CN108622887A - A kind of swollen quick-fried method for preparing graphene of microwave - Google Patents
A kind of swollen quick-fried method for preparing graphene of microwave Download PDFInfo
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Abstract
The present invention relates to a kind of swollen quick-fried methods for preparing graphene of microwave, belong to technical field of graphene preparation.The swollen quick-fried method for preparing graphene of microwave of the present invention, includes the following steps：1) graphite raw material and intercalator are mixed and carries out acidification intercalation, obtain level-one intercalated graphite slurry；2) OH is added into the level-one intercalation acidifying graphite slurry of gained‑Ion concentration is that strong base solution to the system of 0.1~8mol/L is in neutrality, and obtains two level intercalated graphite slurry；3) by the two level intercalated graphite slurry microwave heating of gained or it is dry after microwave heating to get.The method of the present invention, it helps to open the capillary diffusion channel between graphite flake layer using acidification intercalation processing, again by highly basic with acid in graphite layers and, eliminate the introduced oxide group of acidification intercalation processing, it is heated later by rapid microwave, the high-efficiency layered for realizing graphite, directly prepares the three-dimensional grapheme powder being made of ultra-thin graphene sheet layer cluster.
Description
Technical field
The present invention relates to technical field of graphene preparation, and in particular to a kind of swollen quick-fried method for preparing graphene of microwave.
Background technology
Graphene is as a kind of carbon atom with Sp2Hydridization in conjunction with and constitute single layer two dimensional crystal, because of its special physics
Chemical property increasingly gets more and more people's extensive concerning.The study found that the carrier in graphene follows near fermi level
A kind of linear dispersion relationship is similar with the dirac fermion of massless, this assigns its many outstanding performance, such as quantum is suddenly
That effect and Dual-polarized electricity field-effect.In addition, graphene shows on-dispersive transmission characteristic, electron mobility is high at room temperature
Up to 1500cm2/ (Vs) is far above traditional semi-conducting material.Using the conductivity that graphene is excellent, transparency and higher
Thermal stability and chemical stability, in enhancing metal ion battery plus-negative plate material specific capacity, cyclical stability and environment
The fields such as catalytic substrate material are widely used.
So far, there are many method for preparing single layer or few layer graphene piece, such as adhesive tape mechanical stripping graphite method,
SiC epitaxial growth methods, electronation graphite oxide method, graphite liquid phase stripping method, the methods of chemical vapour deposition technique.Adhesive tape machinery
Stripping method is a kind of simple preparation method, however this method yield is extremely low, and will produce adhesive tape and the residue of dispersion solvent
And influence the proper property of graphene；SiC epitaxial growth methods are higher to preparation condition and equipment requirement, and the graphene synthesized is difficult
To be detached from substrate；Electronation graphite oxide method introduces a large amount of oxygen-containing functional group, and graphene obtained contains a large amount of lack
It falls into, preparation process generates a large amount of chemical waste fluids；There are low yields for conventional graphite liquid phase stripping method, and graphene sheet layer is made and reunites,
And cause a large amount of chemical waste fluid pollution environment；Then there is technical sophistication in chemical vapour deposition technique, low yield is of high cost, be not suitable for
In prepare powder body material the problems such as.
A kind of process preparing graphene oxide is disclosed in the patent that Authorization Notice No. is CN102583328B, it should
Process includes the following steps：1) natural flake graphite is mixed with oxidant, after isothermal reaction, washing filters, is dry
To the graphite particle of oxidation intercalation；2) to step 1) obtained graphite particle carries out microwave heating, obtain the swollen graphite that rises；3) to
Dispersant is added in the swollen graphite that rises that step 2) obtains, graphene oxide is obtained by ultrasound stripping, suction filtration, drying.It is used
Oxidant be the concentrated sulfuric acid and potassium permanganate combination, the group of the combination of concentrated nitric acid and perchloric acid or concentrated phosphoric acid and potassium permanganate
It closes.This method relies on a large amount of strong oxidizers progress intercalation processings and prepares the expanded graphite of interlevel oxidation, since expansion rate is not good enough,
Graphene oxide powder must be made by solution dispersion and excusing from death stripping expanded graphite.In addition, as conventional oxidation method
One of technology mutation, the technology equally generate a large amount of chemical waste fluids, and product defects rate is excessively high, and yield is undesirable.
