CN108383114A - The method of conjugate ion liquid up-stripping preparing graphite alkene - Google Patents
The method of conjugate ion liquid up-stripping preparing graphite alkene Download PDFInfo
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- CN108383114A CN108383114A CN201810347524.6A CN201810347524A CN108383114A CN 108383114 A CN108383114 A CN 108383114A CN 201810347524 A CN201810347524 A CN 201810347524A CN 108383114 A CN108383114 A CN 108383114A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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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
- C01B2204/04—Specific amount of layers or specific thickness
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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
- C01B2204/32—Size or surface area
Abstract
The present invention relates to a kind of methods of conjugate ion liquid up-stripping preparing graphite alkene, by graphite, after ionic liquid and conventional ionic liquid with the pi-conjugated structures of π react at 150~200 DEG C more than 60min, separation product is up to graphene film, wherein conventional ionic liquid is 1 butyl, 3 methylimidazole hexafluorophosphate, 1 hexyl, 3 methylimidazole hexafluorophosphate, 3 methylimidazole hexafluorophosphate of 1 ethyl, 3 methylimidazole hexafluorophosphate or 1 octyl, ionic liquid with the pi-conjugated structures of π is the conjugate ion liquid of the ring containing pyrene, conjugate ion liquid containing anthracene nucleus or naphthalene-ring containing conjugate ion liquid.The method of the conjugate ion liquid up-stripping preparing graphite alkene of the present invention, simple for process, of low cost, graphene good for the peeling effect of graphite and obtained has the advantages that size is big, the number of plies is few and defect is few, great application prospect.
Description
Technical field
The invention belongs to field of preparation of graphene, are related to a kind of side of conjugate ion liquid up-stripping preparing graphite alkene
Method.
Background technology
Graphene is because its excellent performance is widely studied and applied, and there are many preparation method, such as mechanical grinding
Grind stripping method, chemistry redox method, chemical vapor infiltration, silicon carbide pyrolysismethod and liquid phase stripping method etc., preparation side
Method has tended to be ripe, however all there is certain disadvantages for these methods.The efficiency of mechanical lapping stripping method is very low, it is difficult to from production
The graphene of single layer or few layer is filtered out in object, and the size of the graphene sheet layer of gained is difficult to control, it also can not be a large amount of
Prepare large-sized graphene, the shortcomings that chemical vapor infiltration is that the condition of reaction is harsher, and the cost of production compares
Height, the number of plies and thickness of graphene are uncontrolled, and the disadvantage of chemistry redox method is that the raw material used in it is graphite oxide, this
It can contain there are many hydroxyl and carboxyl functional group, the fault of construction caused by oxidation can not be restored completely, this can influence graphite
The electric conductivity of alkene contains a large amount of fault of construction so as to cause obtained redox graphene.Silicon carbide pyrolysismethod is main
It is influenced by silicon carbide substrate, usually the uneven thickness one of prepared graphene, while the quality of graphene is by the shadow of substrate
It rings.
In recent years, relatively low, less pollution and better simply liquid phase stripping method, scientists were operated to study to consume energy
Natural graphite flakes can be distributed to certain specific solvents or table by the trial for having done many effort using liquid phase stripping method
In the activating agent of face, directly graphite flake layer is removed by the effect of external force, obtains the dispersion liquid of graphene in a solvent, this
Kind method can keep graphene than more complete pattern and excellent performance.Liquid phase stripping method uses cheap cheap natural
For graphite flake as raw material, technological process is very easy, and operating process is also very simple, preparation to graphene and should possess very
Important impetus.But there is also many shortcomings for liquid phase stripping method：For example obtained graphene dispersing solution is dense
Degree is still very low, and graphene obtained needs to be further improved in the number of plies and size, for Jie removed
Matter either has toxicity or boiling point is very high is not easily separate, and adjuvant or surfactant are not easy from finally obtained graphene
Separated in product, prolonged grinding or ultrasonic degradation be easy to reduce the size of graphite ene product to stone
The structure of black alkene causes different degrees of destruction.
Therefore, a kind of easy to operate, green non-pollution, free from admixture are developed and removes the high liquid phase stripping graphite of quality and prepares
The great realistic meaning of method of graphene.
