CN106744843A - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN106744843A CN106744843A CN201611199524.3A CN201611199524A CN106744843A CN 106744843 A CN106744843 A CN 106744843A CN 201611199524 A CN201611199524 A CN 201611199524A CN 106744843 A CN106744843 A CN 106744843A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- C01P2002/00—Crystal-structural characteristics
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a kind of preparation method of Graphene, comprise the following steps：(1) formalin, phenol and NaOH are well mixed, in confined conditions, reaction is cooled to room temperature, obtains kermesinus phenol resin solution；(2) phenol resin solution is well mixed with catalyst solution, obtains mixture one, or by solid catalyst incipient impregnation in phenol resin solution, obtain mixture two, the mixture one or mixture two are placed in an oven, is dried to constant weight, grind to form fine powder；(3) fine powder is warming up to 600 1000 DEG C of 2 12h of activation in a nitrogen atmosphere in retort, room temperature is cooled to；Soaked with 0.1 0.5M aqueous hydrochloric acid solutions, be washed to neutrality, dried, that is, obtain graphene powder.Method of the present invention preparation process is simple, and cost of material is low, it is adaptable to industrial mass production.The Graphene thickness for being obtained is 13 layers, and lamella size is up to tens microns.
Description
Technical field
The invention belongs to field of inorganic materials, it is related to a kind of preparation method of Graphene.
Background technology
It, by a kind of two-dimensional material of only one of which carbon atom thickness, is a kind of carbon atom with sp2 hybridized orbits that Graphene is
The flat film of the hexagonal honeycomb shape lattice structure of composition.This special structure causes Graphene in mechanics, calorifics, electricity
Excellent characteristic is demonstrated by with the aspect such as optics, so as to receive significant attention.
The preparation method of current Graphene mainly include micromechanics stripping method, graphite oxide reducing process, epitaxial growth method with
Metal catalysed processes etc..But there is preparation process complexity in these preparation methods, preparation cost is high and cannot mass produce
Problem, so that presently commercially available Graphene is expensive, the further exploitation for limiting Graphene is used.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of cost of material is low, preparation process is easy and
It is suitable to the preparation method of the Graphene of large-scale production.
Technical scheme is summarized as follows：
A kind of preparation method of Graphene, comprises the following steps：：
(1) by formalin, phenol and NaOH that volumetric concentration is 37% with mass ratio be 1:0.1~1:0.05
~0.2 ratio is well mixed, and in confined conditions, is reacted 0.5~3 hour in 60~100 DEG C, is cooled to room temperature, obtains dark red
Color phenol resin solution；
(2) it is 1 by specific volume by the phenol resin solution and catalyst solution:1~10 ratio is well mixed, and obtains mixed
Compound one, or by solid catalyst incipient impregnation in phenol resin solution, obtain mixture two, by the mixture one or
Mixture two is placed in an oven, and 50-100 DEG C of drying grinds to form fine powder to constant weight；
(3) by step (2) obtain fine powder in retort in a nitrogen atmosphere with the programming rate liter of 2-10 DEG C/min
To 600-1000 DEG C of activation 2-12h, room temperature is cooled to；Soaked with 0.1-0.5M aqueous hydrochloric acid solutions, be washed to neutrality, dried, i.e.,
Obtain graphene powder.
Catalyst solution is concentration of metal ions for Li, Na, K, Ru, Cs, Mg, Ca, Sr or Ba ion of 0.5-3M are water-soluble
Liquid.
Solid catalyst is to have loaded Fe2O3Or the catalyst of CoO, catalyst carrier is CaO, MgO, CaCO3、SrCO3、
MgCO3、BaCO3, the mass percent of Fe or Co is 2%-20% in solid catalyst.
Method of the present invention preparation process is simple, and cost of material is low, it is adaptable to industrial mass production.The graphite for being obtained
Alkene thickness is 1-3 layers, and lamella size is up to tens microns.
Brief description of the drawings：
Fig. 1 is that embodiment 1 prepares Graphene XRD piece with embodiment 10.Embodiment 1 prepares Graphene institute with embodiment 10
The graphene powder XRD of acquisition is as shown in Figure 1.23 ° or so is Graphene characteristic peak.
Fig. 2 is the SEM pictures and TEM pictures that embodiment 1 and embodiment 10 prepare Graphene.A, b are respectively the stone of embodiment 1
Black alkene SEM and TEM photos, c, d are respectively the Graphene SEM of embodiment 10 and TEM photos.Graphene thickness is 1-3 layers, lamella chi
It is very little reachable tens microns.
