CN103420362A - Preparation method for graphene - Google Patents
Preparation method for graphene Download PDFInfo
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- CN103420362A CN103420362A CN2012101604334A CN201210160433A CN103420362A CN 103420362 A CN103420362 A CN 103420362A CN 2012101604334 A CN2012101604334 A CN 2012101604334A CN 201210160433 A CN201210160433 A CN 201210160433A CN 103420362 A CN103420362 A CN 103420362A
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Abstract
The invention discloses a preparation method for graphene. The method comprises the following steps: graphite is subjected to ball milling treatment in an organic solvent, the dosage ratio of the graphite to the organic solvent is 1g:30ml-50ml, and milling balls used in the ball milling treatment are steel balls or agate balls; the graphite after the ball milling treatment and the organic solvent are subjected to centrifugal separation, and the centrifugal liquid is saved; the centrifugal liquid is then subjected to distillation to remove the organic solvent and the graphene is obtained. In the preparation method for the graphene, the graphene is prepared through the ball milling method with steel balls or agate balls, which increases the defects of the graphene effectively, and furthermore increases the specific surface area of the graphene. The method employs less amount of the organic solvent, reduces production cost, and reduces pollution to the environment. In addition, the method is simple in preparation technology, conditions are easy to control, and the method is suitable for industrial production.
Description
Technical field
The invention belongs to the Graphene technical field, specifically relate to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) etc. is found, and obtains the physics Nobel prize in 2010, again causes the carbon material research boom.Because its unique structure and photoelectric property make it become the study hotspot in the fields such as carbon material, nanotechnology, Condensed Matter Physics and functional materials, many scientific workers have been attracted.Single-layer graphene has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g, can be used for effect transistor, electrode materials, matrix material, liquid crystal display material, sensor.The method for preparing at present Graphene mainly contains graphite breakaway, chemistry redox method, ultrasonic stripping method, chemical Vapor deposition process etc.The place that these methods come with some shortcomings at present, the Graphene performance prepared as chemical Vapor deposition process is high but yield poorly, the high but poor performance of Graphene output prepared by oxidation reduction process.Domesticly also occurred adopting ball milling to prepare the method for Graphene, this method abrading-ball adopts soft polymer parcel, has reduced the friction between abrading-ball and graphite, though it is good to prepare the crystalline structure of Graphene, need to use a large amount of organic solvents, cost is high, specific surface area is little, and unfriendly to environment.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of preparation method of Graphene is provided, Graphene output prepared by the method is high, and specific surface area is large, and cost is low.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of preparation method of Graphene, comprise the steps:
Graphite is carried out in organic solvent to ball milling; Wherein, graphite is with consumption of organic solvent than being 1g:30～50ml, and the ball milling ball of described ball milling is steel ball or agate ball;
Described graphite after ball-milling processing and described organic solvent are carried out to centrifugation, leave and take centrifugate;
Described centrifugate is distilled and removed organic solvent, obtain described Graphene.
The preparation method of above-mentioned Graphene adopts steel ball or agate ball to carry out ball milled to prepare Graphene, effectively increase the defect of Graphene, and then increases specific surface area, has increased the range of application of this Graphene.Simultaneously, the method consumption of organic solvent is few, has reduced production cost, reduces the pollution to environment.In addition, the method preparation technology is simple, and condition is easily controlled, and is applicable to suitability for industrialized production.
The accompanying drawing explanation
Fig. 1 is preparation method's process flow diagram of Graphene of the present invention;
Fig. 2 is the electron-microscope scanning figure of the Graphene that makes of the embodiment of the present invention 1.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides a kind of can improve Graphene output, increases its surface-area, reduces the graphene preparation method of its cost.Preparation method's technical process of this Graphene refers to Fig. 1, and the method comprises the steps:
S01, Graphite: graphite is carried out in organic solvent to ball milling; Wherein, graphite is with consumption of organic solvent than being 1g:30～50ml, and the ball milling ball of described ball milling is steel ball or agate ball;
S02, centrifugation: the described graphite after ball-milling processing and described organic solvent are carried out to centrifugation, leave and take centrifugate;
Organic solvent is removed in S03, distillation: described centrifugate is distilled and removed organic solvent, obtain described Graphene.
