CN106882796A - A kind of preparation method of three-dimensional grapheme structure/high-quality graphene - Google Patents
A kind of preparation method of three-dimensional grapheme structure/high-quality graphene Download PDFInfo
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/00—Physical properties of inorganic compounds
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Abstract
The invention provides a kind of preparation method of three-dimensional grapheme structure/high-quality graphene, natural flake graphite or Delanium are carried out into intercalation processing, compound between graphite layers are obtained；The compound between graphite layers that will be obtained carry out expansion process in swelling agent, obtain high specific surface area three-dimensional graphene structure.By treatment such as ball milling, shearing, high-velocity fluid crushing or ultrasounds, high quality monolayer and few layer graphene dispersion liquid are obtained.Three-dimensional structure obtained by the present invention has more than 1000 m2The specific surface area of/g, and piece layer lattice structure keeps complete.It is by mechanically pulling off the Graphene lattice structure for obtaining to remain intact, with excellent electric property, film volumetric electrical conductivity is up to 1000 more than S/cm.Grapheme material prepared by the present invention can be widely applied to the fields such as energy storage, composite, electrically conductive ink, conductive film.Three-dimensional grapheme structure can be used directly as high-specific surface area carbon skeleton, can be combined with the various types of materials such as polymer, metal oxide, metal sulfide, carbonitride, prepare the composite with various specific functionalities.
Description
Technical field
The invention belongs to field of material technology, it is related to the preparation method of three-dimensional grapheme structure/high-quality graphene, has
Body is, as intercalator, to obtain compound between graphite layers with oxidant and acid；By the compound between graphite layers of gained in swelling agent
Expanded, obtained three-dimensional grapheme structure；Gained three-dimensional structure is sanded, ball milling, shearing, ultrasound and high velocity stream
The physical mechanical effect such as body crushing, obtains graphene dispersing solution.
Background technology
Carbon can form miscellaneous material due to its unique electronic structure by different hybrid forms.Its
In, with sp2All kinds of carbon nanomaterials that hybrid form is present（Including fullerene, CNT, Graphene etc.）Due to excellent
The properties such as electricity, mechanics, calorifics, it has also become the study hotspot of Material Field.To give full play to the advantage of carbon material, exploitation is provided
There is the carbon material of high-specific surface area most important.High-specific surface area carbon material has more exposed reactivity sites, enriches
Gap structure, it is possible to increase various performances of the carbon material in application process.For example, by high specific area carbon materials application in
During the fields such as ultracapacitor, lithium ion battery, the electricity of its unit volume or unit mass storage compares block carbon material tool
There is significant advantage.
From Graphene 2004 using adhesive tape technology by since successfully preparing, be single construction with graphene nano lamella
It is widely studied by various countries researcher that unit prepares three-dimensional grapheme material.Carbon nanosheet layer can reduce ion expansion in the solution
Distance is dissipated, it is assembled rear with abundant gap structure, it is widely used in fields such as energy storage, catalysis.With mesoporous silicon, calcium oxide
Deng being template, graphene nanometer sheet is grown in template hole by the method for chemical vapor deposition, template is gone
After removing, three-dimensional preparing high-specific surface area graphene material is can obtain.But these method high costs, route is tediously long and is difficult to industrialize.Oxygen
Graphite alkene is the presoma of the three-dimensional preparing high-specific surface area graphene material of most commonly seen preparation.Graphene oxide is original by graphite
Material, in being dispersed in water or polar organic solvent by modes such as ultrasound, shearing or concussions after chemical oxidation.Graphene oxide water
Solution is assembled under finite concentration by hydro-thermal or electronation, and the three-dimensional grapheme structure of high-specific surface area can be obtained.
Additionally, the disturbance such as stirring is not added with graphene oxide solution reduction process, by way of standing reduction, it is also possible to this is obtained
Class three-dimensional structure.However, have more defect on the grapheme material lamella obtained by oxidation-reduction method, the mechanics of reduction,
Electrically and thermally its practical application of performance impact, such as in energy storage material, therefore cyclical stability can reduce.Thus, exploitation
With carbon nanosheet high-specific surface area of the layer as structural unit and the complete graphene three-dimensional structure material of lattice structure to closing weight
Will.
