CN106395806B - A kind of hydrophilic graphene and preparation method thereof - Google Patents
A kind of hydrophilic graphene and preparation method thereof Download PDFInfo
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- CN106395806B CN106395806B CN201610835622.5A CN201610835622A CN106395806B CN 106395806 B CN106395806 B CN 106395806B CN 201610835622 A CN201610835622 A CN 201610835622A CN 106395806 B CN106395806 B CN 106395806B
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- ball grinder
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention provides a kind of hydrophilic graphenes and preparation method thereof, and this approach includes the following steps：(1), after ball grinder being added in graphite powder, additive and liquid intercalation medium, the ball grinder is sealed；Wherein, the mass ratio of the graphite powder and additive is 5 20:1, liquid intercalation medium is added by every gram of 0 1.5mL of graphite powder；(2), gaseous state intercalation medium is passed through into the ball grinder, and pressure is set to control in 2 12MPa by adjusting the air inflow of gaseous state intercalation medium, at this pressure, system temperature is risen to 35 150 DEG C and carries out ball milling original position accessory molecule intercalation, after reaction, the hydrophilic graphene is obtained.
Description
Technical field
The present invention relates to a kind of hydrophilic graphenes and preparation method thereof, belong to grapheme material technical field.
Background technology
Since being found from graphene in 2004, the universal blueness from physics and Material Field researcher has just been received always
It looks at.Graphene be one kind by carbon atom with sp2The hexangle type of hybridized orbit composition is in the flat film of honeycomb lattice.Although graphite
Alkene is one kind most thin in known materials only there are one carbon atomic layer thickness, however but unusual rigid.Graphene
It is to be currently known the most outstanding material of electric conductivity.In addition, there are many more excellent performances for graphene：Such as higher Young's modulus,
Thermal conductivity, huge specific surface area etc..Due to the property of graphene, it electronics, optics, magnetics, biomedicine,
Sensor, energy storage etc. are widely used.But the coagulation phenomenon of graphene in water seriously affected graphene this
The application of kind excellent material.
Therefore it provides the technology that a kind of hydrophilic graphene and preparation method thereof has become this field urgent need to resolve is asked
Topic.
Invention content
In order to solve above-mentioned disadvantage and deficiency, the purpose of the present invention is to provide a kind of preparation sides of hydrophilic graphene
Method.
The hydrophilic graphene obtained the present invention also aims to provide the preparation method of above-mentioned hydrophilic graphene.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of preparation methods of hydrophilic graphene comprising with
Lower step：
(1), after ball grinder being added in graphite powder, additive and liquid intercalation medium, the ball grinder is sealed；Wherein, described
The mass ratio of graphite powder and additive is 5-20:1, liquid intercalation medium is added by every gram of graphite powder 0-1.5mL；
(2), gaseous state intercalation medium is passed through into the ball grinder, and the air inflow by adjusting gaseous state intercalation medium makes pressure
Power is controlled in 2-12MPa, at this pressure, it is anti-that system temperature is risen to 35-150 DEG C of progress ball milling original position accessory molecule intercalation
It answers, after reaction, obtains the hydrophilic graphene.
Preparation method according to the present invention, wherein the present invention does not make specific requirement, this field skill to graphite powder used
Art personnel can need to select suitable graphite powder according to field operation, in the specific embodiment of the invention, graphite powder used
Including expanded graphite powder and crystalline flake graphite.
Preparation method according to the present invention, wherein to graphite powder, additive and liquid intercalation medium in step (1)
Addition sequence be not required.
Preparation method according to the present invention, it is preferable that liquid intercalation medium described in step (1) presses every gram of graphite powder
0.5-1.5mL is added.
Preparation method according to the present invention, it is preferable that additive includes dodecyl benzene sulfonic acid described in step (1)
Sodium (SDBS), lauryl sodium sulfate (SDS), polyvinylpyrrolidone (PVP) and diallyl dimethyl ammoniumchloride
One or more of (PDDA) combination.