Therefore, a kind of method that efficient, of low cost, environmental-friendly magnanimity prepares low defect graphene is developed, is had
Important technical meaning and wide application prospect.
Invention content
The object of the present invention is to provide a kind of swollen quick-fried methods for preparing graphene of microwave, can solve prior art preparation
The excessively high technical problem of graphene defect.
In order to achieve the goal above, the technical solution adopted in the present invention is：
A kind of swollen quick-fried method for preparing graphene of microwave, includes the following steps：
1) graphite raw material is mixed with intercalator and carries out acidification intercalation, obtain level-one intercalated graphite slurry；
2) OH is added into the level-one intercalated graphite slurry obtained by step 1)-Ion concentration is the highly basic of 0.1~8mol/L
Solution to system is in neutrality, and obtains two level intercalated graphite slurry；
3) by the two level intercalated graphite slurry microwave heating obtained by step 2), or by the two level intercalation stone obtained by step 2)
Microwave heating after the drying of black slurry, obtain three-dimensional grapheme powder to get；The microwave heating is in 5~300s by micro-wave oven
Interior temperature of charge rises to 400~1000 DEG C.
The swollen quick-fried method for preparing graphene of microwave of the present invention uses the efficient intercalation processing of two step of Acid-Base to graphite raw material
Rapid microwave heat treatment is carried out afterwards.After carrying out acidification level-one intercalation to graphite, carried out at two level intercalation using strong base solution
It manages and significantly strengthens intercalation effect, then handled by microwave fast heating by directly prepare three-dimensional grapheme powder.Wherein
Level-one acidification intercalation processing helps to open the capillary diffusion channel of graphene film interlayer, and when two level intercalation processing, soda acid is in interlayer
Neutralization reaction generation salt occurs and water avoids or eliminate oxygen to eliminate the introduced interlayer acidic molecular of level-one intercalation processing
Change group, heated later by rapid microwave, realize the high-efficiency layered of graphite, directly prepares and be made of ultra-thin graphene sheet layer cluster
Three-dimensional grapheme powder.It can cause the interlayer of secondary intercalation graphite especially by microwave heating secondary intercalation graphite slurry
The Quick-gasifying of water fully improves the effect of graphite laminated.
In order to avoid the forfeiture of the water of the interlayer of two level intercalation introducing, used when being dried to intercalated graphite slurry
Temperature should be no more than 80 DEG C, the dry time is preferably 20~40min.Using above-mentioned condition to secondary intercalation graphite slurry into
When row is dry, the moisture on secondary intercalation graphite particle surface layer can be removed, while avoiding the funeral of the intermediary water of two level intercalation introducing
It loses, obtains secondary intercalation graphite siccative.
The present invention is using, with progress intercalation processing, the two level intercalation processing that strong base solution is brought can be effectively in Acid-Base
Intercalation effect is improved, enhancing intercalation efficiency is cooperateed with level-one acidification intercalation, is conducive to, by quick swollen quick-fried layering, directly prepare
The three-dimensional reduced graphene particle being made of petal-shaped thin graphene piece；It can be also effectively reduced microwave power simultaneously,
And acid mist will not be generated in microwave heating, reduce the corrosion to equipment and the harm to health, it is environmentally protective, it is high
It imitates energy saving.
The swollen quick-fried method for preparing graphene of microwave of the present invention, simple process and low cost is honest and clean, without first by graphite oxidation system
It is standby to obtain graphene oxide, then graphene oxide restored to obtain graphene；But by the swollen quick-fried processing of disposable microwave, directly
The extremely low three-dimensional grapheme powder of ratio of defects is prepared, is suitable for mass producing high quality low defect graphene, have great
Technical meaning and wide application prospect.
Preferably, the grain size of the graphite raw material is less than 2mm.It is further preferred that the granularity mesh number of the graphite raw material
For 10~500 mesh.Still more preferably, the granularity mesh number of the graphite raw material is 30~500 mesh.
Preferably, in step 1), the acidification intercalation is stood at normal temperatures after mixing graphite raw material with intercalator, institute
The time for stating standing is 20min~3h.It stands at normal temperatures, oxidation of the intercalator to graphite can be largely reduced.