The content of the invention
It is an object of the invention to overcome above-mentioned difficulties, there is provided a kind of three-dimensional grapheme structure/high-quality graphene
Preparation method.Graphene three-dimensional structure body prepared by the inventive method has more than 1000 m2The high-specific surface area of/g, higher than with
Graphene oxide is the three-dimensional grapheme structure that raw material assembling is obtained, and Graphene lattice structure is complete, remains carbon materials
The excellent physicochemical properties of material.The three-dimensional structure of preparation is sanded, ball milling, shearing, high-velocity fluid crush or ultrasound
Deng mechanical treatment, the graphene dispersing solution of stabilization can be formed.The present invention prepare grapheme material can apply to energy storage, catalysis,
The fields such as composite, with operating process is simple, the advantage such as low cost, controllability are good, are adapted to large-scale production and industrialization
Using.
A kind of preparation method of three-dimensional grapheme structure/high-quality graphene proposed by the present invention, comprises the following steps that：
（1）Raw graphite is carried out into intercalation processing in intercalator, intercalator is entered graphite layers, graphite layers chemical combination is obtained
Thing；
（2）By step（1）The compound between graphite layers for obtaining are put into swelling agent, and stirring stands 1-48h after 15 minutes, makes
Swelling agent decomposes to give off gas well into graphite layers in interlayer, increases the interlamellar spacing of Graphene so that graphene sheet layer
It is separated from one another, form the three-dimensional grapheme structure with superhigh specific surface area；
（3）By step（2）The three-dimensional grapheme structure for obtaining passes through ultrasound, sand milling, ball milling, high-velocity fluid powder in inorganic agent
After any one of broken or shearing mode or the treatment of their associated form, graphene dispersing solution is obtained.
In the present invention, described raw graphite is natural flake graphite or Delanium.
In the present invention, step（1）Described in intercalator by acid and oxidant constitute, it is described acid be sulfuric acid, phosphoric acid or nitre
In acid any one, the oxidant be sulfuric acid, phosphoric acid, nitric acid, potassium permanganate, potassium ferrate, potassium bichromate, chromium trioxide or double
One kind of oxygen water or the combination between them.The purpose of intercalation is to weaken the Van der Waals force between graphite flake layer, is introduced a small amount of
Oxygen-containing functional group.The above-mentioned intercalator species listed can select one of them carry out intercalation, or between them appoint
Meaning combination, but not limited to this.
In the present invention, step（1）Described in the addition of oxidant be 0.1-20 times of raw graphite quality；Sour adds
It is 10-100 times of raw graphite quality to enter amount.
In the present invention, step（2）Described in swelling agent be made up of acid and oxidant, the acid in sulfuric acid or phosphoric acid to appoint
One kind, the oxidant is one kind in sulfur trioxide, hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate or they it
Between combination.In swelling agent, oxidant and acid can enter graphite layers, and oxidant decomposes to give off gas in interlayer.The product of gas
Life overcomes the Van der Waals force of graphite layers, expands graphite.
In the present invention, step（2）Described in oxidant addition be 0.1-20 times of raw graphite, sour consumption is raw material stone
10-200 times of ink.
In the present invention, step（3）Described in ultrasound when control ultrasonic power be 50-5000 W, ultrasonic time is 15
min-5 h；Sand mill rotating speed is controlled during the sand milling for 150-1600 rpm, the sand milling time is 0.5-12h；The ball milling time control
Drum's speed of rotation processed is 150-1600 rpm, and Ball-milling Time is 0.5-12h；Control pressure is 10- when the high-velocity fluid is crushed
150 MPa, flow velocity：300-40000 L/h；Control shear rate for 1000-30000 rpm during the shearing, shear time is
0.5-10h。
In the present invention, the inorganic agent uses N, N- dimethylformamides, N- methyl pyrrolidones, o-dichlorohenzene, two
One or more in the mixed solvent of methyl sulfoxide, toluene, the tert-butyl alcohol, isopropanol or ethanol and water, or containing active
The aqueous solution of auxiliary agent, coagent is polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, sodium n-alkylbenzenesulfonate, α-alkene
Base sodium sulfonate, sodium sulfate of polyethenoxy ether of fatty alcohol, lauryl sodium sulfate, APES, alkylolamides, fat
Fat alcohol APEO, dodecyldimethylammonium hydroxide inner salt, hexadecyldimethyl benzyl ammonium ammonium chloride, NaOH, nonionic are organic
In fluorine surfactant or polyether-modified polysiloxane etc. any one.
In the present invention, the three-dimensional grapheme structure/high-quality graphene specific surface area for preparing is up to 1000 m2/g
More than, graphene sheet layer crystal structure is remained intact, and yield is close to 100%；Gained three-dimensional grapheme structure is by being sanded, ball
The effects such as mill, ultrasound, high-velocity fluid are crushed, shearing, are capable of achieving to be completely exfoliated, in organic solvent or aqueous surfactant solution
Form the graphene dispersing solution of stabilization.The gained Graphene number of plies is 1-10 layers, and yield is up to 100%, and graphite lattice integrity degree is high,
Electrical conductivity is up to 1000 more than S/cm.
