CN108314022A - A kind of method that the direct stripping of ionic liquid prepares graphene - Google Patents
A kind of method that the direct stripping of ionic liquid prepares graphene Download PDFInfo
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- CN108314022A CN108314022A CN201810258389.8A CN201810258389A CN108314022A CN 108314022 A CN108314022 A CN 108314022A CN 201810258389 A CN201810258389 A CN 201810258389A CN 108314022 A CN108314022 A CN 108314022A
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- ionic liquid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Abstract
The invention discloses the methods that a kind of direct stripping of ionic liquid prepares graphene.This method for preparing graphene includes the following steps：1) it after mixing graphite and ionic liquid, is stirred to react, adds water stirring, collect sediment；2) dry by sediment undergoes washing, obtain graphene.The present invention prepares graphene under mild conditions using alkali ionic liquid and surface coefficient and anion similar in graphene to the dipping and swelling action of graphite platelet structure, has advantage of low cost, environmentally protective, easy to operate and efficient.
Description
Technical field
The present invention relates to the methods that a kind of direct stripping of ionic liquid prepares graphene.
Background technology
Graphene be it is a kind of by carbon atom with sp2 be hybridized to combination form hexagon be in honeycomb-patterned ordered arrangement two
Tie up material.The carbon material of this novel bi-dimensional cellular shape structure has excellent performance in all various aspects, such as fabulous saturating
Photosensitiveness only absorbs 2.3% light, and thermal coefficient is up to 5300W/mK, and the electron mobility under room temperature is more than 15000cm2/
Vs, resistivity only have 10-6Ω cm, in addition graphene be still currently known most thin but most hard material.These are unique
It is high that property so that graphene has in various fields such as energy storage, photoelectric device, gas sensor and composite materials
Application value and potentiality.
There are many preparation methods of graphene, mainly include chemical vapour deposition technique, oxidation-reduction method, liquid phase stripping method and
Mechanical stripping method etc..Micromechanics stripping method can only the extremely limited graphene film of production quantity, unsuitable industrialization and scale
Production requirement.Chemical vapour deposition technique can meet the requirement of prepare with scale high-quality graphene, but of high cost, and technique is multiple
It is miscellaneous.Oxidation-reduction method can prepare graphene on a large scale, but obtained quality of graphene is not high, and will produce a large amount of sour water,
Easily environment is damaged.Liquid phase stripping method can prepare high-quality graphene, but yield is very low, and the business for limiting it is answered
With.
Ionic liquid refers to the low temperature molten salt by being made of zwitterion, with steam forces down, stability is good, pollution-free
And outstanding advantages of easily recycling, and it is known as " green solvent ".In addition, ionic liquid low-surface-energy, polarity is strong, can dissolve more
Kind inorganic material, it is of increased attention in the preparation of inorganic nano molecule and composite material in recent years.
Surface coefficient similar in ionic liquid and graphene so that it, which can be applied to stripping and prepares the application of graphene, works as
In.CN102730676A discloses a kind of preparation method of graphene, by crystalline graphite powder and ionic liquid mixture in anaerobic
Under the conditions of grind, obtain the mixture of graphene-containing, then mixture ultrasonic disperse is obtained into graphene dispersing solution.Though can obtain
Graphene, but need 1.5 × 105-8.0×105The pressure of Pascal, it is also necessary to oxygen-free atmosphere, preparation condition is relatively harsh,
And it is higher to equipment requirement.The preparation method of graphene disclosed in CN103626162A leads to graphite dispersion in ionic liquid
Ball-milling method dispersion stripping is crossed, then washs and is dried to obtain the high graphene of specific surface area.But in preparation process, do not need largely and not
Similar organic solvent could remove the ionic liquid in graphene completely, that is, improve manufacturing cost, and these organic wastes
Liquid processing also brings along many environmental problems.CN103708442A discloses a kind of method that ionic liquid prepares graphene,
Graphene oxide is prepared using ionic liquid and acid, oxidant hybrid reaction, then by hydrazine hydrate reduction at graphene.Although subtracting
The dosage of few acid and oxidant, but the graphene oxide for using, and obtaining cannot be avoided to need to be restored with hydrazine hydrate completely, poison
Property is big, big to the harm of environment.CN 103626164A disclose a kind of preparation method of graphene, after graphite is carried out intercalation,
It is removed with ionic liquid under the action of externally-applied magnetic field, although the production efficiency of graphene can be improved, intercalation process
460-550 DEG C of hot conditions are needed, and post-processing step is cumbersome, production cost is higher, is not suitable for large-scale promotion.
Invention content
The purpose of the present invention is to provide the methods that a kind of direct stripping of ionic liquid prepares graphene.
The technical solution used in the present invention is：
A kind of method that the direct stripping of ionic liquid prepares graphene, includes the following steps：
1) it after mixing graphite and ionic liquid, is stirred to react, adds water stirring, collect sediment；
2) dry by sediment undergoes washing, obtain graphene.