Invention content
The purpose of the present invention is overcome the above prior art high energy consumption, stripping it is of poor quality, complicated for operation, have pollution etc. lack
It falls into, a kind of easy to operate, green non-pollution, free from admixture and the side for removing the high liquid phase stripping preparing graphite alkene of quality is provided
Method.
In order to achieve the above objectives, the technical solution adopted by the present invention is as follows：
The method of conjugate ion liquid up-stripping preparing graphite alkene, graphite, the ionic liquid with the pi-conjugated structures of π-
After body and conventional ionic liquid react at 150~200 DEG C, separation product is up to graphene film.Reaction temperature is set as 150~
200 DEG C are because of the excessively high boiling point that can reach ionic liquid of reaction temperature；Reaction temperature is too low to lead to stripping process slowly very
It can not extremely remove.
As preferred technical solution：
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, it is described that there is the pi-conjugated knots of π-
The ionic liquid of structure is conjugate ion liquid, the conjugate ion liquid containing anthracene nucleus or the naphthalene-ring containing conjugate ion liquid of the ring containing pyrene
Body；The conventional ionic liquid be 1- butyl -3- methylimidazoles hexafluorophosphate, 1- hexyl -3- methylimidazoles hexafluorophosphate,
- 3 methylimidazole hexafluorophosphate of 1- ethyls or 1- octyl -3- methylimidazole hexafluorophosphates.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the conjugation of the ring containing pyrene from
Sub- liquid is specially 1- methyl -3- pyrene methyl-imidazoles hexafluorophosphates；The conjugate ion liquid containing anthracene nucleus is specially 1- first
Base -3- (9- anthracenes methyl) limidazolium hexafluorophosphate；The naphthalene-ring containing conjugate ion liquid is specially 1- (2- menaphthyls) -3 first
Base limidazolium hexafluorophosphate.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the graphite have π-π total
The ionic liquid of yoke structure and the mass ratio of conventional ionic liquid are 1:1:690~920.Graphite with the pi-conjugated structures of π-
Ionic liquid mass ratio is 1:1, with the pi-conjugated structures of π-ionic liquid addition it is excessive or it is very few can influence gained graphite
The yield of alkene；Conventional ionic liquid addition is very few to cause graphite that can not be completely dispersed, and addition can excessively cause to waste.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the separation refer to successively into
Row crushing, cleaning, centrifuge washing, drying process, separation of the invention are not limited to that other can be isolated by product
The means of graphene film also can be suitably used for the present invention.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the reaction are to be placed in microwave
It is reacted in reactor, reaction time ＞ 60min, rotating speed>300r/min, the microwave reactor power>500W.When reaction
Between too short peeling effect it is poor.Reaction is in power>500W, rotating speed>It is carried out in the microwave reactor of 300r/min, improves reaction
The uniformity of system, improves reaction rate to a certain extent.Reaction time is too short, and peeling effect is bad.
The method of the conjugate ion liquid up-stripping preparing graphite alkene as described above, the crushing refer to
At least 30min is handled in cell pulverizer, the power of the cell pulverizer is 300~400W.The purpose of crushing is to entire
Mixed system forces an active force, further promotes stripping process, and part graphite is prevented to be not peeled off.Processing time it is too short or
Power is too low to be not achieved ideal effect, and processing time is long or the excessively high size that can destroy graphene film of power.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the cleaning refers in ultrasound
At least 30min, the power of the ultrasonic cleaning machine are handled in washer>100W.Cleaning is to reduce graphene and ionic liquid
Adhesive force between body, to make graphene preferably be separated with ionic liquid.Processing time is too short or power is crossed down to not
To the effect.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the centrifuge washing refers to elder generation
With dichloromethane or chloroform centrifuge washing 15min, then with ethyl alcohol centrifuge washing 5min, to remove a small amount of residual ion liquid
Body, centrifuge speed are 10000~12000rpm, and phenomenon is that black powder forms precipitation in bottom.The purpose of centrifuge washing is
The ionic liquid of graphite surface is removed, protection scope of the present invention is not limited in two kinds of dichloromethane, chloroform solvents, washes
Except organic solvent used has the characteristics of can dissolving each other with ionic liquid, wash time be also not limited to 15min and
5min, as long as ensureing that washing is abundant.
The method of conjugate ion liquid up-stripping preparing graphite alkene as described above, the drying are dry for vacuum
Dry, drying temperature is 70~80 DEG C, and drying time is 8~12h, vacuum degree>0.1MPa.It was being tested by being dried in vacuo to remove
Mixed moisture in journey.
