CN108033440A - A kind of preparation method of high specific surface area porous fold graphene - Google Patents
A kind of preparation method of high specific surface area porous fold graphene Download PDFInfo
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- CN108033440A CN108033440A CN201810039873.1A CN201810039873A CN108033440A CN 108033440 A CN108033440 A CN 108033440A CN 201810039873 A CN201810039873 A CN 201810039873A CN 108033440 A CN108033440 A CN 108033440A
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Abstract
The present invention provides a kind of preparation method of high specific surface area porous fold graphene, and graphene oxide solution and water-soluble nitrogenous compound are mixed, and after certain temperature reacts certain time, adds pore creating material and is uniformly mixed to obtain mixed liquor；Heated by mixed liquor ultrasonic atomizatio and in certain temperature so that the solvent in mixed liquor volatilizees and obtains graphene oxide/pore creating material powder particle；Collect gained graphene oxide/pore creating material powder particle and be heat-treated under inert gas shielding to obtain high-specific surface area fold graphene product, wherein heat treatment temperature is 600 1100 DEG C, pore creating material NaOH, KOH and K2CO3Deng the specific surface area of products obtained therefrom is 1000 to 2000m2Between/g.The present invention can obtain high-specific surface area while the pattern of fold graphene is kept.
Description
Technical field
The invention belongs to chemical field, is related to a kind of graphene, specifically a kind of high specific surface area porous fold stone
The preparation method of black alkene.
Background technology
Graphene is with sp2The bi-dimensional cellular shape crystal that hydbridized carbon atoms are formed.In theory, two-dimensional graphene has superelevation
Specific surface area, good electrical conductivity, high carrier mobility, high mechanical properties etc. make it standby in two-dimensional material application aspect
It is concerned.At present, an obstacle of the commercial application of grapheme material is that there are Van der Waals force between graphene sheet layer so that
It is easy to assemble between layers, this is greatly lowered its specific surface area, limits its performance and application.It is a kind of
Feasible method is exactly that two-dimensional nano lamellar structure is converted into the fold bulk structure of three-dimensional.Different from smooth lamella, tool
There is height fold bulk structure graphite alkene that there is very high free volume, and excellent compressive property.
To fold graphene pore-creating, while its fold pattern is kept, its specific surface area is will further improve, so as to carry
Its high performance.But directly activate fold graphene using pore creating material, although obtaining high-specific surface area, lose completely
Its pleated structure.Graphene oxide and pore creating material are sprayed fold at the same time, porous fold graphene can be prepared, but it is common
Pore creating material usually has reproducibility, can be by graphene oxide partial reduction, therefore changes aqueous solvent in spray-drying process
Active force between graphene oxide, while also so that the graphene oxide that is reduced can produce part stacking, preparation it is more
Hole fold graphene specific surface area is than relatively low, generally below 1000m2/ g, therefore, prepares the porous fold graphite of high-specific surface area
Alkene has important practical significance for the practical application for widening graphene.
The content of the invention
For above-mentioned technical problem of the prior art, the present invention provides a kind of high specific surface area porous fold graphene
Preparation method, the preparation method of this high specific surface area porous fold graphene will connect preparation of the prior art
Porous fold graphene specific surface area is than relatively low technical problem.
The present invention provides a kind of preparation method of high specific surface area porous fold graphene, include the following steps：
1) graphene oxide solution and water-soluble nitrogenous compound are mixed, the concentration of the graphene oxide solution is
0.1-5mg/ml, the water-soluble nitrogenous compound are selected from ammonium hydroxide, ethylenediamine, aniline, triethylene tetramine or four ethene five
Any one in amine, the mass ratio of the water-soluble nitrogenous compound and graphene oxide is 1:10-100:1, in 0-100
0.1-24h is reacted at a temperature of DEG C, pore creating material is added and is uniformly mixed to obtain mixed liquor；The pore creating material for NaOH, KOH or
Person K2CO3, the mass ratio of graphene oxide and pore creating material is 1:1-1:5；
2) by mixed liquor ultrasonic atomizatio, and heated at a temperature of 100-600 DEG C, obtain graphene oxide/pore creating material powder particle；
3) graphene oxide/pore creating material powder particle is heat-treated under inert gas shielding, heat treatment temperature 400-1100
DEG C, high specific surface area porous fold graphene is obtained, the specific surface area of the high specific surface area porous fold graphene of gained is 1000
To 2000m2Between/g.
Further, in step 1）In, graphene oxide solution is with ammonium hydroxide in mass ratio with 1:10 mass ratio mixing, 60
DEG C reaction 6h, then add with graphene oxide mass ratio be 4：1 KOH, is uniformly mixed and obtains mixed liquor.
The present invention is to mix the hydrophily reducing agent such as graphene oxide solution and water-soluble nitrogenous compound, in a constant temperature
After degree reaction certain time, add pore creating material and be uniformly mixed to obtain mixed liquor；By mixed liquor ultrasonic atomizatio and in certain temperature
Heat so that the solvent in mixed liquor volatilizees and obtains graphene oxide/pore creating material powder particle；Graphene oxide obtained by collecting/make
Agent powder particle in hole is simultaneously heat-treated to obtain high-specific surface area fold graphene product under inert gas shielding.
The present invention is first reduced graphene oxide using hydrophilic nitrogenous compound, keeps the premise of its water-wet behavior
Under, then add pore creating material and carry out ultrasonic atomizatio processing, reduce the reunion after graphene oxide is reduced, obtain Gao Bibiao
The porous fold graphene of area.