The mass ratio of the graphite raw material and intercalator is 1:(2~10).
The intercalator is at least one of concentrated nitric acid, concentrated phosphoric acid or both potassium permanganate and concentrated nitric acid, concentrated phosphoric acid
At least one mixture.The concentration of the concentrated nitric acid is not less than 65%wt.The concentration of the concentrated phosphoric acid is not less than 85%wt.
The intercalator is the mixed acid of concentrated nitric acid and concentrated phosphoric acid, H in the mixed acid3PO4With HNO3Mass ratio it is little
In 5.
Contain potassium permanganate in the intercalator, the mass ratio of potassium permanganate and graphite raw material is not more than 1.5.Mandatory declaration
, excessive potassium permanganate can introduce oxidation defect, be unfavorable for preparing high-quality graphene product.
Preferably, in step 2), the solute of the strong base solution be in sodium hydroxide, potassium hydroxide or lithium hydroxide extremely
Few one kind.When intercalation, the two level intercalation that strong base solution is brought can effectively improve intercalation effect, be cooperateed with level-one acidification intercalation
Enhance intercalation efficiency, is conducive to through quick swollen quick-fried layering, while level-one intercalator can be neutralized.Using nitrate or/or phosphoric acid
Salt is acid intercalator, and when sodium hydroxide and/or potassium hydroxide solution are as strong base solution, generated waste liquid can directly be made
It is utilized for chemical fertilizer, it is environmentally protective.
At 20 DEG C, dissolving 12.8g lithium hydroxides are merely able in 100g water, the strong base solution used is lithium hydroxide solution
When, OH in solution at service temperatures-Ion concentration, which differs, surely reaches 8mol/L, and highest is according to the OH that can be reached at this temperature-
The maximum concentration use of ion.
Preferably, concentrated phosphoric acid is contained in the intercalator of use, the solute of strong base solution is sodium hydroxide, potassium hydroxide or hydrogen
At least one of lithia.
Preferably, in step 3), when by two level intercalated graphite slurry microwave heating, water in two level intercalated graphite slurry
Mass percent is no more than 10%.OH in the strong base solution of use-When ion concentration is relatively low, obtained two level intercalated graphite slurry
In water content it is bigger, before microwave heating, a large amount of solvents can be removed so that water content (mass percent) is no more than
10%.The mode for directly filtering or being heated under conditions of no more than 80 DEG C such as may be used and remove a large amount of solvents.
When carrying out microwave heating to secondary intercalation graphite slurry or secondary intercalation graphite siccative, secondary intercalation graphite layers
Water can be rapidly heated gasification, play the role of remove two level intercalated graphite.
The power of microwave heating is related with quality of material.Preferably, the power of the microwave heating is 80~600W/g, i.e.,
The power setting microwave heating power of 80~600W is corresponded to according to every g materials.Under normal conditions, the power of heating be 0.3~
3000kW。
The above-mentioned swollen quick-fried method for preparing graphene of microwave, can also include by the three-dimensional graphite after microwave heating in step 3)
Alkene powder carries out ball milling, prepares graphene powder.The rotating speed of ball milling is 300~450rpm, and the time of ball milling is 1~3h.
Dry ball milling may be used in ball milling, can also use wet ball grinding.The dispersant that wet ball grinding uses is polyethylene
The aqueous solution of pyrrolidones.For example, every 5~15g polyvinylpyrrolidones can be dissolved into 100ml deionized waters, obtain
Dispersant.Graphene suspension will be obtained after wet ball grinding, 15~25min of centrifugation is carried out with the rotating speed of 2500~3500rpm, so
After take upper layer suspension with 7000~9000rpm centrifuge, taking precipitate drying, can further obtain the number of plies be less than 3 graphene
Powder.
The above-mentioned swollen quick-fried method for preparing graphene of microwave further includes using the three-dimensional grapheme powder of gained in step 3)
Neutral flux is washed, then in 60~120 DEG C of dry 0.5~3h.Three-dimensional grapheme powder is carried out using neutral flux
Washing is to remove remaining salt in graphene.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (b) of crystalline flake graphite (S0) scanning electron microscope (SEM) photograph (a) and graphene (S2) in embodiment 1；
Fig. 2 is the Raman collection of illustrative plates of crystalline flake graphite (S0) in embodiment 1, neutral graphite siccative (S1) and graphene (S2).