Invention mechanism：
Graphite is that multi-layer graphene lamella compact reactor under the action of Van der Waals force is stacked together and formed, and is only destroyed
Van der Waals force could separate these graphene sheet layers.The surface tension of ionic liquid and the surface energy phase of graphite flake layer
Match, therefore ionic liquid can be with exfoliated graphite layer, this is that peel test is successfully crucial.Conventional ionic liquid and graphite flake layer
Between interaction mainly by cation-π interaction, π-π interactions are very weak, and conjugate ion liquid not only possesses sun
Ion-π interactions, due to the presence of pyrene ring, anthracene nucleus or naphthalene nucleus, possess the pi-conjugated planes of larger π-, therefore and graphite flake layer
π-π interaction it is clearly more powerful, finally under the collective effect of π-π and cation-π, graphite flake layer is gradually lifted off of, most
After obtained graphene film, which not only has the characteristics that the graphene that lamella is few, size is big, defect is few but also micro
The electric conductivity that polyetherimide can be significantly improved, makes it have broad application prospects in electronic field.
Advantageous effect：
(1) method of conjugate ion liquid up-stripping preparing graphite alkene of the invention, used ionic liquid
By chemical reaction be synthetically prepared, raw materials used relatively cheap, operating process is fairly simple, ionic liquid it is nontoxic and
It can recycle, more environmentally-friendly, safety and economy；
(2) method of conjugate ion liquid up-stripping preparing graphite alkene of the invention, it is simple for process, at low cost
It is honest and clean, and graphene obtained has the advantages that size is big, the number of plies is few and defect is few, great application prospect；
(3) method of conjugate ion liquid up-stripping preparing graphite alkene of the invention, graphene obtained can
It is dispersed in high polymer such as polyetherimide without reuniting.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- methyl -3- pyrene methyl-imidazoles hexafluorophosphates and 1- butyl -3- methylimidazole hexafluorophosphates
By 1:1:800 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 175 DEG C, and the reaction time is
The rotating speed of 90min, microwave reactor are 500r/min, power 700W；
(2) 40min, wherein cell powder first are cleaned through being crushed in 40min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 350W, and the power of ultrasonic cleaning machine is 150W, and dichloromethane centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 11000rpm, is finally the true of 0.2MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 75 DEG C, drying time 10h.
The yield of final graphene film obtained is 41.6wt%, and with 3 × 4 μm of large scale, thickness is 4nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 3~5 layers, ID/IG(size of the ratio has reacted graphite
The number of the fault of construction of alkene, ratio is bigger, and defect is more) ratio size be only 0.02, fault of construction is considerably less, organic
Preferably, graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are in wavelength 270nm for dispersibility in solvent
The ultraviolet absorptivity at place is about 1.00, and the micro graphene film can significantly improve the electric conductivity of PEI, by the graphene film with
PEI is compound, and when graphene content is 0.75wt%, the resistivity of composite material has reached 1.67 × 105Ω·cm。
Comparative example 1
A kind of method of conventional ionic liquid up-stripping preparing graphite alkene, preparation process are basic with embodiment 1
It is identical, the difference is that, it is by graphite and 1- butyl -3- methylimidazole hexafluorophosphates in step (1) by 1:800 quality
It is reacted than being placed in microwave reactor, the yield of final obtained graphene film is 26.9wt%, big with 2 × 3 μm
Size, thickness are 6nm or so, are calculated in 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 6~8 layers, ID/IG's
Ratio is 0.06, and dispersibility in organic solvent is general, and the graphene-DMF dispersion liquids of 1.00mg/mL are in wavelength 270nm
The ultraviolet absorptivity at place is about 1.00, which can improve the electric conductivity of PEI, and the graphene film is compound with PEI, works as stone
When black alkene content is 8.00wt%, the resistivity of composite material has reached 1.23 × 105Ω·cm.By embodiment 1 and comparative example 1
It compares as can be seen that compared to graphene film obtained in comparative example 1, the size bigger of graphene film produced by the present invention,
The number of plies is less, defect is less, good dispersion in organic solvent, which improves more preferably the electric conductivity of PEI.It utilizes
The peeling effect for the graphene film that the conjugate ion liquid up-stripping graphite of the present invention is prepared will be substantially better than existing skill
Art, the present invention achieve significant progress compared with the prior art.
