CN108190867A - A kind of method for preparing graphene - Google Patents
A kind of method for preparing graphene Download PDFInfo
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- CN108190867A CN108190867A CN201810178060.0A CN201810178060A CN108190867A CN 108190867 A CN108190867 A CN 108190867A CN 201810178060 A CN201810178060 A CN 201810178060A CN 108190867 A CN108190867 A CN 108190867A
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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
- C01B2204/22—Electronic properties
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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
- C01B2204/30—Purity
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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
Abstract
The invention discloses a kind of methods for preparing graphene, and metal powder is mixed with magnesia, are placed in high-temperature furnace body being warming up to 650 1000 DEG C in nitrogen or inert gas atmosphere；CO gases are inputted into high-temperature furnace body to be reacted, and are stopped the input of CO gases after the completion of reaction, are cooled to room temperature in nitrogen or inert gas atmosphere, obtain black powder；Black powder is impregnated with the acid solution of a concentration of 0.1 8mol/L, reaction 1 is for 24 hours；Then it is fully washed with deionized water to neutrality, freeze-drying 8 is for 24 hours to get to graphene.A kind of method for preparing graphene of the present invention, CO is replaced with CO gases2Gas reacts to prepare graphene with magnesium, and the utilization rate for making magnesium is double, and cost substantially reduces, which has the tendency of strong spontaneous progress, and the temperature of reactant rises to obtain higher, is conducive to improve the conductivity of graphene obtained；By adding in magnesium oxide particle, magnesium oxide particle is as catalyst so that reaction can be only generated graphene, and the purity for making graphene obtained is higher.
Description
Technical field
The present invention relates to carbon material technical field, more particularly to a kind of method for preparing graphene.
Background technology
Graphene is a kind of individual layer sheetlike material being made of carbon atom, because of its high intensity, high heat conductance, highly conductive
The advantages that property and high-specific surface area, receives the extensive attention of researcher.The method for preparing graphene at present mainly has：Micromechanics
Stripping method, redox chemistry stripping method, solvent-thermal method, plane of crystal epitaxial growth method, surface of SiC graphitization method, chemical gas
Phase sedimentation etc., however, existing method has the shortcomings that can not mass producing, most common solvent-thermal method uses natural stone
Ink, potassium permanganate, the concentrated sulfuric acid and concentrated nitric acid prepare graphene, has of high cost, and aftertreatment technology is complicated and easily causes environment dirt
The problem of dye.Therefore, searching is a kind of has many advantages, such as what industrialization simple for process, cheap, easy to implement mass produced
Graphene preparation method becomes the research hotspot invention content in the field.
With CO2Reaction【CO2(g)+2Mg(l)→C(s)+2MgO(s)】A large amount of heat is can release, mole gibbs freedom
Can be 680kJ/mol, the tendency for having strong spontaneous progress.Therefore by CO2Gas is converted into various carbon materials（Such as graphite
Alkene, carbon nanotube etc.）It is the new method to gradually grow up in recent years.It is reported in the patent for being CN 103332681B in application publication number
A kind of CO for restoring flowing in high temperature furnace with metal magnesium powder in road2Gas prepares the method for graphene.The patent is with metal
Magnesium powder is reducing agent, and nano magnesia is template, by magnesium powder in CO2Self-propagating combustion mode in atmosphere, is successfully prepared
Graphene rich in meso-hole structure.MgO in system acts not only as the growth that template promotes graphene, while MgO is equably
It is dispersed between graphene sheet layer, can also play the role of that graphene is prevented to reunite.The manufacturing cost of this method is mainly derived from
The reducing agent magnesium of higher price.However, with CO2Gas reacts to prepare graphene with magnesium, and two magnesium atoms just displace one
Carbon atom, cost of manufacture are higher；Meanwhile template is done with the MgO of reaction generation, the purity of graphene obtained is relatively low.