In view of the shortcomings of the prior art, the present inventor is by long-term practice and research, it is proposed that skill of the invention
Art scheme, the program can realize efficient, inexpensive, the extensive preparation of three-dimensional grapheme structure/high-quality graphene, solve
The key issue of three-dimensional grapheme structure and high-quality graphene dispersion liquid prepare with scale, to realize Graphene at each
Field（Such as energy storage material, composite, catalysis, conducting film, heat dissipation film）In practical application provide effective way.
The present invention has the advantage that compared with prior art：
（1）With Delanium or natural flake graphite as raw material, raw material sources are extensively, with low cost.
（2）Operating condition of the present invention is gentle, and the oxidation-reduction process of graphite is not related to, it is not necessary to use larger strong of toxicity
Reducing agent, it is not required that reduced at high temperature using pure hydrogen, it is to avoid the danger exploded.
（3）The present invention without graphite complete oxidation is turned into graphene oxide, then it is assembled obtain three-dimensional grapheme, but
With graphite as raw material, directly obtained by expansion fashion, enormously simplify the flow for preparing graphene three-dimensional structure body, significantly carried
The quality of graphene three-dimensional structure body high.Obtained three-dimensional grapheme structure specific surface area of the invention is high, and degree of oxidation is low,
Be conducive to further surface modification and form composite with other materials.
（4）Graphene dispersion liquid and preparation method thereof has the characteristics of yield is high, quality is high, energy consumption is low in the present invention.
Brief description of the drawings
Fig. 1 is the scanning electron microscope image of three-dimensional grapheme structure.
Fig. 2 is graphite, the Raman spectrum of the three-dimensional grapheme structure of the acquisition of embodiment 1 and 16.
Specific embodiment
Technical scheme is illustrated below by way of instantiation.It should be understood that the present invention mention one or more
Step is not repelled before and after the combination step also and is existed between other method and steps, or these specifically mentioned steps also
May be inserted into other method and steps.It should also be understood that these examples are merely to illustrate the present invention rather than limit of the invention
Scope.Unless otherwise indicated, the numbering of various method steps is only the purpose for differentiating various method steps, rather than to limit each method
Ordering or limit practical range of the invention, its relativeness is altered or modified, without substantial technological content alteration
Under conditions of, when being also considered as enforceable category of the invention.
Embodiment 1
（1）By 90 milliliters of concentrated sulfuric acids（98%）30 milliliters of concentrated nitric acids are slowly added under the conditions of ice-water bath（65%）In, it is well mixed
Afterwards, to 3 grams of crystalline flake graphites of addition in reaction solution（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir at ambient temperature
Mix 24 hours.Then, reaction solution is filtered to remove, gained solid is compound between graphite layers.
（2）By 240 milliliters of concentrated sulfuric acids（98%）60 milliliters of hydrogen peroxide are slowly added under the conditions of ice-water bath（30%）In, cooling
Afterwards by mixed liquor 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, room temperature is stirred
Expansion 48 hours are stood after mixing 15 minutes, filtering, washing obtain three-dimensional grapheme structure, the m of specific surface area 13602/ g, produces
Rate 100%.Fig. 1 gives SEM result, and Fig. 2 is corresponding Raman spectrum.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL 1-METHYLPYRROLIDONEs, water bath sonicator is used
30 min, obtain black suspension, wherein containing individual layer and few layer graphene, peeling off yield about 100%.
Embodiment 2
（1）By 660 milliliters of concentrated sulfuric acids（98%）220 milliliters of concentrated nitric acids are slowly added under the conditions of ice-water bath（65%）In, mixing is equal
After even, to 3 grams of crystalline flake graphites of addition in reaction solution（150 microns of particle diameter, phosphorus content is higher than 95%）, and at ambient temperature
Stirring 24 hours.Then, reaction solution is filtered to remove, gained solid is compound between graphite layers.
（2）By 240 milliliters of concentrated sulfuric acids（98%）60 milliliters of hydrogen peroxide are slowly added under the conditions of ice-water bath（30%）In, cooling
Afterwards by mixed liquor 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, room temperature is stirred
Expansion 24 hours are stood after mixing 15 minutes, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 12502/ g, produces
Rate 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL 1-METHYLPYRROLIDONEs with 35% output work
The min of rate Probe Ultrasonic Searching 30, obtains individual layer and few layer graphene, yield about 100%.