Embodiment 2
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- methyl -3- (9- anthracenes methyl) limidazolium hexafluorophosphates and 1- butyl -3- methylimidazole hexafluoro phosphorus
Hydrochlorate presses 1:1:800 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 175 DEG C, and the reaction time is
The rotating speed of 90min, microwave reactor are 500r/min, power 700W；
(2) 40min, wherein cell powder first are cleaned through being crushed in 40min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 350W, and the power of ultrasonic cleaning machine is 150W, and dichloromethane centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 11000rpm, is finally the true of 0.2MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 75 DEG C, drying time 10h.
The yield of final graphene film obtained is 33.7wt%, and with 2 × 4 μm of large scale, thickness is 5nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 4~6 layers, ID/IGRatio size be only 0.03, structure
Defect is considerably less, and graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are ultraviolet at wavelength 270nm
Absorbance is about 0.75, and preferably, the micro graphene film can significantly improve the conduction of PEI to dispersibility in organic solvent
Property, graphene and PEI is compound, and when graphene content is 2.00wt%, the resistivity of composite material has reached 1.38 × 105
Ω·cm。
Embodiment 2 and comparative example 1 are compared and can be seen that compared to graphene film obtained in comparative example 1, the present invention
Size bigger, the number of plies of graphene film obtained are less, defect is less, good dispersion in organic solvent, the graphene film
The electric conductivity of PEI is improved more preferably.The graphene film being prepared using the conjugate ion liquid up-stripping graphite of the present invention
Peeling effect to be substantially better than the prior art, the present invention achieves significant progress compared with the prior art.
Embodiment 3
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- methyl -3- pyrene methyl-imidazoles hexafluorophosphates and 1- hexyl -3- methylimidazole hexafluorophosphates
By 1:1:690 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 150 DEG C, and the reaction time is
The rotating speed of 65min, microwave reactor are 320r/min, power 550W；
(2) 30min, wherein cell powder first are cleaned through being crushed in 30min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 300W, and the power of ultrasonic cleaning machine is 110W, and chloroform centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 10000rpm, is finally the true of 0.11MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 70 DEG C, drying time 8h.
The yield of final graphene film obtained is 35.0wt%, and with 2 × 4 μm of large scale, thickness is 4nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 3~5 layers, ID/IGRatio size be only 0.02, structure
Defect is considerably less, and graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are ultraviolet at wavelength 270nm
Absorbance is about 0.80, and preferably, the micro graphene film can significantly improve the conduction of PEI to dispersibility in organic solvent
Property, graphene and PEI is compound, and when graphene content is 2.00wt%, the resistivity of composite material has reached 1.28 × 105
Ω·cm。
Embodiment 4
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- methyl -3- pyrene methyl-imidazoles hexafluorophosphates and 1- ethyl-3-methylimidazole hexafluorophosphates
By 1:1:920 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 200 DEG C, and the reaction time is
The rotating speed of 120min, microwave reactor are 700r/min, power 700W；
(2) 60min, wherein cell powder first are cleaned through being crushed in 60min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 400W, and the power of ultrasonic cleaning machine is 200W, and dichloromethane centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 12000rpm, is finally the true of 0.5MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 80 DEG C, drying time 12h.
The yield of final graphene film obtained is 35.7wt%, and with 3 × 4 μm of large scale, thickness is 5nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 4~6 layers, ID/IGRatio size be only 0.025, knot
Structure defect is considerably less, the purple of graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL at wavelength 270nm
Outer absorbance is about 0.95, and preferably, the micro graphene film can significantly improve leading for PEI to dispersibility in organic solvent
Electrically, graphene is compound with PEI, when graphene content is 1.00wt%, the resistivity of composite material reached 1.38 ×
105Ω·cm。
Embodiment 5
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- methyl -3- (9- anthracenes methyl) limidazolium hexafluorophosphates and 1- octyl -3- methylimidazole hexafluoro phosphorus
Hydrochlorate presses 1:1:720 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 160 DEG C, and the reaction time is
The rotating speed of 70min, microwave reactor are 400r/min, power 600W；
(2) 40min, wherein cell powder first are cleaned through being crushed in 40min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 400W, and the power of ultrasonic cleaning machine is 200W, and dichloromethane centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 10500rpm, is finally the true of 0.15MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 75 DEG C, drying time 9h.
