CN103626164B - The preparation method of Graphene - Google Patents
The preparation method of Graphene Download PDFInfo
- Publication number
- CN103626164B CN103626164B CN201210310132.5A CN201210310132A CN103626164B CN 103626164 B CN103626164 B CN 103626164B CN 201210310132 A CN201210310132 A CN 201210310132A CN 103626164 B CN103626164 B CN 103626164B
- Authority
- CN
- China
- Prior art keywords
- graphene
- chloride
- graphite
- intercalated graphite
- ionic liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The preparation method of a kind of Graphene, including following five steps: step one: graphite and chloride intercalator are mixed to get reactant, are reacted by described reactant and obtain intermediate product at temperature 460 DEG C ~ 550 DEG C；Step 2: described intermediate product is cleaned, obtains pure intercalated graphite after drying；Step 3: form intercalated graphite and the mixture of ionic liquid after intercalated graphite, ionic liquid mixing, the mixture of described intercalated graphite Yu ionic liquid is placed in stationary magnetic field, be centrifuged processing；Step 4: the precipitate obtained after described centrifugal treating is carried out, obtains Graphene；Step 6: vacuum drying.The preparation method of above-mentioned Graphene is simple to operate, and production efficiency is higher, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to the synthesis field of material, particularly to the preparation method of a kind of Graphene.
Background technology
Graphene is peace moral strong K sea nurse (Andre K.Geim) etc. of Univ Manchester UK in 2004
A kind of Two-dimensional Carbon atomic crystal found, and obtain physics Nobel Prize in 2010, re-initiation material with carbon element grinds
Study carefully upsurge.Owing to structure and the photoelectric property of its uniqueness become material with carbon element, nanotechnology, condensed state thing
The study hotspot in the fields such as reason and functional material, has attracted many scientific workers.Graphene has excellent
Conduction, heat conductivility and low thermal coefficient of expansion, can be used for electrode material, composite etc..Current system
Preparation Method has graphite oxide reducing process, but this method can cause the destruction of graphene-structured；Also make
Prepare Graphene by pyrolytic carbon source, but this method production efficiency is relatively low.
Summary of the invention
In consideration of it, the method being necessary to provide a kind of simple to operate and that efficiency is higher Graphene.
The preparation method of a kind of Graphene, comprises the steps:
Step one: graphite and chloride intercalator are mixed to get reactant, by described reactant in temperature
At 460 DEG C ~ 550 DEG C, reaction obtains intermediate product；
Step 2: described intermediate product is cleaned, obtains pure intercalated graphite after drying；
Step 3: form intercalated graphite and the mixture of ionic liquid after intercalated graphite, ionic liquid mixing,
The mixture of described intercalated graphite Yu ionic liquid is placed in stationary magnetic field, is centrifuged processing；
Step 4: the precipitate obtained after described centrifugal treating is carried out, obtains Graphene；
Step 5: vacuum drying.
Wherein in an embodiment, described graphite is natural flake graphite or Delanium.
Wherein in an embodiment, described chloride intercalator selected from iron chloride, Nickel dichloride., copper chloride,
At least one in cobaltous chloride, potassium chloride, magnesium chloride, lead chloride, zinc chloride, calcium chloride and barium chloride.
Wherein in an embodiment, described graphite with the mass ratio of described chloride intercalator is
1: 0.8 ~ 1: 1.2, the time of described insulation reaction is 2 hours ~ 6 hours.
Wherein in an embodiment, the magnetic field intensity of described stationary magnetic field is 0.01 tesla～1 tesla.
Wherein in an embodiment, described centrifugal treating condition is: rotating speed 1000 revs/min～10000 turns
/ minute, process 10 minutes time～100 minutes.Wherein in an embodiment, described cleaning comprises organic
Solvent clean, described organic solvent is N-Methyl pyrrolidone or dimethylformamide.An enforcement wherein
In example, described ionic liquid is selected from 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole trifluoro
Methylsulfonimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-
Ethyl-3-methylimidazole fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-first
Base imidazoles two cyaniding nitrogen, 1-ethyl-3,5-methylimidazole fluoroform sulfimide, 1,3-diethyl-4-methyl miaow
At least one of azoles fluoroform sulfimide and 1,3-diethyl-5-Methylimidazole. fluoroform sulfimide.