Embodiment 3
（1）By 90 milliliters of concentrated sulfuric acids（98%）30 milliliters of concentrated nitric acids are slowly added under the conditions of ice-water bath（65%）In, it is well mixed
Afterwards, to 3 grams of crystalline flake graphites of addition in reaction solution（500 microns of particle diameter, phosphorus content is higher than 95%）, and stir at ambient temperature
Mix 24 hours.Then, by reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）By 540 milliliters of concentrated sulfuric acids（98%）135 milliliters of hydrogen peroxide are slowly added under the conditions of ice-water bath（30%）In, it is cold
But afterwards by mixed liquor 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, room temperature
Stirring stands expansion 3 hours after 15 minutes, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 13202/ g, produces
Rate 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL 1-METHYLPYRROLIDONEs in 18000 rpm
Condition down cut 1h, obtains individual layer and few layer graphene, yield about 100%.
Embodiment 4
（1）Under the conditions of ice-water bath, by 90 milliliters of concentrated sulfuric acids（98%）It is slowly added to 30 milliliters of concentrated nitric acids（65%）In, it is well mixed
Afterwards, to 3 grams of crystalline flake graphites of addition in reaction solution（500 microns of particle diameter, phosphorus content is higher than 95%）, stir at ambient temperature
After 24 hours, by reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 300 milliliters of sulfuric acid, and by step（1）In compound between graphite layers add
In entering mixed liquor, 35 DEG C of stirrings stand expansion 1 hour after 15 minutes, and washing, filtering, until filtrate is neutrality, obtain three-dimensional stone
Black alkene structure.The m of specific surface area 12502/ g, yield 100%.
（3）Hygrometric state three-dimensional grapheme structure 1-METHYLPYRROLIDONE is cemented out water, the hygrometric state thing after suction filtration
Material is placed in ball grinder, ball milling 5h under the conditions of 300 rpm.To 1-METHYLPYRROLIDONE is added in the material after ball milling, obtain black
Color suspension, is centrifuged 15 min under 12000 rpm, removes supernatant, 1-METHYLPYRROLIDONE is added, 1000
30 min are centrifuged under rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 5
（1）Under the conditions of ice-water bath, 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature, will be anti-
Liquid sand core funnel suction filtration, gained solid is answered to be compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 20 milliliters of sulfuric acid, and by step（1）In compound between graphite layers add
In mixed liquor, 35 DEG C stirring 15 minutes after stand expansion 3 hours, washing, filtering, until filtrate for neutrality, obtain three-dimensional graphite
Alkene structure.The m of specific surface area 13002/ g, yield 100%.
（3）Hygrometric state three-dimensional grapheme structure 1-METHYLPYRROLIDONE is cemented out water, the hygrometric state thing after suction filtration
Material is placed in ball grinder, and 6h is sanded under the conditions of 500 rpm.To 1-METHYLPYRROLIDONE is added in the material after sand milling, obtain black
Color suspension, is centrifuged 15 min under 12000 rpm, removes supernatant, 1-METHYLPYRROLIDONE is added, 1000
30 min are centrifuged under rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless
Embodiment 6
（1）90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid under the conditions of ice-water bath, after being well mixed, are added in reaction solution
Enter 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir 24 hours at ambient temperature.Then, will
Reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）240 milliliters of sulfuric acid are slowly added in 60 milliliters of hydrogen peroxide under the conditions of ice-water bath, mixed liquor is moved after cooling
In entering 40 DEG C of water-baths.Then, by step（1）In compound between graphite layers add mixed liquor in, it is quiet after being stirred at room temperature 15 minutes
Expansion 3 hours is put, filtering, washing obtain three-dimensional grapheme structure.The m of specific surface area 13202/ g, yield 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL ethanol and water mixed liquid, water bath sonicator 30
Min, obtains black suspension, and 15 min are centrifuged under 12000 rpm, removes supernatant, adds ethanol and water mixed liquid,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 7
（1）660 milliliters of sulfuric acid are slowly added in 220 milliliters of nitric acid under the conditions of ice-water bath, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir 24 hours at ambient temperature.Then,
Reaction solution sand core funnel suction filtration, gained solid are compound between graphite layers.
