CN103626167B - A kind of preparation method of Graphene - Google Patents

A kind of preparation method of Graphene Download PDF

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CN103626167B
CN103626167B CN201310364515.5A CN201310364515A CN103626167B CN 103626167 B CN103626167 B CN 103626167B CN 201310364515 A CN201310364515 A CN 201310364515A CN 103626167 B CN103626167 B CN 103626167B
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graphene
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CN103626167A (en
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张玉清
张航
赫玉欣
姚大虎
郑喜俊
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Henan University of Science and Technology
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Henan University of Science and Technology
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Abstract

The invention discloses a kind of preparation method of Graphene, comprise the following steps: 1) graphite to be added in the vitriol oil and to disperse, after add potassium permanganate and SODIUMNITRATE successively; 2) add distilled water, after stirring, add hydrogen peroxide, obtain jonquilleous reaction system A; 3) pH regulating reaction system A is 6, ultrasonic disperse 2 ~ 5h, resulting dispersion system; 4) in dispersion system, add high boiling organic solvent and reductive agent, stirring reaction 5 ~ 10h, obtains reaction system B; 5) by reaction system B stratification, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, to obtain final product.The preparation method of Graphene of the present invention, eliminate that graphite oxide filters, washing, drying and other steps, save a large amount of disengaging times and bath water, have save time, saving of labor, water saving, decreasing pollution, cost is low, preparation amount is large advantage.

