CN103738947A - Preparation method for single-layer graphene ethylene glycol solution - Google Patents
Preparation method for single-layer graphene ethylene glycol solution Download PDFInfo
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- CN103738947A CN103738947A CN201310592691.4A CN201310592691A CN103738947A CN 103738947 A CN103738947 A CN 103738947A CN 201310592691 A CN201310592691 A CN 201310592691A CN 103738947 A CN103738947 A CN 103738947A
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Abstract
The invention relates to a preparation method for a single-layer graphene ethylene glycol solution. The method includes: soaking graphite into an intercalation agent to make solvent molecules intercalated into interlayers of graphite so as to obtain a graphite intercalation compound, i.e. expansible graphite; then heating the expansible graphite rapidly under argon protection to make the solvent molecular in the interlayers of graphite largen and expand quickly in volume, letting the force greater than the Van der Waals' force between graphite layers expand the graphite layers, thus obtaining expanded graphite; then carrying out stripping screening by an ultrasonic dispersion liquid phase stripping technique to obtain a graphene solution, and then carrying out pumping filtering, washing and drying to obtain graphene solid powder; subjecting the graphene solids to ultrasonic dispersion in an ethylene glycol solution, thus obtaining the graphene ethylene glycol solution easy to combine with polyester and polyester resin.
Description
Technical field
The invention belongs to Graphene technical field, be specifically related to a kind of single-layer graphene ethylene glycol solution preparation method.
Background technology
Graphene is the Two-dimensional Carbon atomic crystal of monatomic thickness, is the thinnest material manually making at present, and it is considered to form the basic structural unit of soccerballene, carbon nanotube and graphite.Graphene has the performances such as excellent electricity, calorifics, mechanics, has obtained investigator's extensive concern since 2004 find.It is with a wide range of applications in matrix material, solar cell, sensor field, and be expected to replace silicon materials at semiconductor applications, in various fields such as unicircuit of future generation, energy storage material, flexible display material, bio-pharmaceuticals, aerospace, environment-friendly materials, thermally conductive material, High Strength Steels, having broad application prospects, is impact and the strategic novel material that leads new round Industrial Revolution.Therefore urgently seek a kind of method of preparing in a large number Graphene.
Prior art comprises physical method and chemical process to the preparation method of Graphene, and every kind of method has superiority, and also has shortcoming separately simultaneously.To prepare single crystal graphene film lattice imperfection few for the physical method of graphite to utilize micromechanics to come off, excellent performance, but the method needs the temperature condition of superelevation, and complex process, preparation time is long, and the shortcoming such as yield poorly, is only limited to laboratory fundamental research.Template epitaxial method is under high temperature and uht conditions, in monocrystal SiC surface epitaxy, prepare Graphene, this preparation method can obtain large-area Graphene, but the promotion and application that its cost is higher, product is difficult for greatly having limited from factors such as substrate separate the method.Based on the limitation of physical method, chemical process because of its productive rate high, cost is low, the advantage that also can carry out chemically modified to Graphene has caused investigator's concern.The method is under strong acid and strong oxidizer effect, Graphite Powder 99 to be oxidized to intercalation to generate graphite oxide, more ultrasonic peeling off be separated into individual layer and be prepared into the graphene oxide water-sol, finally its deoxidation and reduction is become to Graphene.Wherein, selecting suitable reductive agent is the problem that investigator very pays close attention to.Conventional reductive agent has hydrazine hydrate, Resorcinol, sodium borohydride, reducing sugar, aluminium powder etc., but hydrazine hydrate and Resorcinol have very strong toxicity, harmful to human body and environment; Though xitix is a kind of efficient, environmentally friendly reductive agent, but it is expensive, be unfavorable for large-scale industrialization production.
Based on existing technology, by N-Methyl pyrrolidone, carry out the graphene aqueous solution that intercalation adds thermal expansion and obtained initial success, but in part industrial use, the aqueous solution does not possess the substance characteristics of other organic compound, cannot meet diversified industrial use.
