CN106395806A - Hydrophilic graphene and preparation method thereof - Google Patents
Hydrophilic graphene and preparation method thereof Download PDFInfo
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- CN106395806A CN106395806A CN201610835622.5A CN201610835622A CN106395806A CN 106395806 A CN106395806 A CN 106395806A CN 201610835622 A CN201610835622 A CN 201610835622A CN 106395806 A CN106395806 A CN 106395806A
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- ball grinder
- graphite powder
- hydrophilic graphene
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- C—CHEMISTRY; METALLURGY
- 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 invention provides hydrophilic graphene and a preparation method thereof. The preparation method comprises (1) adding graphite powder, additives and a liquid intercalation medium into a ball mill pot and sealing the ball mill pot, wherein a mass ratio of the graphite powder to the additives is 5-20: 1 and 0-1.5mL of the liquid intercalation medium is added into each gram of the graphite powder, and (2) feeding a gaseous intercalation medium into the ball mill pot, adjusting the inlet volume of the gaseous intercalation medium to control the pressure to 2 to 12MPa, under this pressure, increasing the temperature of the system to 35 to 150 DEG C, and carrying out a ball milling in-situ assisted molecular intercalation reaction process so that hydrophilic graphene is obtained after the reaction.
Description
Technical field
The present invention relates to a kind of hydrophilic graphene and preparation method thereof, belong to grapheme material technical field.
Background technology
Since Graphene in 2004 is found, it just enjoys the universal green grass or young crops from physics and Material Field researcher always
Look at.Graphene be a kind of by carbon atom with sp2The hexangle type of hybrid orbital composition is in the flat film of honeycomb lattice.Although graphite
Alkene only one of which carbon atomic layer thickness, and be the thinnest one kind in known materials, but but unusual rigid.Graphene
It is to be currently known electric conductivity material outstanding.Additionally, Graphene also has many excellent performances：As higher Young's moduluss,
Thermal conductivity, huge specific surface area etc..Due to the property of Graphene, it electronics, optics, magnetics, biomedicine,
The aspects such as sensor, energy storage are all widely used.But coagulation phenomenon in water for the Graphene had a strong impact on Graphene this
Plant the application of excellent material.
Therefore it provides the technology that a kind of hydrophilic graphene and preparation method thereof has become as this area urgent need to resolve is asked
Topic.
Content of the invention
In order to solve above-mentioned shortcoming and defect, it is an object of the invention to provide a kind of preparation side of hydrophilic graphene
Method.
The present invention also aims to providing the hydrophilic graphene that the preparation method of above-mentioned hydrophilic graphene obtains.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of preparation method of hydrophilic graphene, it include with
Lower step：
(1), graphite powder, additive and liquid intercalation medium are added after ball grinder, seal this ball grinder；Wherein, described
Graphite powder is 5-20 with the mass ratio of additive:1, liquid intercalation medium is added by every gram of graphite powder 0-1.5mL；
(2), it is passed through gaseous state intercalation medium in described ball grinder, and pressure is made by the air inflow adjusting gaseous state intercalation medium
Power controls in 2-12MPa, and at this pressure, system temperature is risen to 35-150 DEG C, and to carry out ball milling original position accessory molecule intercalation anti-
Should, after reaction terminates, obtain described hydrophilic graphene.
According to preparation method of the present invention, wherein, the present invention does not make specific requirement, this area 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.
According to preparation method of the present invention, wherein, to graphite powder, additive and liquid intercalation medium in step (1)
Addition sequence be not required.
According to preparation method of 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.
According to preparation method of the present invention it is preferable that additive described in step (1) includes DBSA
Sodium (SDBS), sodium lauryl sulphate (SDS), Polyvinylpyrrolidone (PVP) and diallyl dimethyl ammoniumchloride
One or more of (PDDA) combination.
According to preparation method of the present invention it is preferable that liquid intercalation medium described in step (1) include ethanol and/
Or water.
According to preparation method of the present invention it is preferable that gaseous state intercalation medium described in step (2) includes titanium dioxide
One of carbon, nitrogen and propane.
According to preparation method of the present invention it is preferable that ball grinder rotational speed of ball-mill described in step (2) is 100-
1000rpm, the response time is 0.5-8h.
