite oxide chip；Shaking table slowly shakes washing, obtains the graphene oxide of no fragment super large piece（Average-size is
103 um, breadth coefficient is 0.5）.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：4g：40ml, the granularity of graphite
For 1mm.
Embodiment 6
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, in low temperature（20oC）Lower reaction 48h, the graphite oxide for obtaining wide distribution is brilliant
Body；Reaction solution is filtered out graphite oxide crystal with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures（Reaction solution
Reclaim）, and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, H is slowly added to2O2 ,
So that except potassium permanganate unnecessary in dereaction, the appropriate hydrochloric acid of addition disappears until cotton-shaped graphite oxide, then uses titanium alloy mesh screen
Filter out graphite oxide chip；Shaking table slowly shakes washing, obtains the graphene oxide of no fragment super large piece（Average-size is
108 um, breadth coefficient is 0.2）.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：5g：30ml.The granularity of graphite
For 2mm.
Embodiment 7
- 10oPotassium permanganate is slowly added under C in the concentrated sulfuric acid quickly stirred, after after abundant dissolving, adds stone
Ink, 60 revs/min are slowly stirred stopping stirring after 2h, in low temperature（12oC）Lower reaction 10h, the graphite oxide for obtaining wide distribution is brilliant
Body；Reaction solution is filtered out graphite oxide crystal with diluting concentrated sulfuric acid and with the titanium alloy mesh screen in 150um apertures（Reaction solution
Reclaim）, and be poured slowly into the frozen water relative to 10 times of volumes of filtration product quickly stirred, 2h is stood, H is slowly added to2O2 ,
So that except potassium permanganate unnecessary in dereaction, the appropriate hydrochloric acid of addition disappears until cotton-shaped graphite oxide, then uses titanium alloy mesh screen
Filter out graphite oxide chip；Shaking table slowly shakes washing, obtains the graphene oxide of no fragment super large piece（Average-size is 88
Um, breadth coefficient is 0.3）.Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio are：1：4g：40ml, the granularity of graphite is
800um。
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, any modifications and changes made to the present invention both fall within protection scope of the present invention.
Claims (4)
1. a kind of preparation method without fragment super large piece graphene oxide, it is characterised in that：Its step of, is as follows：
（1）After the reaction solution dilution for the oxidized graphite flake that Modified-Hummer methods are obtained, carried out in the mesh screen of 140 mesh
Filter, obtains filtration product；
（2）The filtration product that step 1 is obtained is with frozen water according to volume ratio 1：After 10 is well mixed, 2h is stood, is added dropwise double
Oxygen water, until the color of mixed liquor no longer changes；
（3）Concentrated hydrochloric acid is added dropwise in mixed liquor after being handled to step 2, until cotton-shaped graphite oxide disappearance, then 140 mesh are used
Screen filtration go out graphite oxide chip；
（4）The graphite oxide chip that step 3 is obtained is placed in shaking table, 20 ~ 80 turns/min, concussion washing so that graphite oxide
Chip is peeled off, and obtains the graphene oxide of no fragment super large piece.
2. according to the method described in claim 1, it is characterised in that the Modified-Hummer methods in the step 1 are specific
For：At -10 DEG C, potassium permanganate is completely dissolved in the concentrated sulfuric acid that mass fraction is 98%, adds graphite, 60 revs/min are stirred
Mix and stop stirring after 2h, 6-48h is reacted in a low temperature of -10-20 DEG C, obtain the oxidized graphite flake reaction solution of wide distribution；It is described
Graphite, potassium permanganate and concentrated sulfuric acid mass volume ratio be：1 g：2-4g：30-40ml, the granularity of graphite is more than 150 μm.
3. according to the method described in claim 1, it is characterised in that the mesh screen is acidproof mesh screen.
4. according to the method described in claim 1, it is characterised in that in the step 1, the reaction solution of oxidized graphite flake passes through dense
Sulfuric acid is diluted, and the volume of diluent is 1-10 times of reaction solution volume.
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| CN112010298A (en) * | 2020-08-14 | 2020-12-01 | 兰州大学 | Method for rapidly, efficiently and massively preparing large-sheet-diameter graphene oxide |
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