The graphene oxide (S3) for the graphene and comparative example that Fig. 3 obtains for embodiment 2 (S4) and embodiment 3 (S5),
Raman collection of illustrative plates.
Specific implementation mode
Below in conjunction with specific implementation mode, the following further describes the technical solution of the present invention, the technology that the present invention protects
Parameter area includes but not limited to following case.
Concentrated nitric acid and concentrated phosphoric acid employed in specific implementation mode are that analysis is pure.
Embodiment 1
Graphite used by the present embodiment is crystalline flake graphite, and granularity is 50 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the NaOH solution of a concentration of 1mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by 3g crystalline flake graphites, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：m(HNO3)：m(H3PO4)=1：
2：1 ratio is uniformly mixed, and is stood 30min, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then at 80 DEG C
Following heating evaporation moisture, the mass percent for obtaining water are no more than 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 300W (power), microwave heating 20s make the temperature of neutral graphite slurry reach 500 DEG C or more
(slightly above 500 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder to get.
Electronic Speculum test is scanned with the graphene being prepared to the used crystalline flake graphite of the present embodiment, is as a result seen
Fig. 1.As shown in Figure 1, for crystalline flake graphite after processing, topographical transition is the three-dimensional grapheme being made of petal-shaped thin slice cluster
Powder.
Neutral graphite after being dried to the neutral graphite slurry obtained in crystalline flake graphite, step 2) used by the present embodiment
Siccative, the graphene being prepared carry out Raman spectrum test, and obtained Raman spectrogram is shown in Fig. 2.Graphene (S2) in Fig. 2
D peak intensities be less than neutral graphite siccative (S1), level off to zero, illustrating the ratio of defects of obtained graphene, extremely low (peaks D are opposite
Intensity is suitable with crystalline flake graphite raw material)；The 2D peak symmetries of graphene (S2) are good, and main peak shows 10.1 relative to graphite
The red shift of wave number meets the fingerprint Raman signatures of single-layer graphene；In addition, the secondary compound intercalation of Acid-Base causes swollen quick-fried graphite
The apparent splitting phenomena in the peaks G of alkene (S2), main peak G-The blue shift of 6.2 wave numbers is shown, the peaks G for corresponding to single-layer graphene are blue
Shifting amount, it is main phase composition further to prove single-layer graphene；The secondary peaks G (G+) blue shift about 1, the corresponding number of plies is no more than 5.
Embodiment 2
Graphite used by the present embodiment is crystalline flake graphite, and granularity is 100 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the KOH solution of a concentration of 1mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, potassium permanganate, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：M (potassium permanganate)：m
(HNO3)：m(H3PO4)=1：0.2：1：4 ratio is uniformly mixed, and is stood 3h, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, obtains two level and inserts
Layer graphite slurry；
3) the two level intercalation slurry obtained by step 2) is obtained into two level intercalated graphite siccative, then in 60 DEG C of dry 30min
It is put into micro-wave oven, the ratio setting microwave power of 270W (power), microwave heating is corresponded to according to every g two levels intercalated graphite siccative
20s makes the temperature of neutral graphite slurry reach 450 DEG C or more (slightly above 450 DEG C, be no more than 1000 DEG C), obtains three-dimensional grapheme
Powder to get；
Raman spectrum test, obtained Raman spectrum are carried out to the graphene that method used by the present embodiment is prepared
Figure is shown in Fig. 3 (S4).As a result show that graphene defect is extremely low, according to the peaks G and the variation of the peaks 2D Raman shifts amount it is found that three-dimensional grapheme
Predominantly petal-shaped single-layer graphene film forms, and the few layer graphene piece for having a small amount of number of plies to be not more than 4.