The present invention, can be with partial reduction graphite oxide by the way that water-soluble nitrogenous compound is mixed with graphene oxide solution
The colleague of alkene keeps its hydrophily, and stable solution can be formed after adding pore creating material, easy to the processing of its ultrasonic atomizatio.
The present invention is compared with prior art, its technological progress is significant.The nitrogenous chemical combination of the graphene oxide of the present invention
Thing, which pre-processes, to be ensured to keep hydrophily while it is reduced, the pore creating material with reducing property being subsequently to added into（Such as KOH,
NaOH etc.）The graphene oxide tentatively reduced cannot be further reduced, so that ensureing the graphene oxide of reduction has well
Hydrophily and monodispersity energy, be to prepare the crucial step of high-specific surface area fold graphene.
Brief description of the drawings
Fig. 1 is the shape appearance figure of the porous fold graphene prepared by 1 the method according to the invention of embodiment.
Fig. 2 is the shape appearance figure of the porous fold graphene prepared by 2 the method according to the invention of embodiment.
Fig. 3 is the shape appearance figure of the porous fold graphene prepared by 3 the method according to the invention of embodiment.
Embodiment
The present invention is further illustrated below by embodiment, but it is not intended to limit the invention.
Embodiment 1
The graphene oxide solution 400ml of 1mg/ml is taken, is firstly added the ammonium hydroxide 30ml that mass percent concentration is 25%, 30 DEG C
After reacting 5h, sodium hydroxide is added, sodium hydroxide is 2 with graphene oxide mass ratio:1, it is uniformly mixed, ultrasonic atomizatio processing,
Drying temperature is 500 DEG C, when protecting lower 800 DEG C of heat treatment 1 small the sample nitrogen being collected into, is washed to neutrality.Finally obtain
Porous fold graphene, specific surface area 1100m2/g.Porous fold graphene pattern is as shown in Figure 1.
Embodiment 2
The graphene oxide solution 200ml of 3mg/ml is taken, is firstly added 6g anhydrous ethylenediamines, after 80 DEG C are reacted 12h, adds hydrogen-oxygen
Change potassium, potassium hydroxide is 4 with graphene oxide mass ratio:1, it is uniformly mixed, ultrasonic atomizatio processing, drying temperature is 300 DEG C, will
When the lower 700 DEG C of heat treatment 2 of sample nitrogen protection being collected into is small, wash to neutrality.Porous fold graphene is finally obtained, compares table
Area is 1636m2/g.Porous fold graphene pattern is as shown in Figure 2.
Embodiment 3
The graphene oxide solution 300ml of 2mg/ml is taken, is firstly added 30g tetraethylenepentamine, after 100 DEG C are reacted 20h, adds carbon
Sour potassium, potassium carbonate are 3 with graphene oxide mass ratio:1, it is uniformly mixed, ultrasonic atomizatio processing, drying temperature is 600 DEG C, will be received
When the lower 1000 DEG C of heat treatment 2 of sample nitrogen protection collected is small, wash to neutrality.Porous fold graphene is finally obtained, compares table
Area is 1218m2/g.Porous fold graphene pattern is as shown in Figure 3.
Claims (2)
1. a kind of preparation method of high specific surface area porous fold graphene, it is characterised in that include the following steps：
1）Graphene oxide solution and water-soluble nitrogenous compound are mixed, the concentration of the graphene oxide solution is 0.1-
5mg/ml, the water-soluble nitrogenous compound is in ammonium hydroxide, ethylenediamine, aniline, triethylene tetramine or tetraethylenepentamine
Any one, the mass ratio of the water-soluble nitrogenous compound and graphene oxide is 1:10-100:1, at 0-100 DEG C
At a temperature of react 0.1-24h, add pore creating material and be uniformly mixed to obtain mixed liquor；The pore creating material for NaOH, KOH or
K2CO3, the mass ratio of graphene oxide and pore creating material is 1:1-1:5；
2）By mixed liquor ultrasonic atomizatio, and heated at a temperature of 100-600 DEG C, obtain graphene oxide/pore creating material powder particle；
3）Graphene oxide/pore creating material powder particle is heat-treated under inert gas shielding, heat treatment temperature 400-1100
DEG C, high specific surface area porous fold graphene is obtained, the specific surface area of the high specific surface area porous fold graphene of gained is 1000
To 2000m2Between/g.
A kind of 2. preparation method of high specific surface area porous fold graphene according to claim 1, it is characterised in that：
Step 1）In, graphene oxide solution is with ammonium hydroxide in mass ratio with 1:10 mass ratio mixing, 60 DEG C reaction 6h, then add with
Graphene oxide mass ratio is 4：1 KOH, is uniformly mixed and obtains mixed liquor.
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Cited By (3)
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| CN110247032A (en) * | 2019-05-28 | 2019-09-17 | 北京汽车股份有限公司 | Nitrogen-doped graphene negative electrode material and preparation method thereof and lithium ion battery |
| CN113233448A (en) * | 2021-06-10 | 2021-08-10 | 北京航空航天大学 | Surface modification method for reduced graphene oxide |
| CN114497513A (en) * | 2022-03-05 | 2022-05-13 | 青岛泰达华润新能源科技有限公司 | Graphene negative electrode material for lithium ion battery and preparation method thereof |
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