The yield of final graphene film obtained is 39.7wt%, and with 2 × 4 μm of large scale, thickness is 4nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 3~5 layers, ID/IGRatio size be only 0.02, structure
Defect is considerably less, and graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are ultraviolet at wavelength 270nm
Absorbance is about 0.10, and preferably, the micro graphene film can significantly improve the conduction of PEI to dispersibility in organic solvent
Property, graphene and PEI is compound, and when graphene content is 2.00wt%, the resistivity of composite material has reached 1.23 × 105
Ω·cm。
Embodiment 6
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- methyl -3- (9- anthracenes methyl) limidazolium hexafluorophosphates and 1- ethyl-3-methylimidazole hexafluoro phosphorus
Hydrochlorate presses 1:1:750 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 160 DEG C, and the reaction time is
The rotating speed of 90min, microwave reactor are 400r/min, power 600W；
(2) 45min, wherein cell powder first are cleaned through being crushed in 45min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 400W, and the power of ultrasonic cleaning machine is 200W, and chloroform centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 10800rpm, is finally the true of 0.18MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 78C, drying time 10h.
The yield of final graphene film obtained is 40.7wt%, and with 3 × 4 μm of large scale, thickness is 5nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 4~6 layers, ID/IGRatio size be only 0.02, structure
Defect is considerably less, and graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are ultraviolet at wavelength 270nm
Absorbance is about 0.89, and preferably, the micro graphene film can significantly improve the conduction of PEI to dispersibility in organic solvent
Property, graphene and PEI is compound, and when graphene content is 2.00wt%, the resistivity of composite material has reached 1.68 × 105
Ω·cm。
Embodiment 7
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- (2- menaphthyls) -3- methylimidazoles hexafluorophosphates and 1- hexyl -3- methylimidazole hexafluoro phosphorus
Hydrochlorate presses 1:1:850 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 170 DEG C, and the reaction time is
The rotating speed of 100min, microwave reactor are 500r/min, power 600W；
(2) 50min, wherein cell powder first are cleaned through being crushed in 50min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 400W, and the power of ultrasonic cleaning machine is 300W, and chloroform centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 12000rpm, is in vacuum degree finally>0.1MPa's is true
Graphene film is made under empty condition after drying, wherein drying temperature is 76 DEG C, drying time 11h.
The yield of final graphene film obtained is 38.7wt%, and with 3 × 4 μm of large scale, thickness is 5nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 4~6 layers, ID/IGRatio size be only 0.2, structure
Defect is considerably less, and graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are ultraviolet at wavelength 270nm
Absorbance is about 0.92, and preferably, the micro graphene film can significantly improve the conduction of PEI to dispersibility in organic solvent
Property, graphene and PEI is compound, and when graphene content is 2.00wt%, the resistivity of composite material has reached 1.52 × 105
Ω·cm。
Embodiment 8
A kind of method of conjugate ion liquid up-stripping preparing graphite alkene, it is specific as follows：
(1) by graphite, 1- (2- menaphthyls) -3- methylimidazoles hexafluorophosphates and 1- octyl -3- methylimidazole hexafluoro phosphorus
Hydrochlorate presses 1:1:900 mass ratio, which is placed in microwave reactor, to be reacted, and wherein reaction temperature is 180 DEG C, and the reaction time is
The rotating speed of 110min, microwave reactor are 450r/min, power 700W；
(2) 55min, wherein cell powder first are cleaned through being crushed in 55min and ultrasonic cleaning machine in cell pulverizer after reacting
The power of millstone is 300W, and the power of ultrasonic cleaning machine is 200W, and dichloromethane centrifuge washing is then first used in centrifuge
15min, then with ethyl alcohol centrifuge washing 5min, wherein centrifuge speed is 10000rpm, is finally the true of 0.2MPa in vacuum degree
Graphene film is made under empty condition after drying, wherein drying temperature is 80 DEG C, drying time 12h.