Concrete, in above-mentioned steps S01, the ratio of graphite and organic solvent can make graphite effectively be stripped from the formation Graphene in ball milling, and makes Graphene effectively be scattered in this organic solvent.This abrading-ball is selected steel ball or agate ball, can effectively destroy the crystalline structure of Graphene, increases the defect of Graphene, and then increases specific surface area.This ball milling can carry out as follows: graphite is joined to the stainless steel reaction container again to adding organic solvent according to the ratio of graphite and organic solvent above in the stainless steel reaction container, and add abrading-ball, then reactor is sealed, finally reactor is installed in ball-grinding machine, set ball milling speed, the time is carried out ball milling.
Preferably, in this step S01, the rotating speed of ball milling is 100～800 rev/mins, and Ball-milling Time is 2～24 hours; The mixture that graphite and organic solvent form and the volume ratio of abrading-ball are 1～3:1, add the graphite of 5～20g in the graphite container that addition is every liter capacity in ball mill container.After adding graphite, organic solvent and abrading-ball according to this proportionlity, this three's cumulative volume is preferably 1/4～3/4 of stainless steel reaction vessel volume.This preferred ball milling condition can make graphite better be stripped from into Graphene, and makes Graphene better be dispersed in organic solvent, so that separate with the graphite be not stripped from step S02 hereinafter.Wherein, the mixture that the rotating speed of appropriate design ball milling and time and graphite and organic solvent form and the energy density per unit volume of abrading-ball effectively improve the shock ratio of graphite in ball milling, improve the yield of Graphene, employing rigidity abrading-ball is conducive to increase the defect of Graphene, increasing specific surface area.
Particularly, the graphite in this step S01 is preferably at least one in natural scale graphite, synthetic graphite, agraphitic carbon, expanded graphite; Position polystyrene and 2,5-, bis-octyloxies between organic solvent is preferably-at least one in styrol copolymer (PmPV), r-butyrolactone (GBL), ethylene dichloride (DCE).
In above-mentioned steps S02, before carrying out centrifugation, should first abrading-ball be separated with organic solvent with graphite, the method that abrading-ball separates can adopt screen cloth to separate, and certainly can also adopt its mode commonly used of this area to separate.The purpose of centrifugation is in order to make in mechanical milling process the Graphene of being peeled off acquisition by ball milling separate with the graphite be not stripped from or only part is stripped from, to remove graphite, thereby to obtain the suspension liquid that only contains Graphene.Study discovery through the contriver, the rotating speed of centrifugation is preferably 500～3000 rev/mins, when centrifugation time is preferably 5～30 minutes, removes and is not stripped from or only the graphite effect that is stripped from of part is best, and the purity of the Graphene in the centrifugate of leaving and taking is the highest.
In this step S03, the technique that organic solvent is removed in distillation does not have particular requirement, can realize that the purpose of removing organic solvent gets final product.
Further, the preparation method of above-described embodiment Graphene also comprises that Graphene to obtaining in step S03 is above cleaned, dry step.The purpose of this cleaning is the organic solvent remained in Graphene in order to remove.Drying is in order to remove highly volatile organic solvent and water cruel in cleaning.Particularly, clean and preferably use successively deionized water, ethanol, the described Graphene of washing with acetone, and filter; Drying is preferably dried the Graphene after cleaning 12～24 hours under 60～80 ℃, and preferred bake out temperature is 60 ℃.
Therefore, the preparation method of above-mentioned Graphene adopts steel ball or agate ball to carry out ball milled to prepare Graphene, effectively increase the defect of Graphene, and then increases specific surface area, as shown in Figure 2.The Graphene that just prepared by the method has this advantage, has increased the range of application of this Graphene, as the application at aspects such as ultracapacitors.Simultaneously, the method consumption of organic solvent is few, has reduced production cost, reduces the pollution to environment.In addition, the method preparation technology is simple, and condition is easily controlled, and is applicable to suitability for industrialized production.
Below by concrete a plurality of embodiment, the preparation method of Graphene is described, and the aspect such as Graphene correlated performance.