According to preparation method of the present invention it is preferable that the method is further comprising the steps of：
Reaction terminates, and described ball grinder is carried out be cooled to after pressure release again, takes out product；This product is scrubbed, filtration
After be dried, obtain described hydrophilic graphene.
According to preparation method of the present invention it is preferable that described pressure release is to be let out gauge pressure in ball grinder by vent valve
It is depressed into 0MPa.
According to preparation method of the present invention it is preferable that described be cooled to be cooled to ball grinder under air conditionses
Room temperature.
According to preparation method of the present invention it is preferable that the solvent used by washing includes deionized water and dehydrated alcohol.
According to preparation method of the present invention it is preferable that described drying is dried 6-12h for 70-80 DEG C.
The conventional equipment being used for this area according to preparation method of the present invention, the ball grinder used by the present invention,
In the specific embodiment of the invention, ball grinder used is vertical stirring high speed ball mill, additionally, the present invention joins ball material to ball mill
Matter has no particular/special requirement, and joins ball size and should be advisable and can be issued to uniform rotation effect in the drive of stirring with less.
On the other hand, present invention also offers the hydrophilic graphite for preparing of the preparation method of above-mentioned hydrophilic graphene
Alkene.
The preparation method of hydrophilic graphene provided by the present invention be based under pressure condition pass through molecule intercalation and ball
Mill original position auxiliary law peels off graphite, adds other additives, under certain temperature, pressure, graphite flake in preparation process again
Layer, in the presence of all substances, peels off into the good Graphene of hydrophilic.
In preparation process, intercalation medium can show excellent dispersibility under certain temperature, pressure condition, relatively holds
Easily intercalation enters in graphite flake layer spacing, and on the basis of molecule intercalation, then the shearing strength between layers being provided by ball milling reach stripping
From the purpose of graphite flake layer, and between the hydrophilic group contained by additive and Graphene, carry out grafting, intercalation or surface modification,
Finally prepare hydrophilic graphene.
Brief description
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 is the transmission electron microscope picture of expanded graphite powder raw material in the embodiment of the present invention 1；
Fig. 2 b is the transmission electron microscope picture of the hydrophilic graphene preparing in the embodiment of the present invention 1.
Specific embodiment
In order to be more clearly understood to the technical characteristic of the present invention, purpose and beneficial effect, in conjunction with detail below
Embodiment and Figure of description technical scheme is carried out described further below, but it is not intended that to the present invention can
The restriction of practical range.
Embodiment 1
Present embodiments provide a kind of preparation method of hydrophilic graphene, it comprises the following steps：
Expanded graphite powder, PVP and ethanol are added in ball grinder, wherein expanded graphite powder and the mass ratio of PVP are 10:
1, ethanol is pressed 1mL/ (g graphite powder) and is added, and closes ball grinder；
CO is passed through by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes Stress control in 10MPa；
Set reaction temperature as 50 DEG C (in temperature-rise period, pressure inside the tank can change, adjust outlet valve make pressure keep
In 10MPa), treat that temperature reaches 50 DEG C, setting speed is 300rpm, 2 hours response time；
Question response terminates, and is 0MPa by gauge pressure in vent valve pressure release to tank, reaction unit (as shown in Figure 1) is in air bar
Get final product can opening after being cooled to room temperature under part, take out product；
Product deionized water and absolute ethanol washing are filtered, is then placed in drying baker under 70 DEG C of temperature conditionss
It is dried, you can obtain the hydrophilic graphene of PVP modification.
Respectively transmission electron microscope analysis are carried out to the hydrophilic graphene that expanded graphite powder raw material and the present embodiment prepare,
The transmission electron microscope picture of the two, respectively as shown in Fig. 2 a and Fig. 2 b, can be seen that graphite under transmission electron microscope from Fig. 2 a and Fig. 2 b
Knowable to the number of plies of the hydrophilic graphene that raw material and the present embodiment prepare is contrasted, inserted by ball milling original position accessory molecule
Graphite raw material can be peeled off and obtain form the few-layer graphene alkene by layer.
Again to the Graphene being prepared for raw material using method in prior art with expanded graphite powder and the present embodiment system
The standby hydrophilic graphene obtaining carries out moisture respectively and dissipates test, that is,：Dispersion 15mg the present embodiment preparation in 15mL water respectively
The hydrophilic graphene obtaining and the Graphene using method preparation in prior art, obtain closely millesimal dissolubility, so
Again standing stability test is carried out to this two dispersions afterwards.