Invention content
The object of the present invention is to provide a kind of methods for preparing graphene, process is simple, equipment requirement is low, cost relatively
It is low and can prepare with scale graphene, graphene purity obtained is higher.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
A kind of method for preparing graphene, includes the following steps：
（1）Metal powder with magnesia is mixed, is placed in high-temperature furnace body, with 5-20 in nitrogen or inert gas atmosphere
DEG C/heating rate of min rises to 650-1000 DEG C；
（2）CO gases are inputted into the high-temperature furnace body to be reacted, and after reaction starts, reduce the gas in the high-temperature furnace body
Pressure after the completion of reaction, stops the input of CO gases, is cooled to room temperature in nitrogen or inert gas atmosphere, obtains black powder；
（3）The black powder is impregnated with the acid solution of a concentration of 0.1-8mol/L, reacts 1-24h；Then it is filled with deionized water
Point washing is to neutrality, and freeze-drying 8-24h is to get to graphene.
Preferably, in step（2）In, after reaction starts, the air pressure in the high-temperature furnace body is 0.05-0.099 megapascal.
Preferably, in step（2）In, after reaction starts, stop the input of CO gases after 5-300min.
Preferably, in step（1）In, the metal powder is by one or more kinds of groups in magnesium powder, aluminium powder, lithium powder
Into.
Preferably, in step（1）In, the grain diameter of the magnesia is 0.05-5 microns.
Preferably, in step（1）In, the mass ratio of the metal powder and the magnesia is 1：1-15.
Preferably, in step（1）In, the metal powder is ground with the magnesia in nitrogen or inert gas atmosphere
0.5-3h is ground, is placed into after mixing in the high-temperature furnace body.
Preferably, in step（3）In, the acid solution is by one kind in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, organic acid or one
Kind composition described above.
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art：A kind of system of the present invention
The method of standby graphene, CO is replaced with CO gases2Gas reacts to prepare graphene with magnesium【CO(g)+Mg(l)→C(s)+MgO
(s)】, the utilization rate for making magnesium is double, and cost substantially reduces, and the molar Gibbs free energy of the reaction is 432kJ/mol, is also had
The tendency of strong spontaneous progress, the temperature of reactant rise to obtain higher, are more advantageous to improving the conductivity of graphene obtained；It is logical
It crosses in Mg and CO2Before reaction, magnesium oxide particle being added in, magnesium oxide particle is as catalyst so that reaction can be only generated graphene,
The purity for making graphene obtained is higher；
This method also has following advantages with graphene obtained：
With using high pressure CO2Gases is waited to be compared for the method for carbon source, the equipment used in the present invention is simple and cheap, safe,
Reaction process is more mild, and the Wen Sheng of reactant can easily be accommodated；
Compared with conventional chemical vapor deposition and the graphene preparation methods such as chemical stripping method, preparation process of the present invention is simple, into
Sheet is cheap, favorable reproducibility, is easy to apply；
Grapheme material obtained has very high specific surface, and specific surface area is up to 600-1500m2/g；
Graphene obtained is the excellent electrode material of ultracapacitor；And conductivity is higher than 5000S/m, can be used as lithium from
The conductive material of sub- battery, lithium-air battery and other batteries.
Description of the drawings
The transmission electron microscope photo of graphene of the attached drawing 1 obtained by embodiment 1；
The nitrogen adsorption desorption and pore size distribution curve of graphene of the attached drawing 2 obtained by embodiment 1.
Specific embodiment
The technical solution of the present invention will be further described below with reference to the accompanying drawings.
Embodiment 1
By magnesium metal and magnesium oxide particle with 1:8 mass ratio grinds 2h under the protection of nitrogen, then puts gained mixture
In high-temperature furnace body, 750 DEG C are risen to the heating rate of 5 DEG C/min under argon atmosphere, the CO gases of introducing are in high temperature
It is reacted away in furnace body and forms negative pressure immediately and constantly suck CO gases, it is 0.055 million to keep air pressure during reaction in high-temperature furnace body
Pa.Stop input CO air-flows after reacting 200min.It is cooled to room temperature in argon gas atmosphere, obtains black powder；By black powder
12h is reacted with the hydrochloric acid solution of a concentration of 1mol/L, is then fully washed to neutrality with deionized water, is dried to get to graphite
Alkene.
Fig. 1 is the transmission electron microscope photo of graphene obtained, it was demonstrated that the material has very flourishing mesopore-macropore level
Porous structure, aperture 20-100nm.
