CN108314022B - Method for preparing graphene by directly stripping ionic liquid - Google Patents
Method for preparing graphene by directly stripping ionic liquid Download PDFInfo
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- CN108314022B CN108314022B CN201810258389.8A CN201810258389A CN108314022B CN 108314022 B CN108314022 B CN 108314022B CN 201810258389 A CN201810258389 A CN 201810258389A CN 108314022 B CN108314022 B CN 108314022B
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- C01B2204/00—Structure or properties of graphene
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
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- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Abstract
The invention discloses a method for preparing graphene by directly stripping ionic liquid. The method for preparing graphene comprises the following steps: 1) mixing graphite and ionic liquid, stirring for reaction, adding water, stirring, and collecting precipitate; 2) and cleaning and drying the precipitate to obtain the graphene. According to the preparation method, the graphene is prepared under mild conditions by utilizing the surface coefficient of the alkaline ionic liquid similar to that of the graphene and the impregnation and swelling effects of anions on the graphite lamellar structure, and the preparation method has the advantages of low cost, environmental friendliness, simplicity in operation and high efficiency.
Description
Technical Field
The invention relates to a method for preparing graphene by directly stripping ionic liquid.
Background
Graphene is a two-dimensional material with hexagonal honeycomb-shaped ordered arrangement formed by carbon atoms hybridized in a sp2 bonding mode. The novel carbon material with the two-dimensional honeycomb structure has excellent performances in various aspects, such as excellent light transmission, only 2.3% light absorption, heat conductivity coefficient as high as 5300W/m.K, and electron mobility at normal temperature over 15000cm2V.s, resistivity of only 10-6Ω · cm, and graphene is also the thinnest but hardest material currently known. Due to the unique properties, the graphene has extremely high application value and potential in a plurality of fields such as energy storage, photoelectric devices, gas sensors and composite materials.
The preparation method of graphene is various, and mainly includes a chemical vapor deposition method, a redox method, a liquid phase stripping method, a mechanical stripping method and the like. The micromechanical stripping method can only produce limited graphene sheets, and is not suitable for industrial and large-scale production requirements. The chemical vapor deposition method can meet the requirement of large-scale preparation of high-quality graphene, but has high cost and complex process. The oxidation-reduction method can be used for preparing the graphene on a large scale, but the obtained graphene is not high in quality, can generate a large amount of acid water, and is extremely easy to damage the environment. The liquid phase exfoliation method can produce high quality graphene, but the yield is low, limiting its commercial application.
The ionic liquid is low-temperature molten salt consisting of anions and cations, has the outstanding advantages of low vapor pressure, good stability, no pollution, easy recovery and the like, and is known as a green solvent. In addition, ionic liquids have low surface energy and strong polarity, can dissolve various inorganic materials, and have attracted more and more attention in the preparation of inorganic nano molecules and composite materials in recent years.
The ionic liquid has a surface coefficient similar to that of graphene, so that the ionic liquid can be applied to the application of preparing graphene by stripping. CN102730676A discloses a preparation method of graphene, which is to grind a mixture of crystalline flake graphite powder and an ionic liquid under an oxygen-free condition to obtain a mixture containing graphene, and then ultrasonically disperse the mixture to obtain a graphene dispersion liquid. Although graphene can be obtained, 1.5 × 10 is required5-8.0×105The pressure of Pascal also needs oxygen-free atmosphere, the preparation conditions are relatively harsh, and the requirement on equipment is high. In the preparation method of graphene disclosed in CN103626162A, graphite is dispersed in an ionic liquid and is dispersed and peeled by a ball milling method, and then is washed and dried to obtain graphene with a high specific surface area. However, in the preparation process, a large amount of heterogeneous organic solvents are required to completely remove the ionic liquid in the graphene, which increases the preparation cost, and the treatment of the organic waste liquid also causes many environmental problems. CN103708442A discloses a method for preparing graphene from ionic liquid, which comprises preparing graphene oxide by mixing and reacting ionic liquid with acid and an oxidant, and reducing the graphene oxide into graphene by hydrazine hydrate. Although the use amount of acid and oxidant is reduced, the use amount cannot be completely avoided, and the obtained graphene oxide needs to be reduced by hydrazine hydrate, so that the toxicity is high, and the environmental hazard is large. CN 103626164A discloses a preparation method of graphene, which comprises the steps of intercalating graphite, and then stripping the graphite by using ionic liquid under the action of an external magnetic field, wherein although the production efficiency of the graphene can be improved, the intercalation process needs high temperature conditions of 460 and 550 ℃, the post-treatment step is complicated, the production cost is high, and the preparation method is not suitable for large-scale popularization.
Disclosure of Invention
The invention aims to provide a method for preparing graphene by directly stripping ionic liquid.