The yield of final graphene film obtained is 39.2wt%, and with 2 × 4 μm of large scale, thickness is 4nm or so,
It is calculated for 0.8~1.2nm according to single-layer graphene thickness, the number of plies is 3~5 layers, ID/IGRatio size be only 0.03, structure
Defect is considerably less, and graphene-DMF (n,N-Dimethylformamide) dispersion liquids of 1.00mg/mL are ultraviolet at wavelength 270nm
Absorbance is about 0.79, and preferably, the micro graphene film can significantly improve the conduction of PEI to dispersibility in organic solvent
Property, graphene and PEI is compound, and when graphene content is 3.00wt%, the resistivity of composite material has reached 1.58 × 105
Ω·cm。
Claims (10)
1. the method for conjugate ion liquid up-stripping preparing graphite alkene, it is characterized in that：Graphite has the pi-conjugated structures of π-
Ionic liquid and after conventional ionic liquid reacts at 150~200 DEG C, separation product is up to graphene film.
2. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 1, which is characterized in that
The ionic liquid with the pi-conjugated structures of π-is the conjugate ion liquid of the ring containing pyrene, the conjugate ion liquid containing anthracene nucleus or contains
The conjugate ion liquid of naphthalene nucleus；The conventional ionic liquid is 1- butyl -3- methylimidazoles hexafluorophosphate, 1- hexyl -3- first
Base limidazolium hexafluorophosphate, -3 methylimidazole hexafluorophosphate of 1- ethyls or 1- octyl -3- methylimidazole hexafluorophosphates.
3. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 2, which is characterized in that
The conjugate ion liquid of the ring containing pyrene is specially 1- methyl -3- pyrene methyl-imidazoles hexafluorophosphates；The conjugation containing anthracene nucleus
Ionic liquid is specially 1- methyl -3- (9- anthracenes methyl) limidazolium hexafluorophosphate；The naphthalene-ring containing conjugate ion liquid is specific
For -3 methylimidazole hexafluorophosphates of 1- (2- menaphthyls).
4. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 1, which is characterized in that
The mass ratio of the graphite, the ionic liquid with the pi-conjugated structures of π-and conventional ionic liquid is 1:1:690~920.
5. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 1, which is characterized in that
The reaction is reacted to be placed in microwave reactor, reaction time ＞ 60min, rotating speed>300r/min, the microwave reaction
The power of device>500W.
6. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 1, which is characterized in that
It is described separation refer to crush, clean successively, centrifuge washing, drying process.
7. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 6, which is characterized in that
The crushing refers to that at least 30min is handled in cell pulverizer, and the power of the cell pulverizer is 300~400W.
8. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 6, which is characterized in that
The cleaning refers to that at least 30min is handled in ultrasonic cleaning machine, the power of the ultrasonic cleaning machine>100W.
9. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 6, which is characterized in that
The centrifuge washing refer to first use dichloromethane or chloroform centrifuge washing 15min, then use ethyl alcohol centrifuge washing 5min, centrifuge
Machine rotating speed is 10000~12000rpm.
10. the method for conjugate ion liquid up-stripping preparing graphite alkene according to claim 6, feature exist
In the drying is vacuum drying, and drying temperature is 70~80 DEG C, and drying time is 8~12h, vacuum degree>0.1MPa.
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| CN114023511A (en) * | 2021-11-11 | 2022-02-08 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
| CN115521653A (en) * | 2022-10-10 | 2022-12-27 | 深圳前海石墨烯产业有限公司 | Conjugated ionic liquid stripping modified graphene conductive agent, conductive electrode slice and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110950331A (en) * | 2019-12-02 | 2020-04-03 | 陕西科技大学 | Method for preparing fluorinated graphene dispersion liquid on large scale |
| CN113387348A (en) * | 2020-08-14 | 2021-09-14 | 中国科学院过程工程研究所 | Method for preparing graphene by using composite ionic liquid |
| CN113387348B (en) * | 2020-08-14 | 2022-07-19 | 中国科学院过程工程研究所 | Method for preparing graphene by using composite ionic liquid |
| CN114023511A (en) * | 2021-11-11 | 2022-02-08 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
| CN114023511B (en) * | 2021-11-11 | 2023-10-31 | 中国有色桂林矿产地质研究院有限公司 | Method for preparing high-temperature electronic paste based on organic phosphorus salt |
| CN115521653A (en) * | 2022-10-10 | 2022-12-27 | 深圳前海石墨烯产业有限公司 | Conjugated ionic liquid stripping modified graphene conductive agent, conductive electrode slice and preparation method thereof |
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