Preparation method according to the present invention, it is preferable that liquid intercalation medium described in step (1) include ethyl alcohol and/
Or water.
Preparation method according to the present invention, it is preferable that gaseous state intercalation medium includes titanium dioxide described in step (2)
One kind in carbon, nitrogen and propane.
Preparation method according to the present invention, it is preferable that ball grinder rotational speed of ball-mill described in step (2) is 100-
1000rpm, reaction time 0.5-8h.
Preparation method according to the present invention, it is preferable that this method is further comprising the steps of：
Reaction terminates, and is cooled to again after carrying out pressure release to the ball grinder, takes out product；The product is washed, filters
After dry, obtain the hydrophilic graphene.
Preparation method according to the present invention, it is preferable that the pressure release is to be let out gauge pressure in ball grinder by vent valve
It is depressed into 0MPa.
Preparation method according to the present invention, it is preferable that described to be cooled to be cooled to ball grinder under air conditions
Room temperature.
Preparation method according to the present invention, it is preferable that it includes deionized water and absolute ethyl alcohol to wash solvent used.
Preparation method according to the present invention, it is preferable that the drying is 70-80 DEG C of dry 6-12h.
Preparation method according to the present invention, the ball grinder used in the present invention is the conventional equipment that uses of this field,
In the specific embodiment of the invention, ball grinder used is vertical stirring high speed ball mill, in addition, the present invention matches ball material to ball mill
Matter has no particular/special requirement, and should be advisable with smaller and can be reached uniform rotation effect under the drive of stirring with ball size.
On the other hand, the present invention also provides the hydrophily graphite that the preparation method of above-mentioned hydrophilic graphene is prepared
Alkene.
The preparation method of hydrophilic graphene provided by the present invention is based under pressure condition through molecule intercalation and ball
Mill auxiliary law in situ removes graphite, and other additives are added again in preparation process, under certain temperature, pressure, graphite flake
Layer is removed under the action of all substances into the good graphene of hydrophily.
In preparation process, intercalation medium can show excellent dispersibility under certain temperature, pressure condition, relatively hold
Easy intercalation enters in graphite flake layer spacing, reaches stripping on the basis of molecule intercalation, then by the shearing strength between layers that ball milling provides
Purpose from graphite flake layer, and grafted between the hydrophilic radical and graphene contained by additive, intercalation or surface modification,
Hydrophilic graphene finally is prepared.
Description of the drawings
Fig. 1 is the schematic diagram of the preparation method equipment therefor of hydrophilic graphene provided in an embodiment of the present invention；
Fig. 2 a are the transmission electron microscope picture of expanded graphite powder raw material in the embodiment of the present invention 1；
Fig. 2 b are the transmission electron microscope picture for the hydrophilic graphene being prepared in the embodiment of the present invention 1.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, in conjunction in detail below
Embodiment and Figure of description carry out following detailed description to technical scheme of the present invention, but should not be understood as can to of the invention
The restriction of practical range.
Embodiment 1
Present embodiments provide a kind of preparation method of hydrophilic graphene comprising following steps：
Expanded graphite powder, PVP and ethyl alcohol are added in ball grinder, wherein the mass ratio of expanded graphite powder and PVP are 10:
1, ethyl alcohol is added by 1mL/ (g graphite powders), closes ball grinder；
It is passed through CO by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes pressure control in 10MPa；
Set reaction temperature as 50 DEG C (pressure inside the tank can change in temperature-rise period, adjust outlet valve so that pressure is kept
In 10MPa), wait for that temperature reaches 50 DEG C, setting speed 300rpm, 2 hours reaction time；
It is 0MPa by gauge pressure in vent valve pressure release to tank, reaction unit (as shown in Figure 1) is in air item to the end of reaction
After being cooled to room temperature under part can opening, take out product；
Product deionized water and absolute ethyl alcohol are washed into filtering, are then placed into drying box under 70 DEG C of temperature conditions
It is dry, you can to obtain the hydrophilic graphene of PVP modifications.