Embodiment 1
A kind of preparation method of Graphene, comprises the following steps：
(1) by formalin, phenol and NaOH that volumetric concentration is 37% with mass ratio be 1:0.1:0.05
Ratio is well mixed, and in confined conditions, is reacted 0.5 hour in 60 DEG C, is cooled to room temperature, obtains kermesinus phenol resin solution；
(2) it is 1 by specific volume by phenol resin solution and the 0.5M LiCl aqueous solution:1 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 50 DEG C of drying grind to form fine powder to constant weight；
(3) fine powder that step (2) is obtained is risen to the programming rate of 2 DEG C/min in a nitrogen atmosphere in retort
600 DEG C of activation 2h, are cooled to room temperature；Soaked with 0.1M aqueous hydrochloric acid solutions, be washed to neutrality, dried, that is, obtain graphene powder.
The graphene powder XRD for being obtained is as shown in Figure 1.23 ° or so is Graphene characteristic peak.
The Graphene SEM for being obtained is shown in Fig. 2 a, b with TEM photos.Graphene thickness is 1-3 layers, and lamella size is up to tens
Micron.
Embodiment 2
A kind of preparation method of Graphene, comprises the following steps：：
(1) by formalin, phenol and NaOH that volumetric concentration is 37% with mass ratio be 1:0.5:0.1 ratio
Example is well mixed, in confined conditions, is reacted 1.5 hours in 90 DEG C, is cooled to room temperature, obtains kermesinus phenol resin solution；
(2) by phenol resin solution and 1.5M Na2SO4The aqueous solution is 1 by specific volume:5 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 80 DEG C of drying grind to form fine powder to constant weight；
(3) fine powder that step (2) is obtained is risen to the programming rate of 6 DEG C/min in a nitrogen atmosphere in retort
800 DEG C of activation 6h, are cooled to room temperature；Soaked with 0.3M aqueous hydrochloric acid solutions, be washed to neutrality, dried, that is, obtain graphene powder.
Embodiment 3
A kind of preparation method of Graphene, comprises the following steps：
(1) by formalin, phenol and NaOH that volumetric concentration is 37% with mass ratio be 1:1:0.2 ratio
It is well mixed, in confined conditions, reacted 3 hours in 100 DEG C, room temperature is cooled to, obtain kermesinus phenol resin solution；
(2) it is 1 by specific volume by phenol resin solution and the 3M KOH aqueous solution:10 ratio is well mixed, and obtains mixture
One, mixture one to be placed in an oven, 100 DEG C of drying grind to form fine powder to constant weight；
(3) fine powder that step (2) is obtained is risen to the programming rate of 10 DEG C/min in a nitrogen atmosphere in retort
1000 DEG C of activation 12h, are cooled to room temperature；Soaked with 0.5M aqueous hydrochloric acid solutions, be washed to neutrality, dried, that is, obtain Graphene powder
End.
Embodiment 4
A kind of preparation method of Graphene, comprises the following steps：：
(1) with the step of embodiment 1 (1)；
(2) it is 1 by specific volume by phenol resin solution and the 0.5M RuCl aqueous solution:1 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 50 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 1 (3)
Embodiment 5
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 2 (1)；
(2) by phenol resin solution and 1.5M Cs2SO4The aqueous solution is 1 by specific volume:5 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 80 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 2 (3).
Embodiment 6
A kind of preparation method of Graphene, comprises the following steps：：
(1) with the step of embodiment 3 (1)；
(2) by phenol resin solution and 3M MgCl2The aqueous solution is 1 by specific volume:10 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 100 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 3 (3).
Embodiment 7
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 1 (1)；
(2) by phenol resin solution and 0.5M CaCl2The aqueous solution is 1 by specific volume:1 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 50 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 1 (3)
Embodiment 8
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 2 (1)；
(2) by phenol resin solution and 1.5M SrCl2The aqueous solution is 1 by specific volume:5 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 80 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 2 (3).
Embodiment 9
A kind of preparation method of Graphene, comprises the following steps：：
(1) with the step of embodiment 3 (1)；
(2) by phenol resin solution and 3M BaCl2The aqueous solution is 1 by specific volume:10 ratio is well mixed, and must mix
Thing one, mixture one is placed in an oven, and 100 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 3 (3).
Embodiment 10
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 1 (1)；
(2) by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, mixture two is placed on
In baking oven, 50 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 1 (3).
Solid catalyst is to have loaded Fe2O3Catalyst, catalyst carrier is CaO, the quality hundred of Fe in solid catalyst
Divide than being 2%.