（2）240 milliliters of sulfuric acid are slowly added in 60 milliliters of hydrogen peroxide under the conditions of ice-water bath, mixed liquor is moved after cooling
In entering 40 DEG C of water-baths.Then, by step（1）In compound between graphite layers add mixed liquor in, it is quiet after being stirred at room temperature 15 minutes
Expansion 3 hours is put, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 12302/ g, yield 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL ethanol and water mixed liquid with 35% power output
The min of Probe Ultrasonic Searching 30, obtains black suspension, and 15 min are centrifuged under 12000 rpm, removes supernatant, adds ethanol
And water mixed liquid, 30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 8
（1）90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid under the conditions of ice-water bath, after being well mixed, are added in reaction solution
Enter 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir 24 hours at ambient temperature.Then, will
Reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）540 milliliters of sulfuric acid are slowly added in 135 milliliters of hydrogen peroxide under the conditions of ice-water bath, by mixed liquor after cooling
In 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, after being stirred at room temperature 15 minutes
Expansion 3 hours are stood, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 10502/ g, yield 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL ethanol and water mixed liquid liquid, 18000
Rpm condition down cut 1h, obtain black suspension, and 15 min are centrifuged under 12000 rpm, remove supernatant, add ethanol
And water mixed liquid, 30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 9
（1）Under the conditions of ice-water bath, 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature, will be anti-
Liquid sand core funnel suction filtration, gained solid is answered to be compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 20 milliliters of sulfuric acid, and will（1）In compound between graphite layers add mixing
In liquid, 35 DEG C stirring 15 minutes after stand expansion 3 hours, washing, filtering, until filtrate for neutrality, obtain three-dimensional grapheme knot
Structure body.The m of specific surface area 12502/ g, yield 100%.
（3）To hygrometric state three-dimensional grapheme structure under the conditions of 300 rpm ball milling 5h.To adding second in the material after ball milling
Alcohol and water mixed liquor, obtains black suspension, and 15 min are centrifuged under 12000 rpm, removes supernatant, add ethanol and
Water mixed liquid, is centrifuged 30 min under 1000 rpm, and repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 9
（1）Under the conditions of ice-water bath, 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature, will be anti-
Liquid sand core funnel suction filtration, gained solid is answered to be compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 20 milliliters of sulfuric acid, and by step（1）In compound between graphite layers add
In mixed liquor, 35 DEG C stirring 15 minutes after stand expansion 3 hours, washing, filtering, until filtrate for neutrality, obtain three-dimensional graphite
Alkene structure, the m of specific surface area 11002/ g, yield 100%.
（3）2h is sanded under the conditions of 800 rpm to hygrometric state three-dimensional grapheme structure.To adding second in the material after sand milling
Alcohol and water mixed liquor, obtains black suspension, and 15 min are centrifuged under 12000 rpm, removes supernatant, add ethanol and
Water mixed liquid, is centrifuged 30 min under 1000 rpm, and repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 11
（1）90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid under the conditions of ice-water bath, after being well mixed, are added in reaction solution
Enter 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir 24 hours at ambient temperature.Then, will
Reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）240 milliliters of sulfuric acid are slowly added in 60 milliliters of hydrogen peroxide under the conditions of ice-water bath, mixed liquor is moved after cooling
In entering 40 DEG C of water-baths.Then, by step（1）In compound between graphite layers add mixed liquor in, it is quiet after being stirred at room temperature 15 minutes
Expansion 3 hours is put, filtering, washing obtain three-dimensional grapheme structure.The m of specific surface area 12002/ g, yield 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in the mg/mL aqueous povidone solutions of 100 mL 0.5
In, the min of water bath sonicator 30 obtains black suspension, and 15 min are centrifuged under 12000 rpm, removes supernatant, adds
0.5 mg/mL aqueous povidone solutions, are centrifuged 30 min under 1000 rpm, and repeated centrifugation simultaneously collects upper liquid,
Until upper liquid is colourless.
Embodiment 12
（1）660 milliliters of sulfuric acid are slowly added in 220 milliliters of nitric acid under the conditions of ice-water bath, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir 24 hours at ambient temperature.Then,
Reaction solution sand core funnel suction filtration, gained solid are compound between graphite layers.
（2）240 milliliters of sulfuric acid are slowly added in 60 milliliters of hydrogen peroxide under the conditions of ice-water bath, mixed liquor is moved after cooling
In entering 40 DEG C of water-baths.Then, by step（1）In compound between graphite layers add mixed liquor in, it is quiet after being stirred at room temperature 15 minutes
Expansion 3 hours is put, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 12502/ g, yield 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in 100 mL0.5 mg/mL aqueous povidone solutions
In with the min of 35% power output Probe Ultrasonic Searching 30, obtain black suspension, 15 min are centrifuged under 12000 rpm, go
Clear liquid, adds 0.5 mg/mL aqueous povidone solutions, and 30 min are centrifuged under 1000 rpm, and repeated centrifugation is simultaneously
Upper liquid is collected, until upper liquid is colourless.