Transmission electron microscope analysis is carried out respectively to the hydrophilic graphene that expanded graphite powder raw material and the present embodiment are prepared,
The transmission electron microscope picture of the two respectively as shown in Fig. 2 a and Fig. 2 b, from Fig. 2 a and Fig. 2 b as can be seen that by graphite under transmission electron microscope
The number of plies for the hydrophilic graphene that raw material and the present embodiment are prepared is compared it is found that being inserted by ball milling original position accessory molecule
Layer can remove graphite raw material to obtain form the few-layer graphene alkene.
Again to being the raw material use graphene that method is prepared in the prior art and the present embodiment system using expanded graphite powder
Standby obtained hydrophilic graphene carries out test water-dispersed respectively, i.e.,：Disperse 15mg the present embodiment in 15mL water respectively to prepare
Obtained hydrophilic graphene and the graphene prepared using method in the prior art obtain nearly millesimal solubility, so
Standing stability test is carried out to the two dispersions again afterwards.
Test result shows：After placing 20 days, which remains to keep very stable state,
And the graphene dispersion system prepared as raw material using expanded graphite powder can settle completely in or so hour.Test water-dispersed
The experimental results showed that：For graphene prepared by commonsense method, it is prepared into using preparation method provided by the present invention
To hydrophilic graphene can keep extraordinary stability.
Embodiment 2
Present embodiments provide a kind of preparation method of hydrophilic graphene comprising following steps：
Expanded graphite powder, SDBS and ethyl alcohol are added in ball grinder, the wherein mass ratio of expanded graphite powder and SDBS is
10:1, ethyl alcohol is added by 1mL/ (g graphite powders), closes ball grinder；
It is passed through CO by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes pressure control in 12MPa；
Set reaction temperature as 45 DEG C (pressure inside the tank can change in temperature-rise period, adjust outlet valve so that pressure is kept
In 10MPa), wait for that temperature reaches 45 DEG C, setting speed 200rpm, 2 hours reaction time；
It is 0MPa by gauge pressure in vent valve pressure release to tank to the end of reaction, reaction unit is cooled under air conditions
After room temperature can opening, take out product；
Product deionized water and absolute ethyl alcohol are washed into filtering, are then placed into drying box under 70 DEG C of temperature conditions
It is dry, you can to obtain the hydrophilic graphene of SDBS modifications.
Embodiment 3
Present embodiments provide a kind of preparation method of hydrophilic graphene comprising following steps：
Crystalline flake graphite, PVP and ethyl alcohol are added in ball grinder, wherein the mass ratio of crystalline flake graphite and PVP is 20:1, second
Alcohol is added by 1mL/ (g graphite powders), closes ball grinder；
It is passed through CO by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes pressure control in 11MPa；
Set reaction temperature as 45 DEG C (pressure inside the tank can change in temperature-rise period, adjust outlet valve so that pressure is kept
In 10MPa), wait for that temperature reaches 45 DEG C, setting speed 400rpm, the reaction time is 3 hours；
It is 0MPa by gauge pressure in vent valve pressure release to tank to the end of reaction, reaction unit is cooled under air conditions
After room temperature can opening, take out product；
Product deionized water and absolute ethyl alcohol are washed into filtering, are then placed into drying box under 75 DEG C of temperature conditions
It is dry, you can to obtain the hydrophilic graphene of PVP modifications.