Wherein in an embodiment, described intercalated graphite with the mass volume ratio of ionic liquid is
1g:10mL~100mL。
Wherein in an embodiment, described vacuum drying condition is: temperature 60 C ~ 100 DEG C, response time
10 hours ~ 20 hours.
The preparation method of above-mentioned Graphene, uses intercalator and graphite at high temperature to react preparation intercalated graphite,
And intercalated graphite is scattered in ionic liquid, under magnetic field with centrifugal action, quickly Graphene is prepared in stripping,
Simple to operate, production efficiency is higher, it is easy to accomplish industrialization.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of the Graphene of an embodiment；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the Graphene of embodiment 1 preparation.
Detailed description of the invention
Mainly in combination with drawings and the specific embodiments, the preparation method of Graphene is made further details of theory below
Bright.
As it is shown in figure 1, the preparation method of the Graphene of an embodiment, comprise the steps:
Step S110: graphite and chloride intercalator are mixed to get reactant, by reactant in temperature 460 DEG C
At ~ 550 DEG C, reaction obtains intermediate product.
Wherein, chloride intercalator is selected from iron chloride, Nickel dichloride., copper chloride, cobaltous chloride, potassium chloride, chlorine
Change at least one in magnesium, lead chloride, zinc chloride, calcium chloride and barium chloride.
Under the high temperature of 460 DEG C ~ 550 DEG C, these several chloride intercalators easily form fused salt and quickly insert
Layer reaction, improves preparation efficiency.
Wherein, graphite is graphite commonly used in the art, preferably natural flake graphite or Delanium.
The mass ratio of graphite and intercalator is preferably 1:0.8 ~ 1:1.2.Graphite and chloride intercalator are at 460 DEG C
At ~ 550 DEG C, reaction a period of time obtains intermediate product.The time of reaction is preferably 2 hours ~ 6 hours.Middle
Product contains intercalated graphite.
Step S120: intermediate product is cleaned, obtains pure intercalated graphite after drying.
The intermediate product that step S110 obtains contains intercalated graphite.In order to obtain pure intercalated graphite, in inciting somebody to action
Between product filter after, clean filtering residue with deionized water, and be dried, obtain that be dried, pure intercalated graphite.
The condition being dried is, under vacuum, is dried 4 hours ~ 6 hours at 80 DEG C ~ 100 DEG C.
Step S130: form intercalated graphite and the mixing of ionic liquid after intercalated graphite, ionic liquid mixing
Thing, is placed in the mixture of intercalated graphite Yu ionic liquid in stationary magnetic field, is centrifuged processing.
Wherein, stationary magnetic field is that magnetic field intensity and direction keep constant magnetic field to be referred to as stationary magnetic field or Constant charge soil.
Preferably, the magnetic field intensity of stationary magnetic field is 0.01 tesla (T)～1 tesla (T).Centrifugal place
The condition of reason under rotating speed is 1000 revs/min～10000 revs/min, be centrifuged processing 10 minutes～
100 minutes.
Carrying out high speed centrifugation with 1000 revs/min～10000 revs/min in stationary magnetic field is to make intercalation
Ion in graphite is reached peeling effect by Lorentz force, and negative ions Impact direction forms stripping mutually on the contrary
Intercalated graphite is made to peel off into Graphene from power.
Wherein, ionic liquid is selected from 1-ethyl-3-methylimidazole Tetrafluoroboric acid (EtMeImBF4), 1-ethyl-3-
Methylimidazole. fluoroform sulfimide (EtMeImN (CF3SO2)2), 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid
(EtMeImCF3SO3), 1-ethyl-3-methylimidazole trifluoroacetic acid (EtMeImCF3CO3), 1-ethyl-3-
Methylimidazole. fluoroform sulphonyl carbon (EtMeImC (CF3SO2)3), 1-ethyl-3-methylimidazole five acetyl fluoride imines
(EtMeImN (C2F5SO2)2), 1-ethyl-3-methylimidazole two cyaniding nitrogen (EtMeImN (CN)2), 1-ethyl
-3,5-methylimidazole fluoroform sulfimide (1-Et-3,5-Me2ImN(CF3SO2)2), 1,3-diethyl-4-first
Base imidazoles fluoroform sulfimide (1,3-Et2-4-MeImN(CF3SO2)2) and 1,3-diethyl-5-Methylimidazole.