Embodiment 3
Graphite used by the present embodiment is natural graphite, and granularity is 100 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the KOH solution of a concentration of 1mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by natural graphite, potassium permanganate, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (natural graphite)：M (potassium permanganate)：m
(HNO3)：m(H3PO4)=1：0.6：1：4 ratio is uniformly mixed, and is stood 3h, is obtained acidifying graphite slurry；
2) strong base solution to system is added into the acidifying graphite slurry obtained by step 1) to be in neutrality, obtains two level intercalation stone
Black slurry；
3) the two level intercalated graphite slurry obtained by step 2) is obtained into two level intercalated graphite siccative in 50 DEG C of dry 40min,
It is then placed in micro-wave oven, the ratio setting microwave power of 130W (power), microwave is corresponded to according to every g two levels intercalated graphite siccative
Heating 5s makes the temperature of neutral graphite slurry reach 400 DEG C or more (slightly above 400 DEG C, be no more than 1000 DEG C), obtains three-dimensional stone
Black alkene powder to get；
Raman spectrum test, obtained Raman light are carried out to the graphene that method used by the present embodiment is prepared
Spectrogram is shown in Fig. 3 (S5).As a result display is mainly single-layer graphene composition, and a small amount of layer graphene less corresponds to the number of plies and is not more than 7.
Embodiment 4
The used graphite of the present embodiment is crystalline flake graphite, and granularity is 200 mesh；The mass fraction of the concentrated nitric acid used for
65%；The strong base solution used is the LiOH solution of a concentration of 1mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite and concentrated nitric acid m in mass ratio (crystalline flake graphite)：m(HNO3)=1：2 ratio is uniformly mixed, quiet
20min is set, level-one intercalated graphite slurry is obtained；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass percent for obtaining water are no more than 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 360W (power), microwave heating 20s make the temperature of neutral graphite slurry reach 700 DEG C or more
(slightly above 700 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder；
4) the three-dimensional grapheme powder that 300mg steps 3) obtain is taken to be added in 250ml agate jars, by 8gPVP
(polyvinylpyrrolidone) is added in 100ml deionized waters, then PVP solution is added to above-mentioned ball by ultrasonic disperse 15min
Wet ground 1h is carried out with the rotating speed of 450rpm in mill body system, obtained suspension is centrifuged into 20min with the rotating speed of 3000rpm,
Take upper layer suspension with 8000rpm eccentric cleanings, then taking precipitate drying 8h, collects and obtain the graphene that the number of plies is less than 3.
Embodiment 5
Graphite used by the present embodiment is crystalline flake graphite, and granularity is 200 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the NaOH solution of a concentration of 1.5mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, potassium permanganate, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：M (potassium permanganate)：m
(HNO3)：m(H3PO4)=1：0.05：2：2 ratio is uniformly mixed, and is stood 40min, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass percent for obtaining water do not surpass 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 400W (power), microwave heating 30s make the temperature of neutral graphite slurry reach 800 DEG C or more
(slightly above 800 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder of the number of plies no more than 7 to get.
Embodiment 6
Graphite used by the present embodiment is crystalline flake graphite, and granularity is 500 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the NaOH solution of a concentration of 1mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：m(HNO3)：m(H3PO4)=1：2：
0.05 ratio is uniformly mixed, and is stood 40min, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass fraction for obtaining water do not surpass 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 450W (power), microwave heating 30s make the temperature of neutral graphite slurry reach 850 DEG C or more
(slightly above 850 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder；
4) deionized water is added in the three-dimensional grapheme powder that step obtains and carries out washing removal phosphate and nitrate,
Then at 60 DEG C dry 2h to get.
Embodiment 7
Graphite used by the present embodiment is crystalline flake graphite, and granularity is 500 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 65%；The strong base solution used is the KOH solution of a concentration of 1.5mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：m(HNO3)：m(H3PO4)=1：
0.05：2 ratio is uniformly mixed, and is stood 20min, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass percent for obtaining water do not surpass 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 500W (power), microwave heating 40s make the temperature of neutral graphite slurry reach 900 DEG C or more
(slightly above 900 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder；
4) deionized water is added in the three-dimensional grapheme powder that step obtains and carries out washing removal phosphate and nitrate,
Then at 80 DEG C dry 0.5h to get.