The technical scheme adopted by the invention is as follows:
a method for preparing graphene by directly stripping ionic liquid comprises the following steps:
1) mixing graphite and ionic liquid, stirring for reaction, adding water, stirring, and collecting precipitate;
2) and cleaning and drying the precipitate to obtain the graphene.
In the step 1), the mass ratio of graphite to ionic liquid is 1: (1-10).
In the step 1), the graphite is at least one of crystalline flake graphite, artificial graphite and expanded graphite.
In the step 1), the ionic liquid is alkaline ionic liquid.
In the step 1), the ionic liquid is at least one of 1-butyl-3-methylimidazole hydroxide, 1-ethyl-3-methylimidazole hydroxide, 1-butyl-3-methylimidazole imidazole salt, 1-butyl-3-methylimidazole hydrogen carbonate and 1-butyl-3-methylimidazole acetate.
In the step 1), the temperature of the stirring reaction is 0-100 ℃, and the time of the stirring reaction is 1-15 h.
In the step 1), adding water and stirring for 5-15 min; the added water is deionized water, and the dosage ratio of the deionized water to the graphite is (15-25) mL; 1g of the total weight of the composition.
In the step 1), the method for collecting the precipitate is centrifugal separation and collection.
In the step 2), the washing is specifically to wash the precipitate for 2-5 times by using deionized water.
In the step 2), the drying method is spray drying or freeze drying.
The invention has the beneficial effects that:
according to the preparation method, the graphene is prepared under mild conditions by utilizing the surface coefficient of the alkaline ionic liquid similar to that of the graphene and the impregnation and swelling effects of anions on the graphite lamellar structure, and the preparation method has the advantages of low cost, environmental friendliness, simplicity in operation and high efficiency.
Specifically, the method comprises the following steps:
compared with the existing graphene preparation technology, the alkaline ionic liquid selected by the invention, particularly the imidazole hydroxide ionic liquid, has better swelling and permeability on a graphite structure compared with other ionic liquids, and the graphene can be obtained by stirring, washing and separating graphite at room temperature.
The method for preparing the graphene is simple to operate, low in requirements on production equipment, high in production efficiency, free of oxidation or reduction and other reactions in the stripping process, complete in structure of the produced graphene, few in defects, low in production cost and free of harm to the environment, and the ionic liquid can be recycled.
The method provided by the invention is simple, the cost is low, and the obtained graphene is high in yield, good in quality and suitable for large-scale popularization and application.
Drawings
Fig. 1 is a TEM electron micrograph of graphene prepared in example 1;
fig. 2 is a raman spectrum of graphene prepared in example 1.
Detailed Description
A method for preparing graphene by directly stripping ionic liquid comprises the following steps:
1) mixing graphite and ionic liquid, stirring for reaction, adding water, stirring, and collecting precipitate;
2) and cleaning and drying the precipitate to obtain the graphene.
Preferably, in the step 1), the mass ratio of graphite to the ionic liquid is 1: (1-10).
Preferably, in the step 1), the graphite is at least one of flake graphite, artificial graphite and expanded graphite; further preferably, in step 1), the graphite is flake graphite.
Preferably, in step 1), the ionic liquid is a basic ionic liquid; more preferably, in the step 1), the ionic liquid is at least one of 1-butyl-3-methylimidazole hydroxide, 1-ethyl-3-methylimidazole hydroxide, 1-butyl-3-methylimidazole imidazole salt, 1-butyl-3-methylimidazole hydrogen carbonate and 1-butyl-3-methylimidazole acetate; still more preferably, in the step 1), the ionic liquid is at least one of 1-butyl-3-methylimidazole hydroxide, 1-ethyl-3-methylimidazole hydroxide, 1-butyl-3-methylimidazole hydrogen carbonate and 1-butyl-3-methylimidazole acetate.
Preferably, in the step 1), the stirring reaction temperature is 0-100 ℃, and the stirring reaction time is 1-15 h; more preferably, in the step 1), the stirring reaction temperature is 20-30 ℃, and the stirring reaction time is 4-12 h.
Preferably, in the step 1), water is added and stirred for 5-15 min; the added water is deionized water, and the dosage ratio of the deionized water to the graphite is (15-25) mL; 1g of the total weight of the composition.
Preferably, in step 1), the method for collecting the precipitate is centrifugation collection.
Preferably, in the step 2), the washing is specifically washing the precipitate with deionized water for 2-5 times.
Preferably, in step 2), the drying method is spray drying or freeze drying.
The present invention will be described in further detail with reference to specific examples. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1:
5g of flake graphite and 10mL of ionic liquid 1-butyl-3-methylimidazole hydroxide are mixed, continuously stirred for 4 hours at the temperature of 25 ℃, then 100mL of deionized water is added, and stirring is continued for 10 minutes.
And (3) centrifugally separating the mixture, washing the mixture with deionized water for 3 times, drying the aqueous solution of the ionic liquid for reuse, and freeze-drying the precipitate to obtain the graphene of the embodiment 1.
The graphene prepared in example 1 was subjected to characterization analysis. Fig. 1 is a TEM electron micrograph of graphene prepared in example 1. Fig. 2 is a raman spectrum of graphene prepared in example 1.
Example 2:
5g of crystalline flake graphite and 20mL of ionic liquid 1-ethyl-3-methylimidazole hydroxide are mixed, continuously stirred for 4 hours at the temperature of 25 ℃, then 100mL of deionized water is added, and stirring is continued for 10 minutes.
And (3) centrifugally separating the mixture, washing the mixture with deionized water for 4 times, drying the aqueous solution of the ionic liquid for reuse, and freeze-drying the precipitate to obtain the graphene of the embodiment 2.
Example 3:
5g of flake graphite and 50mL of ionic liquid 1-butyl-3-methylimidazole bicarbonate are mixed, continuously stirred for 12 hours at the temperature of 25 ℃, then 100mL of deionized water is added, and stirring is continued for 10 minutes.
And (3) centrifugally separating the mixture, washing the mixture with deionized water for 5 times, drying the aqueous solution of the ionic liquid for reuse, and freeze-drying the precipitate to obtain the graphene of the embodiment 3.
Example 4:
5g of crystalline flake graphite and 50mL of ionic liquid 1-butyl-3-methylimidazolium acetate are mixed, and then the mixture is continuously stirred for 12 hours at the temperature of 25 ℃, and then 100mL of deionized water is added and the stirring is continued for 10 minutes.
And (3) centrifugally separating the mixture, washing the mixture with deionized water for 5 times, drying the aqueous solution of the ionic liquid for reuse, and freeze-drying the precipitate to obtain the graphene of the embodiment 4.
The embodiment shows that the method for preparing the graphene in a large scale has the advantages of wide raw material source, low cost and simple process route, and is beneficial to industrial popularization and production of the graphene.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method for preparing graphene by directly stripping ionic liquid is characterized by comprising the following steps: the method comprises the following steps:
1) mixing graphite and ionic liquid, stirring for reaction, adding water, stirring, and collecting precipitate;
2) cleaning and drying the precipitate to obtain graphene;
in the step 1), the ionic liquid is alkaline ionic liquid, and specifically is at least one of 1-butyl-3-methylimidazole hydroxide, 1-ethyl-3-methylimidazole hydroxide, 1-butyl-3-methylimidazole hydrogen carbonate and 1-butyl-3-methylimidazole acetate.
2. The method for preparing graphene by directly stripping ionic liquid according to claim 1, wherein the method comprises the following steps: in the step 1), the mass ratio of graphite to ionic liquid is 1: (1-10).
3. The method for preparing graphene by directly stripping ionic liquid according to claim 2, wherein the method comprises the following steps: in the step 1), the graphite is at least one of crystalline flake graphite, artificial graphite and expanded graphite.
4. The method for preparing graphene by directly stripping ionic liquid according to claim 1, wherein the method comprises the following steps: in the step 1), the temperature of the stirring reaction is 0-100 ℃, and the time of the stirring reaction is 1-15 h.
5. The method for preparing graphene by directly stripping ionic liquid according to claim 1, wherein the method comprises the following steps: in the step 1), adding water and stirring for 5-15 min; the added water is deionized water, and the dosage ratio of the deionized water to the graphite is (15-25) mL; 1g of the total weight of the composition.
6. The method for preparing graphene by directly stripping ionic liquid according to claim 1, wherein the method comprises the following steps: in the step 1), the method for collecting the precipitate is centrifugal separation and collection.
7. The method for preparing graphene by directly stripping ionic liquid according to claim 1, wherein the method comprises the following steps: in the step 2), the washing is specifically to wash the precipitate for 2-5 times by using deionized water.
8. The method for preparing graphene by directly stripping ionic liquid according to claim 1, wherein the method comprises the following steps: in the step 2), the drying method is spray drying or freeze drying.
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| CN109052314B (en) * | 2018-09-17 | 2021-01-26 | 柯良节 | Method for stripping multilayer two-dimensional material |
| CN111285361B (en) * | 2020-04-14 | 2022-12-27 | 中北大学 | High-performance liquid-phase mechanical preparation method of low-defect and high-dispersion graphene |
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| 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 |
| CN103626162A (en) * | 2012-08-27 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103896253A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103896259A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| 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 |
| CN107792848A (en) * | 2017-10-27 | 2018-03-13 | 广东烯谷碳源新材料有限公司 | The method that synchronizing ultrasound chemistry prepares functionalization graphene with mechanochemical reaction |
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