Embodiment 1
A kind of preparation method of Graphene, concrete steps are as follows:
S11: according to the proportionlity in table 1 hereinafter, in stainless steel reaction container by natural scale graphite in every liter capacity, add the 10g ratio to join in the stainless steel reaction container, natural scale graphite and PmPV join reactor in the ratio of 1g:30mL, the abrading-ball that diameter is 20mm and the volume ratio of reactant are that 1:1 joins reactor, then seal;
S12: reactor is installed in ball-grinding machine, and ball milling speed is set 800 rev/mins, and ball milling stopped after 4 hours;
S13: reactor is taken out, with screen cloth, spheroid is separated with organic solvent with the natural scale graphite after ball milling in step S12, again by the mixture of the natural scale graphite after ball milling and organic solvent with the whizzer of 2000 rev/mins centrifugal 5 minutes, unstripped natural scale graphite is separated, obtain the mixture of Graphene and organic solvent;
S14: the method that adopts distillation is distilled the organic solvent in the mixture of the Graphene that obtains in step S13 and organic solvent to remove, the Graphene of reentrying cleans, filters with deionized water, ethanol, acetone etc. respectively, by the Graphene collected in vacuum drying oven 60 ℃ dry 12 hours, just obtain dry Graphene.
Graphene sample prepared by the present embodiment 1 is through the specific-surface area detection instrument test and carry out electron-microscope scanning.Wherein, the electron-microscope scanning result as described in Figure 2, as can be seen from Figure 2, the thickness of Graphene is about 0.5～1.5nm, and has abundant fold pattern and pore structure, and specific surface area is large, through the specific-surface area detection instrument test result, show, its specific surface area can be up to 1560m
2/ g, as shown in hereinafter table 2.
Embodiment 2
A kind of preparation method of Graphene, concrete steps are referring to the preparation method of Graphene in embodiment 1, wherein the data in embodiment 2 that vide infra in table 1 of the parameter in each step in this embodiment 2.
The Graphene sample of the present embodiment 2 preparations is tested through specific-surface area detection instrument, the test result demonstration, its specific surface area is 1310m
2/ g, as shown in hereinafter table 2.
Embodiment 3
A kind of preparation method of Graphene, concrete steps are referring to the preparation method of Graphene in embodiment 1, wherein the data in embodiment 3 that vide infra in table 1 of the parameter in each step in this embodiment 3.
The Graphene sample of the present embodiment 3 preparations is tested through specific-surface area detection instrument, the test result demonstration, its specific surface area is 890m
2/ g, as shown in hereinafter table 2.
Embodiment 4
A kind of preparation method of Graphene, concrete steps are referring to the preparation method of Graphene in embodiment 1, wherein the data in embodiment 4 that vide infra in table 1 of the parameter in each step in this embodiment 4.
The Graphene sample of the present embodiment 4 preparations is tested through specific-surface area detection instrument, the test result demonstration, its specific surface area is 1780m
2/ g, as shown in hereinafter table 2.
Embodiment 5
A kind of preparation method of Graphene, concrete steps are referring to the preparation method of Graphene in embodiment 1, wherein, natural scale graphite be and a position polystyrene and 2,5-, bis-octyloxies-mixed solvent of styrol copolymer is joined to reactor in the ratio of 1g:30mL.
The Graphene sample of the present embodiment 5 preparations is tested through specific-surface area detection instrument, the test result demonstration, the Graphene sample specific surface area of its specific surface area and embodiment 4 preparations is very approaching.
The parameter list of each embodiment of table 1
(annotate: graphite volume ratio (g/L) refers in the stainless steel reaction container of every liter capacity and contains the graphite grams)
Table 2BET specific-surface area detection instrument test result
| Embodiment | 1 | 2 | 3 | 4 |
| Specific surface area (m 2/g) | 1560 | 1310 | 890 | 1780 |
The Graphene correlated performance prepared from the various embodiments described above, the preparation method of above-mentioned Graphene adopts steel ball or agate ball to carry out ball milled to prepare Graphene, effectively increase the defect of Graphene, and then increase specific surface area, thereby increased the range of application of this Graphene.Simultaneously, this graphene preparation method, by adjusting the ratio of graphite and organic solvent, effectively reduces the consumption of organic solvent, has reduced production cost, reduces the pollution to environment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. the preparation method of a Graphene, comprise the steps:
Graphite is carried out in organic solvent to ball milling; Wherein, the consumption of graphite and organic solvent is 1g:30ml～50ml, and the abrading-ball that described ball milling is used is steel ball or agate ball;
Described graphite after ball-milling processing and described organic solvent are carried out to centrifugation, leave and take centrifugate;
Described centrifugate is distilled and removed organic solvent, obtain described Graphene.
2. the preparation method of Graphene according to claim 1, it is characterized in that: the rotating speed of described ball milling is 100～800 rev/mins, Ball-milling Time is 2～24 hours.