Fluoroform sulfimide (1,3-Et2-5-MeImN(CF3SO2)2At least one in).
Intercalated graphite is scattered in ionic liquid to be easy to peel off, and the Graphene obtained after stripping is also scattered in ion
In liquid.It is prevented from Graphene with ionic liquid as dispersion liquid to reunite, thus improves the productivity of Graphene.
The quality of intercalated graphite is 1g:10mL ~ 100mL with the ratio of the volume of ionic liquid, so that intercalated graphite and stripping
It is well-dispersed in ionic liquid from the graphite obtained, improves the efficiency and the productivity of Graphene peeled off.
Will not be induced one in stripping process impurity, is filtrated to get filtrate, i.e. ionic liquid can reclaim and again
Utilize, advantageously reduce preparation cost.
Step S140: the precipitate obtained after centrifugal treating is carried out, obtains Graphene.
The precipitate obtained after step S 130 centrifugal treating is carried out, obtains pure Graphene.
Employing organic solvent is carried out.By precipitate organic solvent extraction filter 23 time ~ 5 times, then spend
Ionized water filters, until filtrate is detected without chloride ion with silver nitrate.
Organic solvent is preferably N-Methyl pyrrolidone (NMP) or dimethylformamide (DMF).
Step S150: vacuum drying.
Under vacuum, the precipitate after cleaning is dried 10 hours ~ 20 hours at 60 DEG C ~ 100 DEG C,
Obtain the Graphene being dried.
The preparation method of above-mentioned Graphene, uses chloride intercalator and graphite at high temperature reaction to prepare intercalation
Graphite, and intercalated graphite is scattered in ionic liquid, under magnetic field with centrifugal action, quickly stone is prepared in stripping
Ink alkene, simple to operate, production efficiency is higher, it is easy to accomplish industrialization.
It addition, the preparation method of above-mentioned Graphene, utilize ionic liquid to make solution, and make with centrifugal in magnetic field
Preparing Graphene under with, the Graphene obtained has good dispersibility, monolayer rate up to more than 60%, and
The number of plies concentrates between 1 ~ 5 layer.The preparation method raw material sources of above-mentioned Graphene are wide, the repeatable utilization of solvent,
Low cost.
It is below specific embodiment part:
Embodiment 1
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:0.8 in mass ratio by natural flake graphite and iron chloride, by natural
Crystalline flake graphite and iron chloride are placed in sealed silica envelope, are warming up to 460 DEG C, insulation reaction 2 hours, reaction knot
It is cooled to room temperature after bundle, obtains intercalated graphite.After intercalated graphite is cleaned with deionized water, then it is vacuum dried
Case is dried 6 hours in 80 DEG C, obtains pure intercalated graphite.
(2) it is 1g:10ml according to mass volume ratio, intercalated graphite is joined equipped with EtMeImBF4Ion
In the container of liquid, take the mixture of 1L intercalated graphite and ionic liquid join high speed that capacity is 2L from
Build in scheming, add that at centrifuge top base two ends magnetic field intensity is the stationary magnetic field of 1T, startup magnetic field,
Centrifuge, allows centrifuge peel off intercalated graphite 10 minutes with the centrifugation of 1000 revs/min, will be centrifugal
To precipitate N-Methyl pyrrolidone (NMP) filter 5 times, then filter until filtrate with deionized water
Use AgNO3Detection is without chloride ion；Filtering residue after cleaning is put in vacuum drying oven at 60 DEG C that to be dried 20 little
Time, obtain the Graphene of the present embodiment.