Description

A kind of preparation method of Graphene
Technical field
The invention belongs to grapheme material technical field, relate to a kind of preparation method of Graphene.
Background technology
Graphene is by individual layer sp 2six side's honeycomb two-dirnentional structures of carbon atom composition, its STRUCTURE DECOMPOSITION can become the soccerballene of zero dimension, and the curling carbon nanotube that can form one dimension, superposition can form three-dimensional graphite.Each carbon atom of Graphene is connected to form six-membered ring structure by σ key and other three carbon atoms, and these C-C keys cause graphene sheet layer to have excellent structure rigidity; Simultaneously, each carbon atom contributes the π-electron of a non-Cheng Jian, these π-electrons form π track on the direction parallel with graphite linings, give conduction, heat conductivility, extraordinary specific surface area, Young's modulus and breaking tenacity that Graphene is good, also can match in excellence or beauty with carbon nanotube, also there is the performance of some uniquenesses, as series of properties such as perfect quantum tunneling effect, half-integer quantum hall effect, the specific conductivity that never disappears, and low price.Just because of grapheme material, there is numerous peculiar character like this, it causes the very big research interest of the different field scientists such as physics, chemistry, material, also makes Graphene have great application prospect in fields such as electronics, information, the energy, material and biological medicines.
At present, the preparation method of Graphene mainly contains mechanically peel method, epitaxial growth method, epitaxy method, vapour deposition process and oxidation reduction process.Mechanically peel method is the method being gone out graphene film by mechanical force from the sur-face peeling of body phase graphite crystal, this method raw material is easy to get, and operation is relatively simple, and the purity of the Graphene of synthesis is high, defect is less, but during this method operational cost, low yield, be unsuitable for scale operation.Epitaxial growth method removes Si by heating monocrystalline 6H-SiC, monocrystal SiC face decomposites graphene sheet layer, this method condition harshness (high temperature, high vacuum), and the Graphene manufactured not easily is separated from substrate, is difficult to manufacture Graphene in a large number.Epitaxy method utilizes the atomic structure of growth matrix " kind " to go out Graphene, and Graphene prepared by the method is often in uneven thickness, and the interaction between Graphene and matrix can affect the characteristic of Graphene.Chemical vapour deposition is that reactive material issues biochemical reaction at quite high temperature, gaseous condition, and the solid matter of generation is deposited on the solid matrix surface of heating and then the Technology of obtained solid material.The method is industrial a kind of most widely used method preparing semiconductor film material on a large scale, also be the effective way preparing Graphene at present, can be used for preparing large-area electron device (as electrode, indicating meter etc.), commercial applications for Graphene provides an effective approach, but present stage higher cost, complicated technique and the accurate controlled working conditionality development of the method.
Oxidation reduction process (containing oxidation-modification-reduction method) is divided into Standenmaier method, Brodie method and Hummers method, and wherein the application of Hummers method is more extensive.The chemical reaction that the method relates to has two: 1) with strong protonic acid process graphite, forms compound between graphite layers, then adds strong oxidizer and be oxidized it; 2) reduce after graphene oxide being separated, more effectively chemical reducing agent reduction.Graphene cost prepared by oxidation reduction process is lower; easy and simple to handle, output is large, most possibly realizes Graphene mass-producing preparation; and be convenient to the further modification of Graphene, processing, shaping, for prepared by people, a large amount of single-layer graphene brings hope to this method.But the separation difficulty of the method product, wash with a large amount of water, whole preparation process is tediously long, and therefore efficiency is lower, and environment is unfriendly, and these unfavorable factors limit a large amount of preparation and the applied research thereof of Graphene.
Summary of the invention
The object of this invention is to provide a kind of preparation method of Graphene of efficient, environmental protection.
In order to realize above object, the technical solution adopted in the present invention is: a kind of preparation method of Graphene, comprises the following steps:
1) under agitation, the graphite of 1 weight part to be added in the vitriol oil and to disperse, after add the potassium permanganate of 3 weight parts and the SODIUMNITRATE of 0.5 weight part successively, Keep agitation 2 ~ 5h, obtains mixture;
2) step 1) gained mixture is warming up to 30 ~ 50 DEG C, after insulation 1h, add the distilled water of 45 weight parts, continue to be warming up to 95 DEG C, after reaction 1 ~ 2h, then add the deionized water of 70 weight parts, keep temperature to be 70 ~ 90 DEG C, add the hydrogen peroxide of 5 ~ 8 weight parts after stirring, obtain jonquilleous reaction system A;
3) under agitation, regulating step 2) pH of gained reaction system A is 6, after be warming up to 90 ~ 100 DEG C, ultrasonic disperse 2 ~ 5h, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adds high boiling organic solvent, after add the reductive agent of 15 ~ 50 weight parts, be warming up to reflux temperature, stirring reaction 5 ~ 10h, obtains reaction system B;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, to obtain final product.
Graphite described in step 1) is that granularity is greater than 300 object natural flake graphites.
The consumption of the vitriol oil described in step 1) is: 1g graphite dispersion is in the vitriol oil of 25ml.
The temperature of the described vitriol oil is 5 ~ 15 DEG C.
The method of the pH of reaction system A is regulated to be in step 3): in reaction system A, add sodium carbonate.
High boiling organic solvent described in step 4) is toluene, dimethylbenzene, monochloro-benzene, ethylbenzene or tetraline.
The add-on of described high boiling organic solvent is: the volume of high boiling organic solvent and dispersion system is 1:2 ~ 4.
Reductive agent described in step 4) is hydrazine, Resorcinol, sodium borohydride, citric acid, vitamins C or quadrol.
The preparation method of Graphene of the present invention, utilize graphene oxide wetting ability strong, be easy to disperse in water, the principle that reduced graphene hydrophobic and being easy to disperses in organic solvent, directly reduce in graphite oxide system kind, eliminate that graphite oxide filters, washing, drying and other steps, save a large amount of disengaging times and bath water, have save time, saving of labor, water saving, decreasing pollution, cost is low, preparation amount is large advantage.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 2 gained Graphene;