3. the preparation method of Graphene according to claim 1, it is characterized in that: the mixture that described graphite and organic solvent form and the volume ratio of abrading-ball are 1～3:1.
4. the preparation method of Graphene according to claim 1, is characterized in that: the graphite that adds 5～20g in the container that the addition of described graphite in ball mill container is every liter capacity.
5. according to the preparation method of the arbitrary described Graphene of claim 1 to 4, it is characterized in that: described graphite is at least one in natural scale graphite, synthetic graphite, agraphitic carbon, expanded graphite.
6. according to the preparation method of the arbitrary described Graphene of claim 1 to 4, it is characterized in that: described organic solvent be between position polystyrene and 2,5-, bis-octyloxies-at least one in styrol copolymer, r-butyrolactone, ethylene dichloride.
7. according to the preparation method of the arbitrary described Graphene of claim 1 to 4, it is characterized in that: the rotating speed of described centrifugation is 500～3000 rev/mins, and centrifugation time is 5～30 minutes.
8. the preparation method of Graphene according to claim 1 is characterized in that: also comprise to described Graphene clean, dry step.
9. the preparation method of Graphene according to claim 8, it is characterized in that: described cleaning is to use successively deionized water, ethanol, the described Graphene of washing with acetone, and filters.
10. the preparation method of Graphene according to claim 9, it is characterized in that: described drying is that the Graphene after cleaning is dried 12～24 hours under 60～80 ℃.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104627999A (en) * | 2015-03-03 | 2015-05-20 | 赵社涛 | Production method of anti-overlapping thin-layer graphene |
| CN104629495A (en) * | 2015-02-15 | 2015-05-20 | 江苏金陵特种涂料有限公司 | Preparation method for graphene |
| CN105347332A (en) * | 2015-11-25 | 2016-02-24 | 山东科技大学 | Preparation method for graphene |
| CN106362929A (en) * | 2015-07-20 | 2017-02-01 | 北京中科云腾科技有限公司 | Grapheme-copper foil composite heat-conduction film and preparation method for same |
| CN106365155A (en) * | 2015-07-20 | 2017-02-01 | 北京中科云腾科技有限公司 | Graphene and preparation method thereof |
| CN106809824A (en) * | 2017-02-28 | 2017-06-09 | 北京吉泰亿阳科技有限公司 | The method that two-step method prepares modified graphene |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
| CN107758648A (en) * | 2017-10-24 | 2018-03-06 | 济南大学 | A kind of new way that graphene is prepared using ethanol as liquid phase planetary ball mill wet method |
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| CN101671015A (en) * | 2009-10-13 | 2010-03-17 | 南昌航空大学 | Method of producing graphene |
| CN101704520A (en) * | 2009-11-05 | 2010-05-12 | 华侨大学 | Method for producing graphene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101671015A (en) * | 2009-10-13 | 2010-03-17 | 南昌航空大学 | Method of producing graphene |
| CN101704520A (en) * | 2009-11-05 | 2010-05-12 | 华侨大学 | Method for producing graphene |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104629495A (en) * | 2015-02-15 | 2015-05-20 | 江苏金陵特种涂料有限公司 | Preparation method for graphene |
| CN104627999A (en) * | 2015-03-03 | 2015-05-20 | 赵社涛 | Production method of anti-overlapping thin-layer graphene |
| CN106362929A (en) * | 2015-07-20 | 2017-02-01 | 北京中科云腾科技有限公司 | Grapheme-copper foil composite heat-conduction film and preparation method for same |
| CN106365155A (en) * | 2015-07-20 | 2017-02-01 | 北京中科云腾科技有限公司 | Graphene and preparation method thereof |
| CN105347332A (en) * | 2015-11-25 | 2016-02-24 | 山东科技大学 | Preparation method for graphene |
| CN106809824A (en) * | 2017-02-28 | 2017-06-09 | 北京吉泰亿阳科技有限公司 | The method that two-step method prepares modified graphene |
| CN107029694A (en) * | 2017-05-23 | 2017-08-11 | 中国石油大学(北京) | One kind doping carbon material and preparation method thereof |
| CN107758648A (en) * | 2017-10-24 | 2018-03-06 | 济南大学 | A kind of new way that graphene is prepared using ethanol as liquid phase planetary ball mill wet method |
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Application publication date: 20131204 |