What Fig. 2 represented is the scanning electron microscope (SEM) photograph (SEM) of Graphene prepared by the present embodiment.From Fig. 2 permissible
Learning, the thickness of the lamella of Graphene prepared by the present embodiment is about 0.5 nanometer ~ 2 nanometer, and graphene film
Layer is relatively concentrated, and peeling effect is good.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 2
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:0.9 in mass ratio by Delanium and copper chloride, by Delanium
Being placed in sealed silica envelope with iron chloride, be warming up to 500 DEG C, insulation reaction 3 hours, reaction cools down after terminating
To room temperature, obtain intercalated graphite.After intercalated graphite is cleaned with deionized water, then in 90 DEG C in vacuum drying oven
It is dried 5 hours, obtains pure intercalated graphite.
(2) it is 1g:100ml according to mass volume ratio, intercalated graphite is joined equipped with ionic liquid mixed liquor
Container in, ionic liquid mixed liquor is EtMeImBF4With EtMeImN (CF3SO2)2Mixed liquor,
EtMeImBF4With EtMeImN (CF3SO2)2Volume ratio be 1:1, EtMeImBF4With
EtMeImN(CF3SO2)2Volume sum be 100ml.Take the 1L intercalated graphite mixed liquor with ionic liquid
Mixture joins and builds in the high speed centrifuge that capacity is 2L, at centrifuge top base two ends plus magnetic field
Intensity is the stationary magnetic field of 0.5T, starts magnetic field, centrifuge, allows centrifuge with the speed of 2000 revs/min
Centrifugal stripping intercalated graphite 50 minutes, the precipitate dimethylformamide (DMF) that will centrifugal obtain filters
3 times, then filter until filtrate AgNO with deionized water3Detection is without chloride ion；Filtering residue after cleaning is put
It is dried 10 hours at 80 DEG C in vacuum drying oven, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 3
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:1.2 in mass ratio by natural flake graphite and Nickel dichloride., by natural
Crystalline flake graphite and Nickel dichloride. are placed in sealed silica envelope, are warming up to 480 DEG C, insulation reaction 6 hours, reaction knot
It is cooled to room temperature after bundle, obtains intercalated graphite.After intercalated graphite is cleaned with deionized water, then it is vacuum dried
Case is dried 4 hours in 100 DEG C, obtains pure intercalated graphite.
(2) it is 1g:50ml according to mass volume ratio, intercalated graphite is joined equipped with ionic liquid mixed liquor
Container in, ionic liquid mixed liquor is EtMeImCF3CO3、EtMeImBF4And EtMeImCF3SO3
Mixed liquor, EtMeImCF3CO3、EtMeImBF4And EtMeImCF3SO3Volume ratio be 1:1:2,
EtMeImCF3CO3、EtMeImBF4And EtMeImCF3SO3Volume sum be 50ml.Take 1L intercalation
The mixture of graphite and the mixed liquor of ionic liquid joins to be built in the high speed centrifuge that capacity is 2L, from
Scheming top base two ends plus magnetic field intensity be the stationary magnetic field of 0.1T, start magnetic field, centrifuge, allow from
Scheming peels off intercalated graphite 30 minutes with the centrifugation of 5000 revs/min, is precipitated thing N-by centrifugal
Methyl pyrrolidone (NMP) filter 23 time, then filter until filtrate AgNO with deionized water3Detection nothing
Chloride ion；Filtering residue after cleaning is put in vacuum drying oven and is dried 15 hours at 100 DEG C, obtains this enforcement
The Graphene of example.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 4
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:1.0 in mass ratio by Delanium and cobaltous chloride, by Delanium
Being placed in sealed silica envelope with cobaltous chloride, be warming up to 550 DEG C, insulation reaction 4 hours, reaction cools down after terminating
To room temperature, obtain intercalated graphite.After intercalated graphite is cleaned with deionized water, then in 90 DEG C in vacuum drying oven
It is dried 4.5 hours, obtains pure intercalated graphite.