Summary of the invention
In order to overcome above the deficiencies in the prior art, the invention provides a kind of single-layer graphene ethylene glycol solution preparation method, utilize N-Methyl pyrrolidone as intercalator, selecting natural graphite is raw material, by repeatedly carrying out the homodisperse single-layer graphene solution of ultrasonic preparation, suction filtration, washing, oven dry obtain Graphene pressed powder, and Graphene solid is dispersed in ethylene glycol solution through ultrasonic, obtain finely dispersed Graphene ethylene glycol solution.
The present invention is achieved by the following technical solutions:
A kind of single-layer graphene ethylene glycol solution preparation method, carries out according to following steps:
(1) configure graphite solution in graphite being joined to organic solution at-5 ~ 0 ℃, fully stir 30min ~ 2h, by the ultrasonic interlayer that makes solvent molecule be intercalation into graphite, obtain expansible black lead;
(2) use argon gas to adequately protect expansible black lead, 90 ~ 100
0in the temperature of C, fully heat 10min ~ 2h, obtain expanded graphite;
(3) utilize the liquid phase stripping method of ultrasonic dispersion to peel off screening to expanded graphite, obtain graphene solution;
(4) pass through again suction filtration, washing, oven dry, obtain Graphene pressed powder;
(5) Graphene solid is dispersed in ethylene glycol solution through ultrasonic, obtains finely dispersed Graphene ethylene glycol solution.
Compared with prior art, the invention has the advantages that with N-Methyl pyrrolidone intercalation, adding the product that heat expansion liquid phase stripping method makes can be made into dry powder or be scattered in various dispersion liquids, is conducive to multiple materials such as refinery coke modified activated carbons compound.Graphene is dispersed in conventional aromaticity non-polar organic solvent ethylene glycol, for preparing Graphene-polyester dacron, Graphene-vibrin has important use.
Accompanying drawing explanation
Fig. 1 is Graphene atomic force microscope picture.
Fig. 2 is Graphene altitude distribution figure.
Fig. 3 is Graphene scanning electronic microscope schematic diagram.
embodiment:
Below embodiments of the invention are elaborated, the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
A kind of single-layer graphene ethylene glycol solution preparation method, carries out according to following steps:
(1) solution that preparation 100ml is comprised of with the ratio of 1:2 dodecyl triphenyl bromide phosphine and N-Methyl pyrrolidone, in the environment of-2 ℃, the 900 order natural graphite powders of 4g are dipped in solution, and ultrasonic 90min to make solvent molecule be intercalation into graphite intermolecular, obtain expansible black lead.
(2) under argon shield environment, be heated to 94 ℃ and be incubated 30min, obtain expanded graphite.
(3) at operating frequency 60kHZ, under power 160W effect, expanded graphite solution is carried out to ultrasonic peeling off after 90min, obtain black single-layer graphene solution.
(4) graphene solution is carried out to suction filtration, 2% dilute hydrochloric acid washing 2 times for filter cake, deionized water is washed till after neutrality, dries 4h and obtain black Graphene pressed powder in 60 ℃ of baking ovens.
(5) will make Graphene pressed powder and be dispersed in 100ml ethylene glycol solution, and at operating frequency 60kHZ, after the lower ultrasonic 1h of power 160W effect, graphene uniform will be dispersed in ethylene glycol solution, obtain black single-layer graphene ethylene glycol solution.
Embodiment 2
A kind of single-layer graphene ethylene glycol solution preparation method, carries out according to following steps:
(1) solution that preparation 100ml is comprised of with the ratio of 2:1 dodecyl triphenyl bromide phosphine and N-Methyl pyrrolidone, in the environment of-2 ℃, the 900 order natural graphite powders of 4g are dipped in solution, and ultrasonic 90min to make solvent molecule be intercalation into graphite intermolecular, obtain expansible black lead.
(2) under argon shield environment, be heated to 94 ℃ and be incubated 30min, obtain expanded graphite.
(3) at operating frequency 60kHZ, under power 160W effect, expanded graphite solution is carried out to ultrasonic peeling off after 90min, obtain black single-layer graphene solution.
(4) graphene solution is carried out to suction filtration, 2% dilute hydrochloric acid washing 2 times for filter cake, deionized water is washed till after neutrality, dries 4h and obtain black Graphene pressed powder in 60 ℃ of baking ovens.
(5) will make Graphene pressed powder and be dispersed in 100ml ethylene glycol solution, and at operating frequency 60kHZ, after the lower ultrasonic 1h of power 160W effect, graphene uniform will be dispersed in ethylene glycol solution, obtain black single-layer graphene ethylene glycol solution.
Embodiment 3
A kind of single-layer graphene ethylene glycol solution preparation method, carries out according to following steps:
(1) get 100ml dodecyl triphenyl bromide phosphine solution, in the environment of-2 ℃, the 900 order natural graphite powders of 4g be dipped in solution, and ultrasonic 90min to make solvent molecule be intercalation into graphite intermolecular, obtain expansible black lead.
(2) under argon shield environment, be heated to 94 ℃ and be incubated 30min, obtain expanded graphite.
(3) at operating frequency 60kHZ, under power 160W effect, expanded graphite solution is carried out to ultrasonic peeling off after 90min, obtain black single-layer graphene solution.
(4) graphene solution is carried out to suction filtration, 2% dilute hydrochloric acid washing 2 times for filter cake, deionized water is washed till after neutrality, dries 4h and obtain black Graphene pressed powder in 60 ℃ of baking ovens.
(5) will make Graphene pressed powder and be dispersed in 100ml ethylene glycol solution, and at operating frequency 60kHZ, after the lower ultrasonic 1h of power 160W effect, graphene uniform will be dispersed in ethylene glycol solution, obtain black single-layer graphene ethylene glycol solution.
Embodiment 4
A kind of single-layer graphene ethylene glycol solution preparation method, carries out according to following steps:
(1) get 100ml N-Methyl pyrrolidone solution, in the environment of-2 ℃, the 900 order natural graphite powders of 4g be dipped in solution, and ultrasonic 90min to make solvent molecule be intercalation into graphite intermolecular, obtain expansible black lead.
(2) under argon shield environment, be heated to 94 ℃ and be incubated 30min, obtain expanded graphite.
(3) at operating frequency 60kHZ, under power 160W effect, expanded graphite solution is carried out to ultrasonic peeling off after 90min, obtain black single-layer graphene solution.
(4) graphene solution is carried out to suction filtration, 2% dilute hydrochloric acid washing 2 times for filter cake, deionized water is washed till after neutrality, dries 4h and obtain black Graphene pressed powder in 60 ℃ of baking ovens.
(5) will make Graphene pressed powder and be dispersed in 100ml ethylene glycol solution, and at operating frequency 60kHZ, after the lower ultrasonic 1h of power 160W effect, graphene uniform will be dispersed in ethylene glycol solution, obtain black single-layer graphene ethylene glycol solution.
In the preparation process of single-layer graphene ethylene glycol solution, the effect of selecting N-Methyl pyrrolidone, as intercalator, graphite is peeled off into single-layer graphene is better, and individual layer rate, up to more than 99%, is easy to Graphene and is dispersed in other organic solvents.Finally, utilize shown in atomic power electron microscope Fig. 1-2, and shown in scanning electron microscope diagram 3, pattern and structure to Graphene characterize.Shown in atomic force microscope Fig. 1 of Graphene, show that single-layer graphene layer is smooth and level and smooth, shown in thickness chart 2, is about 0.5-1.0nm.Meanwhile, shown in scanning electron microscope diagram sheet Fig. 3 of Graphene, further confirmed the thin layer pattern of Graphene.
Claims (8)
1. a single-layer graphene ethylene glycol solution preparation method, is characterized in that, according to following steps, carries out:
(1) configure graphite solution in graphite being joined to organic solution at-5 ~ 0 ℃, fully stir 30min ~ 2h, by the ultrasonic interlayer that makes solvent molecule be intercalation into graphite, obtain expansible black lead solution;
(2) use argon gas to adequately protect expansible black lead, 90 ~ 100
0in the temperature of C, fully heat 20min ~ 1h, obtain expanded graphite;
(3) utilize the liquid phase stripping method of ultrasonic dispersion to peel off screening to expanded graphite, obtain graphene solution;
(4) pass through again suction filtration, washing, oven dry, obtain Graphene pressed powder;
(5) Graphene solid is dispersed in ethylene glycol solution through ultrasonic, obtains finely dispersed Graphene ethylene glycol solution.
2. single-layer graphene ethylene glycol solution preparation method according to claim 1, is characterized in that, the organic solution described in step (1) is one or both in dodecyl triphenyl bromide phosphine or N-Methyl pyrrolidone.
3. according to the single-layer graphene ethylene glycol solution preparation method described in claim l, it is characterized in that, described graphite is 400 ~ 1000 object natural graphite powders.
4. single-layer graphene ethylene glycol solution preparation method according to claim 1, is characterized in that, the graphite strength of solution described in step (1) is 0.5% ~ 5%.
5. single-layer graphene ethylene glycol solution preparation method according to claim 1, is characterized in that, ultrasonic described in step (1) is at operating frequency 45kHz, under power 160W effect, and ultrasonic 30min ~ 2h.
6. according to the single-layer graphene ethylene glycol solution preparation method described in claim l, it is characterized in that, the liquid phase stripping method of the ultrasonic dispersion described in step (3) is at operating frequency 60kHZ, under power 160W effect, existing expanded graphite solution is carried out to the ultrasonic 30min ~ 2h that peels off.
7. according to the single-layer graphene ethylene glycol solution preparation method described in claim l, it is characterized in that, suction filtration described in step (4), washing, oven dry are for to carry out suction filtration by graphene solution, 2% dilute hydrochloric acid washing 1 ~ 5 time for the filter cake obtaining, the filter cake of suction filtration is extremely neutral with deionized water wash again, after suction filtration, in 60 ℃ of baking ovens, dry 2 ~ 12h.
8. according to the single-layer graphene ethylene glycol solution preparation method described in claim l, it is characterized in that, Graphene solid is dispersed in ethylene glycol solution as the single-layer graphene solid obtaining is added in ethylene glycol solvent through ultrasonic described in step (5), at operating frequency 60kHZ, the lower ultrasonic 30min ~ 2h of power 160W effect, is dispersed in ethylene glycol solution graphene uniform.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556020A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Preparation method of graphene ethanol dispersion solution |
| CN104925786A (en) * | 2015-03-19 | 2015-09-23 | 青岛科技大学 | Novel method for preparing graphene by utilizing low-boiling-point organic solvent in stripping manner |
| CN108559070A (en) * | 2018-05-11 | 2018-09-21 | 山东安恒华盛石墨烯材料科技有限公司 | A kind of single-layer graphene unsaturated polyester resin and preparation method thereof |
| CN110157274A (en) * | 2018-03-28 | 2019-08-23 | 山东佳星环保科技有限公司 | A kind of graphene polymer water-repellent paint masterbatch and preparation method |
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| CN102659096A (en) * | 2012-04-27 | 2012-09-12 | 湖南大学 | Preparation methods of graphene dispersion solution and thin film of graphene |
| CN103213979A (en) * | 2013-05-10 | 2013-07-24 | 山西大同大学 | Method for preparing graphene by solvent-thermal process |
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Patent Citations (2)
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| CN102659096A (en) * | 2012-04-27 | 2012-09-12 | 湖南大学 | Preparation methods of graphene dispersion solution and thin film of graphene |
| CN103213979A (en) * | 2013-05-10 | 2013-07-24 | 山西大同大学 | Method for preparing graphene by solvent-thermal process |
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| YENNY HERNANDEZ ET AL.: "High-yield production of graphene by liquid-phase exfoliation of graphite", 《NATURE NANOTECHNOLOGY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556020A (en) * | 2015-01-23 | 2015-04-29 | 青岛科技大学 | Preparation method of graphene ethanol dispersion solution |
| CN104925786A (en) * | 2015-03-19 | 2015-09-23 | 青岛科技大学 | Novel method for preparing graphene by utilizing low-boiling-point organic solvent in stripping manner |
| CN110157274A (en) * | 2018-03-28 | 2019-08-23 | 山东佳星环保科技有限公司 | A kind of graphene polymer water-repellent paint masterbatch and preparation method |
| CN108559070A (en) * | 2018-05-11 | 2018-09-21 | 山东安恒华盛石墨烯材料科技有限公司 | A kind of single-layer graphene unsaturated polyester resin and preparation method thereof |
| CN108559070B (en) * | 2018-05-11 | 2021-01-22 | 山东安恒华盛石墨烯材料科技有限公司 | Single-layer graphene unsaturated polyester resin and preparation method thereof |
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