In step 1), the mass ratio of graphite and ionic liquid is 1：(1~10).
In step 1), graphite is at least one of crystalline flake graphite, artificial graphite, expanded graphite.
In step 1), ionic liquid is alkali ionic liquid.
In step 1), ionic liquid is 1- butyl -3- methylimidazoles hydroxide, 1- ethyl-3-methylimidazole hydroxides
Object, 1- butyl -3- methylimidazoles imidazole salts, 1- butyl -3- methylimidazoles bicarbonate, 1- butyl -3- N-Methylimidazoleacetic salt
At least one of.
In step 1), the temperature being stirred to react is 0 DEG C~100 DEG C, and the time being stirred to react is 1h~15h.
In step 1), the time that water stirring is added is 5min~15min；The water of addition be deionized water, deionized water with
The amount ratio of graphite is (15~25) mL；1g.
In step 1), the method for collecting sediment is to centrifuge to collect.
In step 2), cleaning is specially to use deionized water washing sediment 2~5 times.
In step 2), dry method is spray drying or freeze-drying.
The beneficial effects of the invention are as follows：
The present invention is using alkali ionic liquid with surface coefficient and anion similar in graphene to graphite platelet structure
Dipping and swelling action, prepare graphene under mild conditions, have it is of low cost, environmentally protective, easy to operate and high
The advantage of effect.
Specifically：
Compared with existing graphene preparation technology, the hydrogen of the alkali ionic liquid that the present invention selects, especially imidazoles
Oxide ion liquid, for other ionic liquids, anion is the ionic liquid of hydroxyl radical negative ion to graphite knot
Structure has preferably swelling and permeability, enables graphite at ambient temperature, and graphene just can be obtained by stirring, washing, separation.
The method that the present invention prepares graphene is not only easy to operate, requires production equipment low, production efficiency height, and remove
In the process that the reactions such as oxidation or reduction do not occur, the graphene-structured of production is complete, and defect is few, while ionic liquid can return
It receives and recycles, production cost is low, will not cause damages to environment.
Method provided by the present invention is simple, of low cost, and obtained graphene yield is high, high-quality, is suitble to big rule
Mould is promoted the use of.
Description of the drawings
Fig. 1 is the TEM electron microscopes of the graphene prepared by embodiment 1；
Fig. 2 is the Raman spectrogram of the graphene prepared by embodiment 1.
Specific implementation mode
A kind of method that the direct stripping of ionic liquid prepares graphene, includes the following steps：
1) it after mixing graphite and ionic liquid, is stirred to react, adds water stirring, collect sediment；
2) dry by sediment undergoes washing, obtain graphene.
Preferably, in step 1), the mass ratio of graphite and ionic liquid is 1：(1~10).
Preferably, in step 1), graphite is at least one of crystalline flake graphite, artificial graphite, expanded graphite；It is further excellent
Choosing, in step 1), graphite is crystalline flake graphite.
Preferably, in step 1), ionic liquid is alkali ionic liquid；It is further preferred that in step 1), ionic liquid
For 1- butyl -3- methylimidazoles hydroxide, 1- ethyl-3-methylimidazoles hydroxide, 1- butyl -3- methylimidazole imidazoles
At least one of salt, 1- butyl -3- methylimidazoles bicarbonate, 1- butyl -3- N-Methylimidazoleacetic salt；Still further preferably
, in step 1), ionic liquid is 1- butyl -3- methylimidazoles hydroxide, 1- ethyl-3-methylimidazoles hydroxide, 1-
At least one of butyl -3- methylimidazoles bicarbonate, 1- butyl -3- N-Methylimidazoleacetic salt.
Preferably, in step 1), the temperature being stirred to react is 0 DEG C~100 DEG C, and the time being stirred to react is 1h~15h；Into
One step is preferred, and in step 1), the temperature being stirred to react is 20 DEG C~30 DEG C, and the time being stirred to react is 4h~12h.
Preferably, in step 1), the time that water stirring is added is 5min~15min；The water of addition be deionized water, go from
The amount ratio of sub- water and graphite is (15~25) mL；1g.
Preferably, in step 1), the method for collecting sediment is to centrifuge to collect.
Preferably, in step 2), cleaning is specially to use deionized water washing sediment 2~5 times.
Preferably, in step 2), dry method is spray drying or freeze-drying.
Present disclosure is described in further detail below by way of specific embodiment.It is former used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1：
After 5g crystalline flake graphites and 10mL ionic liquid 1-butyl-3-methyl imidazolium hydroxide are mixed, in 25 DEG C of conditions
Under, after continuously stirring 4h, adds 100mL deionized waters and continue to stir 10min.
Mixture is centrifuged, and after agent 3 times is washed with deionized water, can be repeated after the aqueous solution drying of ionic liquid
It uses, sediment is after freeze-drying, you can obtains the graphene of embodiment 1.