The left figure of Fig. 2 is isothermal adsorption desorption curve graph, it was found from the figure that：1st, it is in I types during the adsorption curve starting of sample；
It is few to illustrate that micropore exists for low-pressure end gas absorption amount speedup unobvious.2nd, there is the hysteresis loop of different characteristic at mesohigh end,
Belong to H3 types, the slit pore for sheet accumulation.
The right figure of Fig. 2 is pore size distribution curve figure, it was found from the figure that：Most probable pore size is in 1.5nm and 10nm, main distribution
In large micropore and mesoporous concentration.
Embodiment 2
By magnesium metal and magnesium oxide particle with 1:10 mass ratio grinds 2h under the protection of nitrogen, then puts gained mixture
In high-temperature furnace body, 750 DEG C are risen to the heating rate of 5 DEG C/min under argon atmosphere, the CO gases of introducing are in high temperature
It is reacted away in furnace body and forms negative pressure immediately and constantly suck CO gases, it is 0.055 million to keep air pressure during reaction in high-temperature furnace body
Pa.Stop input CO air-flows after reacting 200min.It is cooled to room temperature in argon gas atmosphere, obtains black powder；By black powder
20h is reacted with the sulfuric acid solution of a concentration of 1mol/L, is then fully washed with deionized water to neutrality, is freeze-dried 8-24h, i.e.,
Obtain graphene.
The graphene is level porous carbon materials.The porous carbon materials are calculated according to nitrogen Adsorption and desorption isotherms
Specific surface area is 803m2/ g, Kong Rongwei 0.53cm3/g。
Embodiment 3
By magnesium metal and magnesium oxide particle with 1:12 mass ratio grinds 2h under the protection of nitrogen, then puts gained mixture
In high-temperature furnace body, 750 DEG C are risen to the heating rate of 5 DEG C/min under argon atmosphere, the CO gases of introducing are in high temperature
It is reacted away in furnace body and forms negative pressure immediately and constantly suck CO gases, it is 0.055 million to keep air pressure during reaction in high-temperature furnace body
Pa.Stop input CO air-flows after reacting 200min.It is cooled to room temperature in argon gas atmosphere, obtains black powder；By black powder
It reacts for 24 hours with the hydrochloric acid solution of a concentration of 2mol/L, is then fully washed to neutrality with deionized water, dried to get to graphite
Alkene.
The graphene is level porous carbon materials.The porous carbon materials are calculated according to nitrogen Adsorption and desorption isotherms
Specific surface area is 928m2/ g, Kong Rongwei 1.06cm3/g。
Embodiment 4
By magnesium metal and magnesium oxide particle with 1:8 mass ratio grinds 2h under the protection of nitrogen, then puts gained mixture
In high-temperature furnace body, 750 DEG C are risen to the heating rate of 5 DEG C/min under argon atmosphere, the CO gases of introducing are in high temperature
It is reacted away in furnace body and forms negative pressure immediately and constantly suck CO gases, it is 0.065 million to keep air pressure during reaction in high-temperature furnace body
Pa.Stop input CO air-flows after reacting 150min.It is cooled to room temperature in argon gas atmosphere, obtains black powder；By black powder
20h is reacted with the sulfuric acid solution of a concentration of 1mol/L, is then fully washed with deionized water to neutrality, is freeze-dried 8-24h, i.e.,
Obtain graphene.
Embodiment 5
By magnesium metal and magnesium oxide particle with 1:8 mass ratio grinds 2h under the protection of nitrogen, then puts gained mixture
In high-temperature furnace body, 750 DEG C are risen to the heating rate of 5 DEG C/min under argon atmosphere, the CO gases of introducing are in high temperature
It is reacted away in furnace body and forms negative pressure immediately and constantly suck CO gases, it is 0.085 million to keep air pressure during reaction in high-temperature furnace body
Pa.Stop input CO air-flows after reacting 250min.It is cooled to room temperature in argon gas atmosphere, obtains black powder；By black powder
20h is reacted with the sulfuric acid solution of a concentration of 1mol/L, is then fully washed with deionized water to neutrality, is freeze-dried 8-24h, i.e.,
Obtain graphene.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and be implemented, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made should all cover within the scope of the present invention.