Fig. 2 is the SEM figure of embodiment 5 gained Graphene.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The preparation method of the Graphene of the present embodiment, comprises the following steps:
1) under mechanical agitation, 1g natural flake graphite (> 300 order) is scattered in 25ml, temperature remains in the vitriol oil of 5 DEG C, then slowly add 3g potassium permanganate and 0.5g SODIUMNITRATE successively, stirring reaction 2 hours, obtains mixture;
2) step 1) gained mixture is warming up to 30 DEG C, after insulation 1h, slowly add the distilled water of 45g, the speed controlling to add water makes temperature rise to 95 DEG C, keep mechanical stirring after 1 hour, then add 70g deionized water, keep temperature to be 70 DEG C, add 5g hydrogen peroxide after stirring, obtain jonquilleous reaction system A;
3) under agitation, to step 2) add sodium carbonate in gained reaction system A and regulate the pH of reaction system A to be 6, be then warmed up to 95 DEG C, ultrasonic disperse, reaction 2h in ultrasonic sound appratus, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adds toluene and 15g hydrazine that volume is 1/4 of dispersion system volume, be warming up to reflux temperature, under strong stirring, carry out reduction reaction 5 hours, obtain reaction system B;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, obtain Graphene.
Embodiment 2
The preparation method of the Graphene of the present embodiment, comprises the following steps:
1) under mechanical agitation, 1g natural flake graphite (> 300 order) is scattered in 25ml, temperature remains in the vitriol oil of 10 DEG C, then slowly add 3g potassium permanganate and 0.5g SODIUMNITRATE successively, stirring reaction 3 hours, obtains mixture;
2) step 1) gained mixture is warming up to 35 DEG C, after insulation 1h, slowly add the distilled water of 45g, the speed controlling to add water makes temperature rise to 95 DEG C, keep mechanical stirring after 1 hour, then add 70g deionized water, keep temperature to be 80 DEG C, add 5g hydrogen peroxide after stirring, obtain jonquilleous reaction system A;
3) under agitation, to step 2) add sodium carbonate in gained reaction system A and regulate the pH of reaction system A to be 6, be then warmed up to 90 DEG C, ultrasonic disperse, reaction 3h in ultrasonic sound appratus, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adds toluene and 20g hydrazine that volume is 1/3 of dispersion system volume, be warming up to reflux temperature, under strong stirring, carry out reduction reaction 8 hours, obtain reaction system B;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, obtain Graphene.
Embodiment 3
The preparation method of the Graphene of the present embodiment, comprises the following steps:
1) under mechanical agitation, 1g natural flake graphite (> 300 order) is scattered in 25ml, temperature remains in the vitriol oil of 15 DEG C, then slowly add 3g potassium permanganate and 0.5g SODIUMNITRATE successively, stirring reaction 3 hours, obtains mixture;
2) step 1) gained mixture is warming up to 50 DEG C, after insulation 1h, slowly add the distilled water of 45g, the speed controlling to add water makes temperature rise to 95 DEG C, keep mechanical stirring after 2 hours, then add 70g deionized water, keep temperature to be 90 DEG C, add 6g hydrogen peroxide after stirring, obtain jonquilleous reaction system A;
3) under agitation, to step 2) add sodium carbonate in gained reaction system A and regulate the pH of reaction system A to be 6, be then warmed up to 95 DEG C, ultrasonic disperse, reaction 4h in ultrasonic sound appratus, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adds dimethylbenzene and 20g sodium borohydride that volume is 1/2 of dispersion system volume, be warming up to reflux temperature, under strong stirring, carry out reduction reaction 8 hours, obtain reaction system B;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, obtain Graphene.
Embodiment 4
The preparation method of the Graphene of the present embodiment, comprises the following steps:
1) under mechanical agitation, 1g natural flake graphite (> 300 order) is scattered in 25ml, temperature remains in the vitriol oil of 15 DEG C, then slowly add 3g potassium permanganate and 0.5g SODIUMNITRATE successively, stirring reaction 5 hours, obtains mixture;
2) step 1) gained mixture is warming up to 45 DEG C, after insulation 1h, slowly add the distilled water of 45g, the speed controlling to add water makes temperature rise to 95 DEG C, keep mechanical stirring after 1.5 hours, then add 70g deionized water, keep temperature to be 70 DEG C, add 8g hydrogen peroxide after stirring, obtain jonquilleous reaction system A;
3) under agitation, to step 2) add sodium carbonate in gained reaction system A and regulate the pH of reaction system A to be 6, be then warmed up to 95 DEG C, ultrasonic disperse, reaction 5h in ultrasonic sound appratus, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adds chlorobenzene and 20g vitamins C that volume is 1/2 of dispersion system volume, be warming up to reflux temperature, under strong stirring, carry out reduction reaction 10 hours, obtain reaction system B;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, obtain Graphene.
Embodiment 5
The preparation method of the Graphene of the present embodiment, comprises the following steps:
1) under mechanical agitation, 1g natural flake graphite (> 300 order) is scattered in 25ml, temperature remains in the vitriol oil of 5 DEG C, then slowly add 3g potassium permanganate and 0.5g SODIUMNITRATE successively, stirring reaction 2 hours, obtains mixture;
2) step 1) gained mixture is warming up to 45 DEG C, after insulation 1h, slowly add the distilled water of 45g, the speed controlling to add water makes temperature rise to 95 DEG C, keep mechanical stirring after 1.5 hours, then add 70g deionized water, keep temperature to be 70 DEG C, add 7g hydrogen peroxide after stirring, obtain jonquilleous reaction system A;
3) under agitation, to step 2) add sodium carbonate in gained reaction system A and regulate the pH of reaction system A to be 6, be then warmed up to 95 DEG C, ultrasonic disperse, reaction 5h in ultrasonic sound appratus, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adding volume is the tetraline of 1/4 of dispersion system volume and the quadrol of 50g, is warming up to reflux temperature, carries out reduction reaction 10 hours, obtain reaction system B under strong stirring;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, obtain Graphene.
Experimental example
Embodiment 2 and embodiment 5 gained Graphene have been carried out scanning electron microscope detection by this experimental example, and result as shown in Figure 1, 2.As can be seen from Fig. 1,2, method gained graphene film area of the present invention is comparatively large, has less thickness.
The preparation method of Graphene of the present invention, owing to have employed two-phase (aqueous phase, organic phase) system, Graphene after reduction is transferred in organic phase immediately, departs from completely with the inorganics in aqueous phase, only need wash several times, filters and just can obtain pure Graphene after being separated; Prior art then needs the time of 4-5 days.