Embodiment 13
（1）90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid under the conditions of ice-water bath, after being well mixed, are added in reaction solution
Enter 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, and stir 24 hours at ambient temperature.Then, will
Reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）540 milliliters of sulfuric acid are slowly added in 135 milliliters of hydrogen peroxide under the conditions of ice-water bath, by mixed liquor after cooling
In 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, after being stirred at room temperature 15 minutes
Expansion 3 hours are stood, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 11502/ g, yield 100%.
（3）0.1g hygrometric state three-dimensional grapheme structures are placed in the mg/mL polyvinylpyrrolidones of 100 mL 0.5 water-soluble
In liquid, in 18000 rpm condition down cut 1h, black suspension is obtained, 15 min are centrifuged under 12000 rpm, remove supernatant
Liquid, adds 0.5 mg/mL aqueous povidone solutions, and 30 min are centrifuged under 1000 rpm, and repeated centrifugation is simultaneously received
Collection upper liquid, until upper liquid is colourless.
Embodiment 14
（1）Under the conditions of ice-water bath, 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature, will be anti-
Liquid sand core funnel suction filtration, gained solid is answered to be compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 20 milliliters of sulfuric acid, and by step（1）In compound between graphite layers add
In mixed liquor, 35 DEG C stirring 15 minutes after stand expansion 3 hours, washing, filtering, until filtrate for neutrality, obtain three-dimensional graphite
Alkene structure.The m of specific surface area 10102/ more than g.
（3）To adding 0.5 mg/mL aqueous povidone solutions, 300 rpm in hygrometric state three-dimensional grapheme structure
Under the conditions of ball milling 5h.To 0.5 mg/mL aqueous povidone solutions are added in the material after ball milling, black suspension is obtained
Liquid, is centrifuged 15 min under 12000 rpm, removes supernatant, adds 0.5 mg/mL aqueous povidone solutions,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 15
（1）Under the conditions of ice-water bath, 90 milliliters of sulfuric acid are slowly added in 30 milliliters of nitric acid, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature, will be anti-
Liquid sand core funnel suction filtration, gained solid is answered to be compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 20 milliliters of sulfuric acid, and by step（1）In compound between graphite layers add
In mixed liquor, 35 DEG C stirring 15 minutes after stand expansion 3 hours, washing, filtering, until filtrate for neutrality, obtain three-dimensional graphite
Alkene structure.The m of specific surface area 9102/ more than g.
（3）To adding 0.5 mg/mL aqueous povidone solutions, 600 rpm in hygrometric state three-dimensional grapheme structure
Under the conditions of 4h is sanded.To 0.5 mg/mL aqueous povidone solutions are added in the material after sand milling, black suspension is obtained
Liquid, is centrifuged 15 min under 12000 rpm, removes supernatant, adds 0.5 mg/mL aqueous povidone solutions,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 16
（1）Under the conditions of ice-water bath, 3 grammes per square metre potassium chromates are slowly added in 100 milliliters of concentrated sulfuric acids, after being well mixed, to reaction
3 grams of crystalline flake graphites are added in liquid（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature,
Reaction solution sand core funnel suction filtration, gained solid are compound between graphite layers.
（2）During 0.3 gram of ammonium persulfate added into 20 milliliters of sulfuric acid, and by step（1）In compound between graphite layers add
In mixed liquor, 35 DEG C stirring 15 minutes after stand expansion 3 hours, washing, filtering, until filtrate for neutrality, obtain three-dimensional graphite
Alkene structure.The m of specific surface area 10202/g.Fig. 2 gives corresponding Raman spectrum.
（3）To adding 0.5 mg/mL aqueous povidone solutions, 600 rpm in hygrometric state three-dimensional grapheme structure
Under the conditions of 4h is sanded.To 0.5 mg/mL aqueous povidone solutions are added in the material after sand milling, black suspension is obtained
Liquid, is centrifuged 15 min under 12000 rpm, removes supernatant, adds 0.5 mg/mL aqueous povidone solutions,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 17
（1）Under the conditions of ice-water bath, 18 grams of chromium trioxides are slowly added to 100 milliliters of sulfuric acid, after being well mixed, in reaction solution
Add 3 grams of crystalline flake graphites（150 microns of particle diameter, phosphorus content is higher than 95%）, after stirring 24 hours at ambient temperature, will be anti-
Liquid sand core funnel suction filtration, gained solid is answered to be compound between graphite layers.
（2）240 milliliters of sulfuric acid are slowly added in 60 milliliters of hydrogen peroxide under the conditions of ice-water bath, by mixed liquor after cooling
In 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, after being stirred at room temperature 15 minutes
Expansion 10 hours are stood, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 11602/ g, yield 100%.