(2) it is 1g:20ml according to mass volume ratio, intercalated graphite is joined equipped with EtMeImCF3CO3
In the container of ionic liquid, the mixture taking 1L intercalated graphite and ionic liquid joins the height that capacity is 2L
Build in speed centrifuge, add that at centrifuge top base two ends magnetic field intensity is the stationary magnetic field of 0.05T, open
Moving field, centrifuge, allow centrifuge peel off intercalated graphite 10 minutes with the centrifugation of 8000 revs/min,
By centrifugal precipitate dimethylformamide (DMF) filter 23 obtained, then filter straight with deionized water
To filtrate AgNO3Detection is without chloride ion；Filtering residue after cleaning is put in vacuum drying oven and is dried at 90 DEG C
12 hours, obtain the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 5
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:1.1 in mass ratio by natural flake graphite and potassium chloride, by natural
Crystalline flake graphite and potassium chloride are placed in sealed silica envelope, are warming up to 520 DEG C, insulation reaction 5 hours, reaction knot
It is cooled to room temperature after bundle, obtains intercalated graphite.After intercalated graphite is cleaned with deionized water, then it is vacuum dried
Case is dried 5.5 hours in 85 DEG C, obtains pure intercalated graphite.
(2) it is 1g:80ml according to mass volume ratio, intercalated graphite is joined equipped with EtMeImC (CF3SO2)3
In the container of ionic liquid, the mixture taking 1L intercalated graphite and ionic liquid joins the height that capacity is 2L
Build in speed centrifuge, add that at centrifuge top base two ends magnetic field intensity is the stationary magnetic field of 0.01T, open
Moving field, centrifuge, allow centrifuge peel off intercalated graphite 20 minutes with the centrifugation of 10000 revs/min,
The centrifugal precipitate N-Methyl pyrrolidone (NMP) obtained is filtered 4 times, then filters with deionized water straight
To filtrate AgNO3Detection is without chloride ion；Filtering residue after cleaning is put in vacuum drying oven and is dried at 70 DEG C
18 hours, obtain the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 6
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:0.8 in mass ratio by Delanium and sodium chloride, by Delanium
Being placed in sealed silica envelope with sodium chloride, be warming up to 530 DEG C, insulation reaction 2 hours, reaction cools down after terminating
To room temperature, obtain intercalated graphite.After intercalated graphite is cleaned with deionized water, then in 95 DEG C in vacuum drying oven
It is dried 6 hours, obtains pure intercalated graphite.
(2) be 1g:60ml according to mass volume ratio, intercalated graphite is joined equipped with
EtMeImN(C2F5SO2)2In the container of ionic liquid, the mixture taking 1L intercalated graphite and ionic liquid adds
Enter and build in the high speed centrifuge that capacity is 2L, at centrifuge top base two ends plus magnetic field intensity be
The stationary magnetic field of 0.2T, starts magnetic field, centrifuge, allows centrifuge peel off with the centrifugation of 2000 revs/min
Intercalated graphite 40 minutes, filters the centrifugal precipitate dimethylformamide (DMF) obtained 4 times, then
Filter until filtrate AgNO with deionized water3Detection is without chloride ion；Filtering residue after cleaning is put into vacuum and does
It is dried 20 hours at 60 DEG C in dry case, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 7
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:1.1 in mass ratio by natural flake graphite and magnesium chloride, by natural
Crystalline flake graphite and magnesium chloride are placed in sealed silica envelope, are warming up to 490 DEG C, insulation reaction 3 hours, reaction knot
It is cooled to room temperature after bundle, obtains intercalated graphite.After intercalated graphite is cleaned with deionized water, then it is vacuum dried
Case is dried 3 hours in 90 DEG C, obtains pure intercalated graphite.
(2) it is 1g:40ml according to mass volume ratio, intercalated graphite is joined equipped with EtMeImN (CN)2
In the container of ionic liquid, the mixture taking 1L intercalated graphite and ionic liquid joins the height that capacity is 2L
Build in speed centrifuge, add that at centrifuge top base two ends magnetic field intensity is the stationary magnetic field of 0.4T, open
Moving field, centrifuge, allow centrifuge peel off intercalated graphite 60 minutes with the centrifugation of 2500 revs/min,
By centrifugal precipitate N-Methyl pyrrolidone (NMP) filter 23 obtained, then filter with deionized water
Until filtrate AgNO3Detection is without chloride ion；Filtering residue after cleaning is put in vacuum drying oven at 100 DEG C
It is dried 10 hours, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 8
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:1.0 in mass ratio by Delanium and lead chloride, by Delanium
Being placed in sealed silica envelope with lead chloride, be warming up to 540 DEG C, insulation reaction 6 hours, reaction cools down after terminating
To room temperature, obtain intercalated graphite.After intercalated graphite is cleaned with deionized water, then in 100 DEG C in vacuum drying oven
It is dried 5 hours, obtains pure intercalated graphite.