Claims (8)
- A kind of 1. method for preparing graphene, it is characterised in that：Include the following steps：（1）Metal powder with magnesia is mixed, is placed in high-temperature furnace body, with 5-20 in nitrogen or inert gas atmosphere DEG C/heating rate of min rises to 650-1000 DEG C；（2）CO gases are inputted into the high-temperature furnace body to be reacted, and after reaction starts, reduce the gas in the high-temperature furnace body Pressure after the completion of reaction, stops the input of CO gases, is cooled to room temperature in nitrogen or inert gas atmosphere, obtains black powder；（3）The black powder is impregnated with the acid solution of a concentration of 0.1-8mol/L, reacts 1-24h；Then it is filled with deionized water Point washing is to neutrality, and freeze-drying 8-24h is to get to graphene.
- 2. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（2）In, reaction starts Afterwards, the air pressure in the high-temperature furnace body is 0.05-0.099 megapascal.
- 3. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（2）In, reaction starts Afterwards, stop the input of CO gases after 5-300min.
- 4. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（1）In, the metal Powder is made of the one or more in magnesium powder, aluminium powder, lithium powder.
- 5. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（1）In, the oxidation The grain diameter of magnesium is 0.05-5 microns.
- 6. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（1）In, the metal The mass ratio of powder and the magnesia is 1：1-15.
- 7. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（1）In, by the gold Belong to powder and 0.5-3h is ground in nitrogen or inert gas atmosphere with the magnesia, place into the high temperature furnace after mixing In body.
- 8. a kind of method for preparing graphene according to claim 1, it is characterised in that：In step（3）In, the acid is molten Liquid is made of the one or more in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, organic acid.
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| CN201810178060.0A CN108190867A (en) | 2018-03-05 | 2018-03-05 | A kind of method for preparing graphene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109292757A (en) * | 2018-11-20 | 2019-02-01 | 张家港博威新能源材料研究所有限公司 | A kind of graphene and preparation method thereof |
| CN109354012A (en) * | 2018-11-22 | 2019-02-19 | 哈尔滨工业大学 | A kind of preparation method of low cost high-volume graphene |
| CN109585174A (en) * | 2018-11-09 | 2019-04-05 | 中国科学院电工研究所 | A kind of graphene/absorbent charcoal composite material and preparation method thereof |
| CN110372387A (en) * | 2019-08-06 | 2019-10-25 | 宁夏圣川碳基材料科技有限公司 | A kind of carborundum graphite alkene composite material and preparation method thereof |
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| CN104150472A (en) * | 2014-08-01 | 2014-11-19 | 清华大学 | Graphene hollow nano fiber and preparation method thereof |
| CN106115675A (en) * | 2016-06-24 | 2016-11-16 | 中国科学院电工研究所 | A kind of method preparing mesoporous Graphene |
| CN106256762A (en) * | 2015-06-16 | 2016-12-28 | 光州科学技术院 | The preparation method of multi-layer graphene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104150472A (en) * | 2014-08-01 | 2014-11-19 | 清华大学 | Graphene hollow nano fiber and preparation method thereof |
| CN106256762A (en) * | 2015-06-16 | 2016-12-28 | 光州科学技术院 | The preparation method of multi-layer graphene |
| CN106115675A (en) * | 2016-06-24 | 2016-11-16 | 中国科学院电工研究所 | A kind of method preparing mesoporous Graphene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585174A (en) * | 2018-11-09 | 2019-04-05 | 中国科学院电工研究所 | A kind of graphene/absorbent charcoal composite material and preparation method thereof |
| CN109292757A (en) * | 2018-11-20 | 2019-02-01 | 张家港博威新能源材料研究所有限公司 | A kind of graphene and preparation method thereof |
| CN109354012A (en) * | 2018-11-22 | 2019-02-19 | 哈尔滨工业大学 | A kind of preparation method of low cost high-volume graphene |
| CN109354012B (en) * | 2018-11-22 | 2022-03-25 | 哈尔滨工业大学 | Low-cost preparation method of large-batch graphene |
| CN110372387A (en) * | 2019-08-06 | 2019-10-25 | 宁夏圣川碳基材料科技有限公司 | A kind of carborundum graphite alkene composite material and preparation method thereof |
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