（3）To adding 0.5 mg/mL aqueous povidone solutions, 600 rpm in hygrometric state three-dimensional grapheme structure
Under the conditions of 4h is sanded.To 0.5 mg/mL aqueous povidone solutions are added in the material after sand milling, black suspension is obtained
Liquid, is centrifuged 15 min under 12000 rpm, removes supernatant, adds 0.5 mg/mL aqueous povidone solutions,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Embodiment 18
（1）Under the conditions of ice-water bath, 3 grams of potassium permanganate are slowly added to 80 milliliters of concentrated sulfuric acids and 20 milliliters of SPA mixed liquors
In, after being well mixed, to 3 grams of crystalline flake graphites of addition in reaction solution（150 microns of particle diameter, phosphorus content is higher than 95%）, in room temperature
Under the conditions of stirring 24 hours after, by reaction solution sand core funnel suction filtration, gained solid is compound between graphite layers.
（2）250 milliliters of sulfuric acid are slowly added in 50 milliliters of hydrogen peroxide under the conditions of ice-water bath, by mixed liquor after cooling
In 40 DEG C of water-baths of immigration.Then, by step（1）In compound between graphite layers add mixed liquor in, after being stirred at room temperature 15 minutes
Expansion 6 hours are stood, washing, filtering obtain three-dimensional grapheme structure.The m of specific surface area 12102/ g, yield 100%.
（3）To adding 0.5 mg/mL aqueous povidone solutions, 300 rpm in hygrometric state three-dimensional grapheme structure
Under the conditions of ball milling 5h.To 0.5 mg/mL aqueous povidone solutions are added in the material after ball milling, black suspension is obtained
Liquid, is centrifuged 15 min under 12000 rpm, removes supernatant, adds 0.5 mg/mL aqueous povidone solutions,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Comparative example 1
（1）240 milliliters of sulfuric acid are slowly added in 60 milliliters of hydrogen peroxide under the conditions of ice-water bath, mixed liquor is moved into 40 after cooling
In DEG C water-bath.Then, by 1 gram of raw graphite（150 microns of particle diameter, phosphorus content is higher than 95%）Add in mixed liquor, room temperature is stirred
Expansion 3 hours are stood after mixing 15 minutes, washing, filtering, until filtrate is neutrality, obtain product.Graphite is expanded, specific surface
241 m of product2/g。
（2）By 0.1g（1）Middle hygrometric state product body is placed in 100 mL 1-METHYLPYRROLIDONEs, and the min of water bath sonicator 30 is obtained
To black suspension, 15 min are centrifuged under 12000 rpm, remove supernatant, 1-METHYLPYRROLIDONE is added, 1000
30 min are centrifuged under rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Comparative example 2
（1）During 30 grams of sodium peroxydisulfates are added into 300 milliliters of sulfuric acid, and by 3 grams of raw graphites（150 microns of particle diameter, phosphorus content
Higher than 95%）Add mixed liquor in, 35 DEG C stirring 15 minutes after stand expansion 6 hours, washing, filtering, until filtrate for neutrality,
Obtain product.Graphite is expanded, the m of specific surface area 602/g。
（2）By 0.1g steps（1）Middle hygrometric state product body is placed in 100 mL 1-METHYLPYRROLIDONEs, 35% power output test
Ultrasonic 30 min, obtains black suspension, and 15 min are centrifuged under 12000 rpm, removes supernatant, adds N- methyl
Pyrrolidones, is centrifuged 30 min under 1000 rpm, and repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Comparative example 3
（1）During 30 grams of potassium peroxydisulfates are added into 300 milliliters of sulfuric acid, and by 3 grams of raw graphites（150 microns of particle diameter, phosphorus content
Higher than 95%）Add mixed liquor in, 35 DEG C stirring 15 minutes after stand expansion 6 hours, washing, filtering, until filtrate for neutrality,
Obtain product.Graphite is expanded, the m of specific surface area 642/g。
（2）By step（1）Middle product 1-METHYLPYRROLIDONE（1）Water inside middle product is cemented out, after suction filtration
Hygrometric state material is placed in ball grinder, ball milling 5h under the conditions of 300 rpm.To adding 1-METHYLPYRROLIDONE in the material after ball milling,
Black suspension is obtained, 15 min are centrifuged under 12000 rpm, remove supernatant, add 1-METHYLPYRROLIDONE,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Comparative example 4
（1）During 30 grams of ammonium persulfates are added into 300 milliliters of sulfuric acid, and by 3 grams of raw graphites（150 microns of particle diameter, phosphorus content
Higher than 95%）Add mixed liquor in, 35 DEG C stirring 15 minutes after stand expansion 6 hours, washing, filtering, until filtrate for neutrality,
Obtain product.Graphite is expanded, the m of specific surface area 672/g。
（2）To 0.1g steps（1）Middle hygrometric state product adds 0.5 mg/mL aqueous povidone solutions, 600 rpm bars
4h is sanded under part.To 0.5 mg/mL aqueous povidone solutions are added in the material after sand milling, black suspension is obtained,
15 min are centrifuged under 12000 rpm, supernatant is removed, 0.5 mg/mL aqueous povidone solutions are added,
30 min are centrifuged under 1000 rpm, repeated centrifugation simultaneously collects upper liquid, until upper liquid is colourless.