Embodiment 8
Graphite used by the present embodiment the present embodiment is crystalline flake graphite, and granularity is 30 mesh；The quality of the concentrated nitric acid of use
Score is 65%, and the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the NaOH solution of a concentration of 1.5mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：m(HNO3)：m(H3PO4)=1：1：4
Ratio be uniformly mixed, stand 3h, obtain level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass percent for obtaining water are no more than 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 550W (power), microwave heating 5s make the temperature of neutral graphite slurry reach 920 DEG C or more
(slightly above 920 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder；
4) the three-dimensional grapheme powder that 300mg steps 3) obtain is taken to be added in 250ml agate jars, 5gPVP is (poly-
Vinylpyrrolidone) it is added in 100ml deionized waters, then PVP solution is added to above-mentioned ball milling by ultrasonic disperse 10min
Wet ground 2h is carried out with the rotating speed of 400rpm in system, obtained suspension is centrifuged into 25min with the rotating speed of 2500rpm, is taken
Upper layer suspension with 7000rpm eccentric cleanings, then taking precipitate drying 8h to get.
Embodiment 9
Graphite used by the present embodiment is crystalline flake graphite, and granularity is 10 mesh；The mass fraction of the concentrated nitric acid used for
65%, the mass fraction of concentrated phosphoric acid is 85%；The strong base solution used is the NaOH solution of a concentration of 8mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, potassium permanganate, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：M (potassium permanganate)：m
(HNO3)：m(H3PO4)=1：0.15：2：3 ratio is uniformly mixed, and is stood 2h, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass percent for obtaining water are no more than 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 600W (power), microwave heating 30s make the temperature of neutral graphite slurry reach 1000 DEG C, obtain
To three-dimensional grapheme powder；
4) the three-dimensional grapheme powder that 300mg steps 3) obtain is taken to be added in 250ml agate jars, by 15gPVP
(polyvinylpyrrolidone) is added in 100ml deionized waters, then PVP solution is added to above-mentioned ball by ultrasonic disperse 25min
Wet ground 2h is carried out with the rotating speed of 400rpm in mill body system, obtained suspension is centrifuged into 15min with the rotating speed of 3500rpm,
Take upper layer suspension to be centrifuged with 9000rpm, clean, then taking precipitate drying 7h to get.
Embodiment 10
The used graphite of the present embodiment is crystalline flake graphite, and granularity is 200 mesh；The mass fraction of the concentrated nitric acid used for
65%；The strong base solution used is the NaOH solution of a concentration of 7mol/L.
The swollen quick-fried method for preparing graphene of microwave of the present embodiment, includes the following steps：
1) by crystalline flake graphite, concentrated nitric acid and concentrated phosphoric acid m in mass ratio (crystalline flake graphite)：M (potassium permanganate)：m(HNO3)：m
(H3PO4)=1：1.5：5：5 ratio is uniformly mixed, and is stood 20min, is obtained level-one intercalated graphite slurry；
2) strong base solution to system is added into the level-one intercalated graphite slurry obtained by step 1) to be in neutrality, then filters out
Surplus liquid, the mass percent for obtaining water are no more than 10% two level intercalated graphite slurry；
3) the two level intercalated graphite slurry obtained by step 2) is put into micro-wave oven, according to every g two levels intercalated graphite slurry
The ratio setting microwave power of corresponding 80W (power), microwave heating 300s make the temperature of neutral graphite slurry reach 700 DEG C or more
(slightly above 700 DEG C, be no more than 1000 DEG C), obtain three-dimensional grapheme powder；
4) the three-dimensional grapheme powder that 300mg steps 3) obtain is taken to be added in 250ml agate jars, by 10g PVP
(polyvinylpyrrolidone) is added in 100ml deionized waters, then PVP solution is added to above-mentioned ball by ultrasonic disperse 15min
Wet ground 3h is carried out with the rotating speed of 300rpm in mill body system, obtained suspension is centrifuged into 20min with the rotating speed of 3000rpm,
Take upper layer suspension to be centrifuged with 7000rpm, taking precipitate is cleaned with deionized water, then dry to get.
Comparative example
The preparation method of the graphene oxide of comparative example includes the following steps：
1) natural flake graphite of 350 mesh of 5g is weighed, is sufficiently stirred after the 100ml concentrated sulfuric acids and 10g potassium permanganate is added
It is even, 2h is reacted at room temperature, and the hydrochloric acid 1L and distillation water washing that products therefrom mass percentage is 10% are to neutrality, then
Vacuum filter, 60 DEG C of drying, obtain the graphite particle of oxidation intercalation；
2) graphite particle for the oxidation intercalation that step 1) obtains is placed in micro-wave oven, 20s is heated with the power of 800W, is obtained
To expanded graphite；
3) expanded graphite that step 2) obtains is put into deionized water, ultrasound stripping takes upper layer suspension, filters and do
It is dry to get；The power of ultrasound is 100W, ultrasonic time 30min.Lower sediment is graphite, and graphene oxide yield is only about
28%.In contrast to this, two level intercalation processing method using the present invention can then be prepared only by the swollen quick-fried processing of a microwave
100% three-dimensional grapheme powder product.
Raman spectrum test is carried out to the graphene that comparative example obtains, Raman spectrogram is obtained and sees Fig. 3 (S3).
From the figure 3, it may be seen that the graphene oxide powder prepared using the method, oxidation is generated due to a large amount of introducings of oxidant
Graphene intrinsic a large amount of defects, for Raman collection of illustrative plates similar to standard activity charcoal, the peaks defect D are not only wide but also high, the fingerprint letter of graphene
Cease the peaks 2D missing.
Claims (10)
1. a kind of swollen quick-fried method for preparing graphene of microwave, it is characterised in that：Include the following steps：
1) graphite raw material is mixed with intercalator and carries out acidification intercalation, obtain level-one intercalated graphite slurry；
2) OH is added into the level-one intercalated graphite slurry obtained by step 1)-Ion concentration be 0.1~8mol/L strong base solution extremely
System is in neutrality, and obtains two level intercalated graphite slurry；
3) by the two level intercalated graphite slurry microwave heating obtained by step 2), or by obtained by step 2) two level intercalated graphite starch
Microwave heating after material is dry, obtain three-dimensional grapheme powder to get；The microwave heating is in 5~300s by object in micro-wave oven
Material temperature degree rises to 400~1000 DEG C.
2. the swollen quick-fried method for preparing graphene of microwave according to claim 1, it is characterised in that：The acidification intercalation be by
Graphite raw material is stood at normal temperatures after being mixed with intercalator, and the time of the standing is 20min~3h.
3. the swollen quick-fried method for preparing graphene of microwave according to claim 1 or 2, it is characterised in that：The graphite raw material
Mass ratio with intercalator is 1:(2~10).
4. the swollen quick-fried method for preparing graphene of microwave according to claim 1, it is characterised in that：The intercalator is dense nitre
The mixture of at least one of acid, concentrated phosphoric acid or at least one of both potassium permanganate and concentrated nitric acid, concentrated phosphoric acid.
5. the swollen quick-fried method for preparing graphene of microwave according to claim 1 or 2, it is characterised in that：The intercalator is
The mixed acid of concentrated nitric acid and concentrated phosphoric acid, H in the mixed acid3PO4With HNO3Mass ratio be not more than 5.
6. the swollen quick-fried method for preparing graphene of microwave according to claim 1 or 4, it is characterised in that：In the intercalator
Containing potassium permanganate, the mass ratio of the potassium permanganate and graphite raw material is not more than 1.5.
7. the swollen quick-fried method for preparing graphene of microwave according to claim 1, it is characterised in that：The strong base solution it is molten
Matter is at least one of sodium hydroxide, potassium hydroxide or lithium hydroxide.
8. the swollen quick-fried method for preparing graphene of microwave according to claim 1, it is characterised in that：The work(of the microwave heating
Rate is 80~600W/g.
9. the swollen quick-fried method for preparing graphene of microwave according to claim 1, it is characterised in that：Further including will be in step 3)
The three-dimensional grapheme powder of gained carries out ball milling after microwave heating, and the rotating speed of ball milling is 300~450rpm, and the time of ball milling is 1
~3h.
10. the swollen quick-fried method for preparing graphene of microwave according to claim 1, it is characterised in that：Further include by step 3)
The three-dimensional grapheme powder of middle gained is washed using neutral flux, then in 60~120 DEG C of dry 0.5~3h.
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