The graphene powder XRD for being obtained is as shown in Figure 1.23 ° or so is Graphene characteristic peak.
The Graphene SEM for being obtained is shown in Fig. 2 c, d with TEM photos.Graphene thickness is 1-3 layers, and lamella size is up to tens
Micron.
Embodiment 11
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 2 (1)；
(2) by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, mixture two is placed on
In baking oven, 80 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 2 (3).
Solid catalyst is to have loaded Fe2O3Catalyst, catalyst carrier is MgO, the quality hundred of Fe in solid catalyst
Divide than being 10%.
Embodiment 12
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 3 (1)；
(2) by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, mixture two is placed on
In baking oven, 100 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 3 (3).
Solid catalyst is to have loaded Fe2O3Catalyst, catalyst carrier is CaCO3, the quality of Fe in solid catalyst
Percentage is 20%.
Embodiment 13
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 1 (1)；
(2) by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, mixture two is placed on
In baking oven, 50 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 1 (3).
Solid catalyst is the catalyst for having loaded CoO, and catalyst carrier is SrCO3, the quality of Co in solid catalyst
Percentage is 2%.
Embodiment 14
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 2 (1)；
(2) by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, mixture two is placed on
In baking oven, 80 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 2 (3).
Solid catalyst is the catalyst for having loaded CoO, and catalyst carrier is MgCO3, the quality of Co in solid catalyst
Percentage is 10%.
Embodiment 15
A kind of preparation method of Graphene, comprises the following steps：
(1) with the step of embodiment 3 (1)；
(2) by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, mixture two is placed on
In baking oven, 100 DEG C of drying grind to form fine powder to constant weight；
(3) with the step of embodiment 3 (3).
Solid catalyst is the catalyst for having loaded CoO, and catalyst carrier is BaCO3, the quality of Co in solid catalyst
Percentage is 20%.
Claims (3)
1. a kind of preparation method of Graphene, it is characterized in that comprising the following steps：
(1) by formalin, phenol and NaOH that volumetric concentration is 37% with mass ratio be 1:0.1~1:0.05~
0.2 ratio is well mixed, and in confined conditions, is reacted 0.5~3 hour in 60~100 DEG C, is cooled to room temperature, obtains kermesinus
Phenol resin solution；
(2) it is 1 by specific volume by the phenol resin solution and catalyst solution:1~10 ratio is well mixed, and obtains mixture
One, or by solid catalyst incipient impregnation in phenol resin solution, mixture two is obtained, by the mixture one or mixing
Thing two is placed in an oven, and 50-100 DEG C of drying grinds to form fine powder to constant weight；
(3) fine powder that step (2) is obtained is risen to the programming rate of 2-10 DEG C/min in a nitrogen atmosphere in retort
600-1000 DEG C of activation 2-12h, is cooled to room temperature；Soaked with 0.1-0.5M aqueous hydrochloric acid solutions, be washed to neutrality, dried, obtained final product
To graphene powder.
2. method according to claim 1, it is characterized in that it is 0.5-3M's that the catalyst solution is concentration of metal ions
Li, Na, K, Ru, Cs, Mg, Ca, Sr or Ba deionized water solution.
3. method according to claim 1, it is characterized in that the solid catalyst is to have loaded Fe2O3Or the catalysis of CoO
Agent, catalyst carrier is CaO, MgO, CaCO3、SrCO3、MgCO3、BaCO3, the mass percent of Fe or Co in solid catalyst
It is 2%-20%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624093A (en) * | 2020-11-03 | 2021-04-09 | 中国科学技术大学 | Method for preparing graphene on large scale and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528696A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene and graphene |
| CN105883778A (en) * | 2014-12-31 | 2016-08-24 | 国家电网公司 | Method for preparing graphene |
| CN105923623A (en) * | 2016-04-19 | 2016-09-07 | 广西大学 | Preparation method of graphene powder with three-dimensional hierarchical porous structure |
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- 2016-12-22 CN CN201611199524.3A patent/CN106744843A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528696A (en) * | 2014-12-16 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Preparation method for graphene and graphene |
| CN105883778A (en) * | 2014-12-31 | 2016-08-24 | 国家电网公司 | Method for preparing graphene |
| CN105923623A (en) * | 2016-04-19 | 2016-09-07 | 广西大学 | Preparation method of graphene powder with three-dimensional hierarchical porous structure |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624093A (en) * | 2020-11-03 | 2021-04-09 | 中国科学技术大学 | Method for preparing graphene on large scale and application |
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Application publication date: 20170531 |