Embodiment 4
Present embodiments provide a kind of preparation method of hydrophilic graphene comprising following steps：
Crystalline flake graphite, PDDA and ethyl alcohol are added in ball grinder, wherein the mass ratio of crystalline flake graphite and PDDA is 5:1,
Ethyl alcohol is added by 0.5mL/ (g graphite powders), closes ball grinder；
It is passed through N by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes pressure control in 3.6MPa；
Set reaction temperature as 35 DEG C (pressure inside the tank can change in temperature-rise period, adjust outlet valve so that pressure is kept
In 3.6MPa), wait for that temperature reaches 35 DEG C, setting speed 900rpm, the reaction time is 6 hours；
It waits for after reaction, is 0MPa by gauge pressure in vent valve pressure release to tank, reaction unit is cooling under air conditions
After to room temperature can opening, take out product；
Product is washed with deionized water and absolute ethyl alcohol, is filtered, is then placed into drying box in 70 DEG C of temperature conditions
Lower drying, you can obtain the hydrophilic graphene of PDDA modifications.
Embodiment 5
Present embodiments provide a kind of preparation method of hydrophilic graphene comprising following steps：
Expanded graphite powder, SDBS and ethyl alcohol are added in ball grinder, the wherein mass ratio of expanded graphite powder and SDBS is
10:1, ethyl alcohol is added by 1mL/ (g graphite powders), closes ball grinder；
It is passed through propane gas by ball grinder upper inlet pipeline, adjusting air inflow makes pressure control in 5MPa；
Set reaction temperature as 130 DEG C (pressure inside the tank can change in temperature-rise period, adjust outlet valve so that pressure is kept
In 5MPa), wait for that temperature reaches 130 DEG C, setting speed 600rpm, the reaction time is 7 hours；
It waits for after reaction, is 0MPa by gauge pressure in vent valve pressure release to tank, reaction unit is cooling under air conditions
After to room temperature can opening, take out product；
Product is washed with deionized water and absolute ethyl alcohol, is filtered, is then placed into drying box in 80 DEG C of temperature conditions
Lower drying, you can obtain the hydrophilic graphene of SDBS modifications.
Claims (9)
1. a kind of preparation method of hydrophilic graphene comprising following steps：
(1), after ball grinder being added in graphite powder, additive and liquid intercalation medium, the ball grinder is sealed；Wherein, the graphite
The mass ratio of powder and additive is 5-20:1, liquid intercalation medium is added by every gram of graphite powder 0-1.5mL；
(2), gaseous state intercalation medium is passed through into the ball grinder, and the air inflow by adjusting gaseous state intercalation medium makes pressure control
System is in 2-12MPa, at this pressure, system temperature is risen to 35-150 DEG C and carries out ball milling original position accessory molecule intercalation, instead
After answering, the hydrophilic graphene is obtained；
Additive described in step (1) includes neopelex, lauryl sodium sulfate, polyvinylpyrrolidone and gathers
The combination of one or more of diallyldimethylammonium chloride.
2. preparation method according to claim 1, which is characterized in that liquid intercalation medium includes second described in step (1)
Alcohol and/or water.
3. preparation method according to claim 1, which is characterized in that gaseous state intercalation medium described in step (2) includes two
One kind in carbonoxide, nitrogen and propane.
4. preparation method according to claim 1, which is characterized in that ball grinder rotational speed of ball-mill is described in step (2)
100-1000rpm, reaction time 0.5-8h.
5. preparation method according to claim 1, which is characterized in that this method is further comprising the steps of：
Reaction terminates, and is cooled to again after carrying out pressure release to the ball grinder, takes out product；The product is washed, is done after filtering
It is dry, obtain the hydrophilic graphene.
6. preparation method according to claim 5, which is characterized in that the pressure release is by vent valve by table in ball grinder
Press pressure release to 0MPa.
7. preparation method according to claim 5, which is characterized in that it is described be cooled to it is under air conditions that ball grinder is cold
But to room temperature.
8. preparation method according to claim 5, which is characterized in that it includes deionized water and anhydrous to wash solvent used
Ethyl alcohol.
9. preparation method according to claim 5, which is characterized in that the drying is 70-80 DEG C of dry 6-12h.
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| CN201610835622.5A CN106395806B (en) | 2016-09-20 | 2016-09-20 | A kind of hydrophilic graphene and preparation method thereof |
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