Claims (6)

1. a preparation method for Graphene, is characterized in that: comprise the following steps:
1) under agitation, the graphite of 1 weight part to be added in the vitriol oil and to disperse, after add the potassium permanganate of 3 weight parts and the SODIUMNITRATE of 0.5 weight part successively, Keep agitation 2 ~ 5h, obtains mixture;
2) step 1) gained mixture is warming up to 30 ~ 50 DEG C, after insulation 1h, add the distilled water of 45 weight parts, continue to be warming up to 95 DEG C, after reaction 1 ~ 2h, then add the deionized water of 70 weight parts, keep temperature to be 70 ~ 90 DEG C, add the hydrogen peroxide of 5 ~ 8 weight parts after stirring, obtain jonquilleous reaction system A;
3) under agitation, regulating step 2) pH of gained reaction system A is 6, after be warming up to 90 ~ 100 DEG C, ultrasonic disperse 2 ~ 5h, resulting dispersion system;
4) dispersions obtained for step 3) system is cooled to 80 DEG C, adds high boiling organic solvent, after add the reductive agent of 15 ~ 50 weight parts, be warming up to reflux temperature, stirring reaction 5 ~ 10h, obtains reaction system B;
5) by step 4) gained reaction system B stratification, after removing water layer, with deionized water, organic layer is washed to sulfate radical-free ion, filter and lyophilize, to obtain final product;
High boiling organic solvent described in step 4) is toluene, dimethylbenzene, chlorobenzene, ethylbenzene or tetraline;
The add-on of described high boiling organic solvent is: the volume of high boiling organic solvent and dispersion system is 1:2 ~ 4.
2. the preparation method of Graphene according to claim 1, is characterized in that: graphite described in step 1) is that granularity is greater than 300 object natural flake graphites.
3. the preparation method of Graphene according to claim 1, is characterized in that: the consumption of the vitriol oil described in step 1) is: 1g graphite dispersion is in the vitriol oil of 25ml.
4. the preparation method of the Graphene according to claim 1 or 3, is characterized in that: the temperature of the described vitriol oil is 5 ~ 15 DEG C.
5. according to the preparation method of the Graphene described in claim 1, it is characterized in that: in step 3), regulate the method for the pH of reaction system A to be: in reaction system A, add sodium carbonate.
6. according to the preparation method of the Graphene described in claim 1, it is characterized in that: reductive agent described in step 4) is hydrazine, Resorcinol, sodium borohydride, citric acid, vitamins C or quadrol.
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CN104118868A (en) * 2014-07-07 2014-10-29 苏州世优佳电子科技有限公司 Preparation method for graphene
CN105197921A (en) * 2015-10-19 2015-12-30 南京润屹电子科技有限公司 Preparation method of high-purity graphene
CN106810818B (en) * 2015-11-30 2019-09-13 航天特种材料及工艺技术研究所 A kind of graphene modified epoxy and preparation method thereof
CN105845907A (en) * 2016-04-11 2016-08-10 河南工程学院 Preparation method for lithium titanate-graphene composite negative electrode material
CN107161984B (en) * 2017-06-28 2019-07-16 华南理工大学 A kind of method that ascorbic acid/tea polyphenols synergistic effect prepares graphene
CN109133044B (en) * 2018-09-28 2020-04-21 台州学院 Preparation method of water-soluble graphene material
CN110171819A (en) * 2019-06-11 2019-08-27 北京鼎臣石墨科技有限公司 A method of efficiently preparing graphene
WO2021097660A1 (en) * 2019-11-19 2021-05-27 南京先进生物材料与过程装备研究院有限公司 Method for preparing graphene composite coating

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CN101602504A (en) * 2009-07-16 2009-12-16 上海交通大学 Graphene preparation method based on xitix

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