Test result shows：After placing 20 days, this hydrophilic graphene dispersion remains to keep very stable state,
And the graphene dispersion system prepared for raw material with expanded graphite powder can be settled about a hour completely.Moisture dissipates test
Test result indicate that：For Graphene compared to commonsense method preparation, 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, it comprises the following steps：
Expanded graphite powder, SDBS and ethanol are added in ball grinder, the mass ratio of wherein expanded graphite powder and SDBS is
10:1, ethanol is pressed 1mL/ (g graphite powder) and is added, and closes ball grinder；
CO is passed through by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes Stress control in 12MPa；
Set reaction temperature as 45 DEG C (in temperature-rise period, pressure inside the tank can change, adjust outlet valve make pressure keep
In 10MPa), treat that temperature reaches 45 DEG C, setting speed is 200rpm, 2 hours response time；
Question response terminates, and is 0MPa by gauge pressure in vent valve pressure release to tank, and reaction unit is cooled under air conditionses
Get final product can opening after room temperature, take out product；
Product deionized water and absolute ethanol washing are filtered, is then placed in drying baker under 70 DEG C of temperature conditionss
It is dried, you can obtain the hydrophilic graphene of SDBS modification.
Embodiment 3
Present embodiments provide a kind of preparation method of hydrophilic graphene, it comprises the following steps：
Crystalline flake graphite, PVP and ethanol are added in ball grinder, wherein the mass ratio of crystalline flake graphite and PVP is 20:1, second
Alcohol is pressed 1mL/ (g graphite powder) and is added, and closes ball grinder；
CO is passed through by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes Stress control in 11MPa；
Set reaction temperature as 45 DEG C (in temperature-rise period, pressure inside the tank can change, adjust outlet valve make pressure keep
In 10MPa), treat that temperature reaches 45 DEG C, setting speed is 400rpm, the response time is 3 hours；
Question response terminates, and is 0MPa by gauge pressure in vent valve pressure release to tank, and reaction unit is cooled under air conditionses
Get final product can opening after room temperature, take out product；
Product deionized water and absolute ethanol washing are filtered, is then placed in drying baker under 75 DEG C of temperature conditionss
It is dried, you can obtain the hydrophilic graphene of PVP modification.
Embodiment 4
Present embodiments provide a kind of preparation method of hydrophilic graphene, it comprises the following steps：
Crystalline flake graphite, PDDA and ethanol are added in ball grinder, wherein the mass ratio of crystalline flake graphite and PDDA is 5:1,
Ethanol is pressed 0.5mL/ (g graphite powder) and is added, and closes ball grinder；
N is passed through by ball grinder upper inlet pipeline2Gas, adjusting air inflow makes Stress control in 3.6MPa；
Set reaction temperature as 35 DEG C (in temperature-rise period, pressure inside the tank can change, adjust outlet valve make pressure keep
In 3.6MPa), treat that temperature reaches 35 DEG C, setting speed is 900rpm, the response time is 6 hours；
After question response terminates, it is 0MPa by gauge pressure in vent valve pressure release to tank, reaction unit cools down under air conditionses
Get final product can opening to room temperature, take out product；
By product deionized water and absolute ethanol washing, filter, be then placed in drying baker in 70 DEG C of temperature conditionss
Lower drying, you can obtain the hydrophilic graphene of PDDA modification.
Embodiment 5
Present embodiments provide a kind of preparation method of hydrophilic graphene, it comprises the following steps：
Expanded graphite powder, SDBS and ethanol are added in ball grinder, the mass ratio of wherein expanded graphite powder and SDBS is
10:1, ethanol is pressed 1mL/ (g graphite powder) and is added, and closes ball grinder；
Propane gas are passed through by ball grinder upper inlet pipeline, adjusting air inflow makes Stress control in 5MPa；
Set reaction temperature as 130 DEG C (in temperature-rise period, pressure inside the tank can change, adjust outlet valve make pressure keep
In 5MPa), treat that temperature reaches 130 DEG C, setting speed is 600rpm, the response time is 7 hours；
After question response terminates, it is 0MPa by gauge pressure in vent valve pressure release to tank, reaction unit cools down under air conditionses
Get final product can opening to room temperature, take out product；
By product deionized water and absolute ethanol washing, filter, be then placed in drying baker in 80 DEG C of temperature conditionss
Lower drying, you can obtain the hydrophilic graphene of SDBS modification.