(2) be 1g:30ml according to mass volume ratio, intercalated graphite is joined equipped with
1-Et-3,5-Me2ImN(CF3SO2)2In the container of ionic liquid, take the mixed of 1L intercalated graphite and ionic liquid
Compound joins and builds in the high speed centrifuge that capacity is 2L, strong plus magnetic field at centrifuge top base two ends
Degree is the stationary magnetic field of 0.8T, starts magnetic field, centrifuge, allow centrifuge with the speed of 1000 revs/min from
The heart peels off intercalated graphite 80 minutes, and the centrifugal precipitate dimethylformamide (DMF) obtained is filtered 5
Secondary, then filter until filtrate AgNO with deionized water3Detection is without chloride ion；Filtering residue after cleaning is put into
It is dried 16 hours at 80 DEG C in vacuum drying oven, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 9
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:0.9 in mass ratio by natural flake graphite and zinc chloride, by natural
Crystalline flake graphite and zinc chloride are placed in sealed silica envelope, are warming up to 520 DEG C, insulation reaction 5 hours, reaction knot
It is cooled to room temperature after bundle, obtains intercalated graphite.After intercalated graphite is cleaned with deionized water, then it is vacuum dried
Case is dried 6 hours in 80 DEG C, obtains pure intercalated graphite.
(2) be 1g:100ml according to mass volume ratio, intercalated graphite is joined equipped with
1,3-Et2-4-MeImN(CF3SO2)2In the container of ionic liquid, take the mixed of 1L intercalated graphite and ionic liquid
Compound joins and builds in the high speed centrifuge that capacity is 2L, strong plus magnetic field at centrifuge top base two ends
Degree is the stationary magnetic field of 1T, starts magnetic field, centrifuge, allows centrifuge with the centrifugation of 3000 revs/min
Peel off intercalated graphite 50 minutes, the centrifugal precipitate N-Methyl pyrrolidone (NMP) obtained is filtered 5
Secondary, then filter until filtrate AgNO with deionized water3Detection is without chloride ion；Filtering residue after cleaning is put into
It is dried 12 hours at 90 DEG C in vacuum drying oven, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 10
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 1:1.1 in mass ratio by Delanium and barium chloride, by natural scale
Graphite and barium chloride are placed in sealed silica envelope, are warming up to 550 DEG C, insulation reaction 4 hours, after reaction terminates
It is cooled to room temperature, obtains intercalated graphite.After intercalated graphite is cleaned with deionized water, then in vacuum drying oven
It is dried 4 hours in 90 DEG C, obtains pure intercalated graphite.
(2) be 1g:10ml according to mass volume ratio, intercalated graphite is joined equipped with
1,3-Et2-5-MeImN(CF3SO2)2In the container of ionic liquid, take the mixed of 1L intercalated graphite and ionic liquid
Compound joins and builds in the high speed centrifuge that capacity is 2L, strong plus magnetic field at centrifuge top base two ends
Degree is the stationary magnetic field of 0.1T, starts magnetic field, centrifuge, allow centrifuge with the speed of 5000 revs/min from
The heart peels off intercalated graphite 10 minutes, and the centrifugal precipitate dimethylformamide (DMF) obtained is filtered 4
Secondary, then filter until filtrate AgNO with deionized water3Detection is without chloride ion；Filtering residue after cleaning is put into
It is dried 14 hours at 70 DEG C in vacuum drying oven, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
Embodiment 11
Preparing of the Graphene of the present embodiment is as follows:
(1) preparation of intercalated graphite: be 50% iron chloride by Delanium and mass ratio: 50% copper chloride
Mixture is 1:1.2 in mass ratio, is placed in sealed silica envelope with iron chloride and copper chloride by natural flake graphite,
Being warming up to 460 DEG C, insulation reaction 2 hours, reaction is cooled to room temperature after terminating, obtains intercalated graphite.To insert
After layer graphite cleans with deionized water, then vacuum drying oven is dried 6 hours in 100 DEG C, obtains pure inserting
Layer graphite.