Phenetic analysis is carried out to the graphene prepared by embodiment 1.Attached drawing 1 is the TEM of the graphene prepared by embodiment 1
Electron microscope.Attached drawing 2 is the Raman spectrogram of the graphene prepared by embodiment 1.
Embodiment 2：
After 5g crystalline flake graphites and 20mL ionic liquid 1- ethyl-3-methylimidazole hydroxide are mixed, in 25 DEG C of conditions
Under, after continuously stirring 4h, adds 100mL deionized waters and continue to stir 10min.
Mixture is centrifuged, and after agent 4 times is washed with deionized water, can be repeated after the aqueous solution drying of ionic liquid
It uses, sediment is after freeze-drying, you can obtains the graphene of embodiment 2.
Embodiment 3：
After 5g crystalline flake graphites and 50mL ionic liquid 1-butyl-3-methyl imidazolium bicarbonates are mixed, in 25 DEG C of conditions
Under, after continuously stirring 12h, adds 100mL deionized waters and continue to stir 10min.
Mixture is centrifuged, and after agent 5 times is washed with deionized water, can be repeated after the aqueous solution drying of ionic liquid
It uses, sediment is after freeze-drying, you can obtains the graphene of embodiment 3.
Embodiment 4：
After 5g crystalline flake graphites and 50mL ionic liquid 1-butyl-3-methyl imidazolium acetates are mixed, under the conditions of 25 DEG C,
After continuously stirring 12h, adds 100mL deionized waters and continue to stir 10min.
Mixture is centrifuged, and after agent 5 times is washed with deionized water, can be repeated after the aqueous solution drying of ionic liquid
It uses, sediment is after freeze-drying, you can obtains the graphene of embodiment 4.
Come as can be seen from the above embodiments, not only raw material come the method for prepare with scale graphene provided by the invention
Source is extensive, at low cost, and process route is simple, is conducive to the industrialization promotion and production of graphene.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and
Within principle, made by any modification, it is same replace, improve etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method that the direct stripping of ionic liquid prepares graphene, it is characterised in that：Include the following steps：
1) it after mixing graphite and ionic liquid, is stirred to react, adds water stirring, collect sediment；
2) dry by sediment undergoes washing, obtain graphene.
2. the method that the direct stripping of a kind of ionic liquid according to claim 1 prepares graphene, it is characterised in that：Step
1) in, the mass ratio of graphite and ionic liquid is 1：(1~10).
3. the method that the direct stripping of a kind of ionic liquid according to claim 2 prepares graphene, it is characterised in that：Step
1) in, graphite is at least one of crystalline flake graphite, artificial graphite, expanded graphite.
4. the method that the direct stripping of a kind of ionic liquid according to claim 2 prepares graphene, it is characterised in that：Step
1) in, ionic liquid is alkali ionic liquid.
5. the method that the direct stripping of a kind of ionic liquid according to claim 4 prepares graphene, it is characterised in that：Step
1) in, ionic liquid is 1- butyl -3- methylimidazoles hydroxide, 1- ethyl-3-methylimidazoles hydroxide, 1- butyl -3-
At least one of methylimidazole imidazole salts, 1- butyl -3- methylimidazoles bicarbonate, 1- butyl -3- N-Methylimidazoleacetic salt.
6. the method that the direct stripping of a kind of ionic liquid according to claim 1 prepares graphene, it is characterised in that：Step
1) in, the temperature being stirred to react is 0 DEG C~100 DEG C, and the time being stirred to react is 1h~15h.
7. the method that the direct stripping of a kind of ionic liquid according to claim 1 prepares graphene, it is characterised in that：Step
1) in, the time that water stirring is added is 5min~15min；The water of addition is deionized water, the amount ratio of deionized water and graphite
For (15~25) mL；1g.
8. the method that the direct stripping of a kind of ionic liquid according to claim 1 prepares graphene, it is characterised in that：Step
1) in, the method for collecting sediment is to centrifuge to collect.
9. the method that the direct stripping of a kind of ionic liquid according to claim 1 prepares graphene, it is characterised in that：Step
2) in, cleaning is specially to use deionized water washing sediment 2~5 times.
10. the method that the direct stripping of a kind of ionic liquid according to claim 1 prepares graphene, it is characterised in that：Step
It is rapid 2) in, dry method be spray drying or freeze-drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109052314A (en) * | 2018-09-17 | 2018-12-21 | 柯良节 | A method of removing multilayer two-dimension material |
| CN111285361A (en) * | 2020-04-14 | 2020-06-16 | 中北大学 | High-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene |
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| CN109052314A (en) * | 2018-09-17 | 2018-12-21 | 柯良节 | A method of removing multilayer two-dimension material |
| CN111285361A (en) * | 2020-04-14 | 2020-06-16 | 中北大学 | High-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene |
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| CN108314022B (en) | 2020-06-05 |
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