Claims (9)
1. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene, it is characterised in that comprise the following steps that：
（1）Raw graphite is carried out into intercalation processing in intercalator, intercalator is entered graphite layers, graphite layers chemical combination is obtained
Thing；
（2）By step（1）The compound between graphite layers for obtaining are put into swelling agent, and stirring stands 1-48h after 15 minutes, makes
Swelling agent decomposes to give off gas well into graphite layers in interlayer, increases the interlamellar spacing of Graphene so that graphene sheet layer
It is separated from one another, form the three-dimensional grapheme structure with superhigh specific surface area；
（3）By step（2）The three-dimensional grapheme structure for obtaining passes through ultrasound, sand milling, ball milling, high-velocity fluid powder in inorganic agent
After any one of broken or shearing mode or the treatment of their associated form, graphene dispersing solution is obtained.
2. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 1, its feature exists
In described raw graphite be natural flake graphite or Delanium.
3. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 1, its feature exists
In step（1）Described in intercalator be made up of acid and oxidant, the acid in sulfuric acid, phosphoric acid or nitric acid any one, it is described
Oxidant is one kind or the group between them of sulfuric acid, phosphoric acid, nitric acid, potassium permanganate, potassium bichromate, chromium trioxide or hydrogen peroxide
Close.
4. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 3, its feature exists
In step（1）Described in the addition of oxidant be 0.1-20 times of raw graphite quality；The addition of acid is raw graphite
10-100 times of quality.
5. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 1, its feature exists
In step（2）Described in swelling agent be made up of acid and oxidant, the acid in sulfuric acid or phosphoric acid any one, the oxidant
It is the one kind in sulfur trioxide, hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate or the combination between them.
6. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 5, its feature exists
In step（2）Described in oxidant addition be 0.1-20 times of raw graphite, sour consumption is 10-200 times of raw graphite.
7. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 1, its feature exists
In step（3）Described in ultrasound when control ultrasonic power for 50-5000 W, ultrasonic time is 15 min-5 h；During the sand milling
Sand mill rotating speed is controlled for 150-1600 rpm, the sand milling time is 0.5-12h；It is 150- that drum's speed of rotation is controlled during the ball milling
1600 rpm, Ball-milling Time is 0.5-12h；Control pressure is 10-150 MPa, flow velocity when the high-velocity fluid is crushed：300-
40000 L/h；Control shear rate for 1000-30000 rpm during the shearing, shear time is 0.5-10h.
8. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 1, its feature exists
Use N in the inorganic agent, N- dimethylformamides, N- methyl pyrrolidones, o-dichlorohenzene, dimethyl sulfoxide (DMSO), toluene,
One or more in the mixed solvent of the tert-butyl alcohol, isopropanol or ethanol and water, or the aqueous solution containing coagent, it is living
Property auxiliary agent be polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, sodium n-alkylbenzenesulfonate, α-sodium olefin sulfonate, fatty alcohol
Polyethenoxy ether sodium sulfate, lauryl sodium sulfate, APES, alkylolamides, AEO,
Dodecyldimethylammonium hydroxide inner salt, hexadecyldimethyl benzyl ammonium ammonium chloride, NaOH, nonionic organofluoro surfactants or poly-
In ether modified polyorganosiloxanes any one.
9. a kind of preparation method of three-dimensional grapheme structure/high-quality graphene according to claim 1, its feature exists
In the three-dimensional grapheme structure/high-quality graphene specific surface area for preparing up to 1000 m2/ more than g, graphene sheet layer
Crystal structure is remained intact, and yield is close to 100%；Gained three-dimensional grapheme structure passes through sand milling, ball milling, ultrasound, high-velocity fluid
Crushing, shear action, are capable of achieving to be completely exfoliated, and the Graphene point of stabilization is formed in organic solvent or aqueous surfactant solution
Dispersion liquid；The gained Graphene number of plies is 1-10 layers, and yield is up to 100%, and graphite lattice integrity degree is high, and electrical conductivity is up to 1000 S/cm
More than.
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