(2) it is 1g:50ml according to mass volume ratio, intercalated graphite is joined equipped with EtMeImCF3CO3
In the container of ionic liquid, taking the mixture of 1L intercalated graphite waters ionic liquid and joining capacity is 2L's
Build in high speed centrifuge, add that at centrifuge top base two ends magnetic field intensity is the stationary magnetic field of 0.01T,
Start magnetic field, centrifuge, allow centrifuge peel off intercalated graphite 100 minutes with the centrifugation of 8000 revs/min,
The centrifugal precipitate N-Methyl pyrrolidone (NMF) obtained is filtered 5 times, then filters with deionized water
Until filtrate AgNO3Detection is without chloride ion；Filtering residue after cleaning is put in vacuum drying oven at 100 DEG C
It is dried 12 hours, obtains the Graphene of the present embodiment.
After tested, obtain the monolayer rate of the present embodiment Graphene, be shown in Table 1.
What table 1 represented is the monolayer rate of the Graphene of embodiment 1 ~ embodiment 11 preparation.
Table 1
It is known that the monolayer rate of the Graphene of embodiment 1 ~ embodiment 11 preparation is all 60% from table 1
Above.And the Graphene monolayer rate prepared by chemistry redox method is about about 18%, embodiment 1 ~ enforcement
The quality of the Graphene that example 11 prepares is higher.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, it is also possible to make some deformation and
Improving, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is as the criterion.
Claims (4)
1. the preparation method of a Graphene, it is characterised in that comprise the steps:
Step one: graphite and chloride intercalator are mixed to get reactant, by described reactant in temperature
At 460 DEG C～550 DEG C, reaction obtains intermediate product；
Step 2: described intermediate product is cleaned, obtains pure intercalated graphite after drying；
Step 3: form intercalated graphite and the mixture of ionic liquid after intercalated graphite, ionic liquid mixing,
The mixture of described intercalated graphite Yu ionic liquid is placed in stationary magnetic field, is centrifuged processing；
Step 4: the precipitate obtained after described centrifugal treating is carried out, obtains Graphene；
Step 5: vacuum drying；
Described ionic liquid is selected from 1-ethyl-3-methylimidazole Tetrafluoroboric acid, 1-ethyl-3-methylimidazole fluoroform
Sulfimide, 1-ethyl-3-methylimidazole trifluoromethanesulfonic acid, 1-ethyl-3-methylimidazole trifluoroacetic acid, 1-ethyl
-3-Methylimidazole. fluoroform sulphonyl carbon, 1-ethyl-3-methylimidazole five acetyl fluoride imines, 1-ethyl-3-methyl miaow
Azoles two cyaniding nitrogen, 1-ethyl-3,5-methylimidazole fluoroform sulfimide, 1,3-diethyl-4-methylimidazole three
At least one of fluorine methylsulfonimide and 1,3-diethyl-5-Methylimidazole. fluoroform sulfimide；
Described intercalated graphite is 1g:10mL～100mL with the mass volume ratio of ionic liquid；Described chloride is inserted
Layer agent is selected from iron chloride, Nickel dichloride., copper chloride, cobaltous chloride, potassium chloride, magnesium chloride, lead chloride, chlorination
At least one in zinc, calcium chloride and barium chloride；
Described graphite is 1:0.8～1:1.2 with the mass ratio of described chloride intercalator, and the described response time is 2
Hour～6 hours；The magnetic field intensity of described stationary magnetic field is 0.01 tesla～1 tesla；Described centrifugal place
Reason condition is: rotating speed 1000 revs/min～10000 revs/min, processes 10 minutes time～100 minutes.
The preparation method of Graphene the most according to claim 1, it is characterised in that described graphite is sky
So crystalline flake graphite or Delanium.
The preparation method of Graphene the most according to claim 1, it is characterised in that in step 4, institute
Stating cleaning and comprise organic solvent clean, described organic solvent is N-Methyl pyrrolidone or dimethylformamide.