Claims (10)
1. a kind of preparation method of hydrophilic graphene, it comprises the following steps：
(1), graphite powder, additive and liquid intercalation medium are added after ball grinder, seal this ball grinder；Wherein, described graphite
Powder is 5-20 with the mass ratio of additive:1, liquid intercalation medium is added by every gram of graphite powder 0-1.5mL；
(2), it is passed through gaseous state intercalation medium in described ball grinder, and pressure control is made by the air inflow adjusting gaseous state intercalation medium
System, 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 should terminating, obtain described hydrophilic graphene.
2. preparation method according to claim 1 is it is characterised in that additive described in step (1) includes dodecyl
One or more of benzene sulfonic acid sodium salt, sodium lauryl sulphate, Polyvinylpyrrolidone and diallyl dimethyl ammoniumchloride
Combination.
3. preparation method according to claim 1 is it is characterised in that liquid intercalation medium described in step (1) includes second
Alcohol and/or water.
4. preparation method according to claim 1 is it is characterised in that gaseous state intercalation medium described in step (2) includes two
One of carbonoxide, nitrogen and propane.
5. preparation method according to claim 1 is it is characterised in that ball grinder rotational speed of ball-mill described in step (2) is
100-1000rpm, the response time is 0.5-8h.
6. preparation method according to claim 1 is it is characterised in that the method is further comprising the steps of：
Reaction terminates, and described ball grinder is carried out be cooled to after pressure release again, takes out product；This product is scrubbed, filter after dry
Dry, obtain described hydrophilic graphene；
Preferably described drying is dried 6-12h for 70-80 DEG C.
7. preparation method according to claim 6 is it is characterised in that described pressure release is by table in ball grinder by vent valve
Pressure pressure release is to 0MPa.
8. preparation method according to claim 6 it is characterised in that described be cooled under air conditionses, ball grinder is cold
But to room temperature.
9. preparation method according to claim 6 is it is characterised in that washing solvent used includes deionized water and anhydrous
Ethanol.
10. the hydrophilic graphene that the preparation method of hydrophilic graphene described in any one of claim 1-9 prepares.
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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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610835622.5A CN106395806B (en) | 2016-09-20 | 2016-09-20 | A kind of hydrophilic graphene and preparation method thereof |
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| CN106395806A true CN106395806A (en) | 2017-02-15 |
| CN106395806B CN106395806B (en) | 2018-08-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113200538A (en) * | 2021-04-07 | 2021-08-03 | 北京化工大学 | Method for preparing graphene aqueous phase dispersion liquid through mechanical stripping and prepared graphene aqueous phase dispersion liquid |
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| CN104876218A (en) * | 2015-06-10 | 2015-09-02 | 北京化工大学 | Room-temperature preparation method for water-soluble functionalized graphene |
| CN105800603A (en) * | 2016-04-22 | 2016-07-27 | 华侨大学 | Method for quickly preparing high-quality graphene |
| CN105883763A (en) * | 2014-12-09 | 2016-08-24 | 戴加龙 | Efficient preparation method of graphene |
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| CN105883763A (en) * | 2014-12-09 | 2016-08-24 | 戴加龙 | Efficient preparation method of graphene |
| CN104876218A (en) * | 2015-06-10 | 2015-09-02 | 北京化工大学 | Room-temperature preparation method for water-soluble functionalized graphene |
| CN105800603A (en) * | 2016-04-22 | 2016-07-27 | 华侨大学 | Method for quickly preparing high-quality graphene |
Non-Patent Citations (2)
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| LEI LI ET AL.: "Preparation of graphene nanosheets by shear-assisted supercritical CO2 exfoliation", 《CHEMICAL ENGINEERING JOURNAL》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113200538A (en) * | 2021-04-07 | 2021-08-03 | 北京化工大学 | Method for preparing graphene aqueous phase dispersion liquid through mechanical stripping and prepared graphene aqueous phase dispersion liquid |
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