The preparation method of Graphene the most according to claim 1, it is characterised in that described vacuum drying
Condition is: temperature 60 C～100 DEG C, 10 hours response time～20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210310132.5A CN103626164B (en) | 2012-08-28 | 2012-08-28 | The preparation method of Graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210310132.5A CN103626164B (en) | 2012-08-28 | 2012-08-28 | The preparation method of Graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626164A CN103626164A (en) | 2014-03-12 |
| CN103626164B true CN103626164B (en) | 2016-12-21 |
Family
ID=50207671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210310132.5A Active CN103626164B (en) | 2012-08-28 | 2012-08-28 | The preparation method of Graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626164B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314628B (en) * | 2015-11-09 | 2017-08-01 | 新乡市远东电子科技股份有限公司 | A kind of graphene and preparation method thereof, the application in terms of lithium ion cell positive conductive agent |
| CN105776187A (en) * | 2016-01-27 | 2016-07-20 | 复旦大学 | Method for green environmental-protection preparation of high-concentration ultra-clean graphene dispersion liquid |
| CN107032334B (en) * | 2017-06-15 | 2018-03-20 | 成都新柯力化工科技有限公司 | A kind of method that stretch release prepares graphene in magnetostriction system |
| CN113371699B (en) * | 2020-03-09 | 2024-02-06 | 中国科学院上海硅酸盐研究所 | Green method for preparing high-quality graphene powder in large scale and ultra-low cost |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| US20110017587A1 (en) * | 2009-07-27 | 2011-01-27 | Aruna Zhamu | Production of chemically functionalized nano graphene materials |
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
-
2012
- 2012-08-28 CN CN201210310132.5A patent/CN103626164B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110017587A1 (en) * | 2009-07-27 | 2011-01-27 | Aruna Zhamu | Production of chemically functionalized nano graphene materials |
| CN101993061A (en) * | 2009-08-19 | 2011-03-30 | 中国科学院金属研究所 | Method for preparing high-quality graphene with controllable layer number |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN102167313A (en) * | 2011-04-25 | 2011-08-31 | 同济大学 | Method for preparing graphene oxide through peeling in electric field |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626164A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102167311B (en) | Method for preparing graphene on large scale | |
| WO2020057042A1 (en) | Method for extracting lithium from amblygonite and preparing iron-containing phosphate | |
| JP6612506B2 (en) | Disposal of used lithium ion batteries | |
| CN103626163A (en) | Graphene preparation method | |
| CN103626164B (en) | The preparation method of Graphene | |
| CN104386678B (en) | A kind of preparation method of Graphene | |
| CN106622170A (en) | Preparation method and application of lithium-titanium type ion sieve composite membrane | |
| CN103588195A (en) | Preparation method of graphene | |
| CN104071777B (en) | A kind of preparation method of Graphene | |
| CN108840330A (en) | A kind of method that waste acid resource circulation prepares graphene oxide | |
| CN102464312B (en) | Preparation method of graphene | |
| CN103553030A (en) | Preparation method of few-layer graphene | |
| Tang et al. | Facile hydroxyl-assisted synthesis of morphological Cu 2 O architectures and their shape-dependent photocatalytic performances | |
| CN104129781B (en) | A kind of situ Nitrogen Doping porous graphene and preparation method thereof | |
| CN103626166A (en) | Graphene preparation method | |
| CN103359714A (en) | Preparation method of graphene | |
| CN104003373A (en) | Graphene material and preparation method thereof | |
| CN106587033B (en) | A method of preparing graphene | |
| CN103935982A (en) | Graphene nanoribbon preparation method | |
| CN103449414B (en) | There is the preparation method of the Graphene of loose structure | |
| KR20180112935A (en) | Method for preparing high purity graphite isolated from secondary cell battery | |
| CN107176600A (en) | A kind of cube pattern graphene powder and preparation method and application | |
| CN103626165A (en) | Graphene preparation method | |
| CN104876219B (en) | A kind of method of easy synthesis graphene oxide under room temperature | |
| CN103628082A (en) | Graphene preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |