CN110357081A - A kind of method that alkali metal intercalation prepares graphene - Google Patents
A kind of method that alkali metal intercalation prepares graphene Download PDFInfo
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- CN110357081A CN110357081A CN201810312337.4A CN201810312337A CN110357081A CN 110357081 A CN110357081 A CN 110357081A CN 201810312337 A CN201810312337 A CN 201810312337A CN 110357081 A CN110357081 A CN 110357081A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
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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
- C01B2204/04—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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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The present invention provides a kind of method that alkali metal intercalation prepares graphene, the following steps are included: (1) is in inert environments, graphite type material and alkali metal are mixed, obtain uniformly mixed graphite carbon material-alkali metal composite material, and it is stood in inert environments, make that metal intercalation reaction occurs, (2) resulting composite material is put into the liquid medium that can be reacted and is reacted, remove intercalation object, by concussion, cleaning, separation, grapheme material is obtained.The present invention also proposes the graphene that the method is prepared.In the preparation method of high-quality graphene of the present invention, golden yellow composite material after using lithium or other high activity alkali metals and graphite carbon material mixing generation intercalation is presoma, it can be carried out under the conditions ofs room temperature, air etc. in the preparation process of later period graphene, be suitble to large scale preparation graphene.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material, and in particular to a kind of preparation method of graphene.
Background technique
Graphene has excellent material properties, including with huge specific surface area, higher Young's modulus, and electronics moves
Shifting rate and the thermal conductivity of superelevation etc..Graphene is by single layer sp2Hydbridized carbon atoms rearrange, and are be currently known most thin and most
Hard nano-carbon material, and it is almost transparent, it is light, there is excellent flexibility and superpower thermal conductivity
Can, there is relatively broad application in fields such as energy storage, catalysis, composite materials.
The preparation method of graphene mainly has method from top to bottom and from bottom to top method at present.Growth method from bottom to top,
Such as traditional chemical vapor deposition method, but chemical vapor deposition method growth graphene needs harsh growing environment,
Such as higher temperature and high vacuum degree, and also need to be added catalyst growth during the deposition process, it is growing
A large amount of energy is consumed in the process, and in addition this method speed of growth is slow, and production cost greatly improves, and this greatly limits this
The application field of the graphene of class growth.Method from top to bottom, such as liquid phase stripping method, from natural graphite, using removing
Method prepares graphene oxide, and further reduction prepares graphene, and such methods generally require higher energy during the preparation process
The pre-processing of amount or Strong oxdiative object, after method by reduction prepare graphene, the graphene meeting that this method is prepared
Many flaws are caused in oxidation-reduction process, manufacturing cycle is also longer.
In order to realize large scale preparation, the commercial applications of graphene, and meet current environmental requirement, how low
Energy consumption, it is extensive, environmental protection, efficiently prepare high-quality graphene, be at present still a greatly challenge, while being also graphite
The opportunity of alkene development.
Summary of the invention
For shortcoming existing for this field, the purpose of the present invention is to propose to a kind of efficient alkali metal intercalations to prepare stone
The method of black alkene, using graphite carbon material as raw material, using lithium metal or other high activity alkali metals as intercalation material, based on gold
Belong to intercalated graphite expansion and fast reaction removal intercalation metal obtains single layer or form the few-layer graphene alkene.
The graphene obtained it is another object of the present invention to propose the preparation method.
Realize the technical solution of the object of the invention are as follows:
A kind of method that alkali metal intercalation prepares graphene, comprising the following steps:
(1) in inert environments, graphite type material and alkali metal are mixed, obtain uniformly mixed graphite-like carbon materials
Material-alkali metal composite material, and stood in inert environments, make that metal intercalation reaction occurs, until composite material is become by black
At golden yellow；
(2) resulting composite material is put into the liquid medium that can be reacted and is reacted, remove intercalation object,
By concussion, cleaning, separation, grapheme material is obtained.
Wherein, the alkali metal is one or more of lithium, sodium, potassium；The graphite type material can be natural stone
Ink or artificial graphite, specially graphite paper, graphite powder, crystalline flake graphite, expanded graphite, spherical graphite, in highly oriented pyrolytic graphite
It is one or more.
Further, the mass ratio of graphite type material and alkali metal described in step (1) is 1~10:1；Graphite type material
With alkali metal mixing after folding roll-in to be uniformly mixed；Or heating alkali metal is melted after that graphite type material stirring is added is mixed
It closes uniform.
Wherein, in step (1), the inert environments be argon atmosphere and/or helium atmosphere, stood in inert environments to
Graphite becomes golden yellow, generally 10h or more, and can be placed on always in inert environments will not further occurrence variation.
Wherein, in step (2), the liquid medium be water, methanol, ethyl alcohol, propyl alcohol, n-butanol, ethylene glycol, formic acid,
One of acetic acid, propionic acid, hydrochloric acid are a variety of.
Concussion described in step (2) can be ultrasonic vibration.
It is the operation of hydrochloric acid solution for liquid medium, the concentration of hydrochloric acid can be, but not limited to 0.05~0.5mol/L.
A kind of optional technical solution of the invention is after step (1), to be operated:
Golden yellow composite material obtained is transferred in non-inert environment and handles a period of time, above-mentioned composite material
Golden yellow is taken off completely；
The non-inert environment is air, nitrogen, carbon dioxide, ammonia, vapor, argon gas-organic acid gaseous mixture, argon
One of gas-Organic Alcohol gaseous mixture is a variety of.
Wherein, it after step (1), is operated: composite material obtained is placed in the vessel, Xiang Suoshu container slowly leads to
Enter one of vapor, argon gas-acetic acid gaseous mixture, argon gas-ethyl alcohol gaseous mixture, the golden yellow to the composite material takes off completely
It goes, takes out composite material, carry out step (2).
Implementing the mass ratio of acetic acid or ethyl alcohol in gaseous mixture can be 1-20%.
Resulting graphene has the feature that graphene thickness is 1-10 layers, and lateral dimension is 0.2-100 microns.
The graphene that the method for the invention is prepared.
The beneficial effects of the present invention are:
In the preparation method of high-quality graphene of the present invention, lithium or other high activity alkali metals and graphite-like carbon materials are used
Golden yellow composite material after material mixing generation intercalation is presoma, can be in room in the preparation process of later period graphene
It is carried out under the conditions of temperature, air etc., is suitble to large scale preparation graphene.And preparation method of the invention has abandoned traditional oxidation also
The preparation method of the high energy consumptions such as the preparation method and mechanical shearing, arc discharge of former agent high pollution, using lithium and graphite-like carbon
The method of material intercalation post-processing intercalation metal obtains the graphene of high quality, and party's legal system graphene yield is high, is obtained
Graphene product single layer rate it is high, and preparation method quickly and efficiently, low energy consumption, pollution it is small, be suitble to industrialization large-scale production.
Detailed description of the invention
Fig. 1 is that the optics after graphite powder-lithium composite material prepared by embodiment 1 is stood 24 hours in inert environments shines
Piece.
Fig. 2 is that the XRD after graphite powder-lithium composite material prepared by embodiment 1 is stood 24 hours in inert environments spreads out
Penetrate style.
Fig. 3 is the electron scanning micrograph for the graphene that embodiment 1 obtains.
Fig. 4 is the electron scanning micrograph for the graphene that embodiment 4 obtains.
Fig. 5 is the atomic force microscopy for the graphene that embodiment 1 obtains.
Specific embodiment
Illustrate technical solution of the present invention below by way of specific embodiment.It should be understood that mention one of the present invention or
Multiple steps do not repel before and after the combination step that there is also between other methods and step or these specifically mentioned steps
Other methods and step can also be inserted into.It should also be understood that these examples are merely to illustrate the present invention rather than the limitation present invention
Range.Unless otherwise indicated, the number of various method steps is only to identify the purpose of various method steps, rather than limit each method
Arrangement order or limit practical range of the invention, relativeness is altered or modified, in no substantial technological content alteration
Under conditions of, it also can be considered the enforceable scope of the present invention.
Raw material employed in embodiment and instrument do not have specific limitation to its source, buy in market or according to this
In field prepared by conventional method known to technical staff.
Embodiment 1:
(1) graphite powder and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 6:1, first passes through and adds
Heat is added graphite powder after melting lithium and is stirred, until graphite powder and lithium metal are placed in inert atmosphere place 24 after evenly mixing
Become golden yellow (attached drawing 1) to said mixture after hour；
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into ethyl alcohol (analysis is pure), intercalation metal is fast
Speed and ethanol synthesis generate gas, and composite material expands rapidly, and dispersion is in ethanol.Solution is ultrasonically treated one after the reaction was completed
Solution is cleaned repeatedly after hour, filters isolated grapheme material.
The XRD diffraction pattern of material is shown in attached drawing 2, and it is alkali metal intercalated graphite that analysis, which can obtain golden yellow material,.Through scanning electricity
Sub- microscope detection graphene is 10 layers, and lateral dimension is 10 microns (see attached drawing 3).It is detected in atomic force microscope obtained
Grapheme material, obtain grapheme material with a thickness of 3.5 nanometers (see attached drawings 5).
Embodiment 2:
(1) crystalline flake graphite and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 5:1, is rolled over repeatedly
Folded roll-in, becomes until crystalline flake graphite and lithium metal are placed in inert atmosphere after evenly mixing after placing 48 hours to said mixture
It is golden yellow；
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into the aqueous hydrochloric acid solution of 0.1mol/L, inserts
Layer metal is quickly and solution reaction generates gas, and composite material is expanded rapidly, is dispersed in aqueous hydrochloric acid solution.After the reaction was completed will
Solution cleans solution after being ultrasonically treated one hour repeatedly, filters isolated grapheme material.
Embodiment 3:
(1) expanded graphite and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 3:1, is rolled over repeatedly
Folded roll-in, becomes until crystalline flake graphite and lithium metal are placed in inert atmosphere after evenly mixing after placing 48 hours to said mixture
It is golden yellow；
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into acetic acid (analysis is pure), intercalation metal is fast
Speed and acetic acidreaction generate gas, and composite material is expanded rapidly, is dispersed in acetic acid.Solution is ultrasonically treated one after the reaction was completed
Solution is cleaned repeatedly after hour, filters isolated grapheme material.
Embodiment 4:
(1) crystalline flake graphite and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 5:1, uses roll-in
The folding roll-in of machine, until crystalline flake graphite and lithium metal are placed in inert atmosphere after placing 48 hours after evenly mixing to above-mentioned mixed
It closes object and becomes golden yellow；
(2) above-mentioned golden yellow composite material is taken out from inert environments, into the water, intercalation metal is quickly reacted with water
Gas is generated, composite material is expanded rapidly, is dispersed in water.It reacts after solution is ultrasonically treated one hour by 30s after the completion to molten
Liquid is cleaned repeatedly, filters isolated grapheme material (see attached drawing 4).
Comparing embodiment 1-4, composite material are put in different solvents such as ethyl alcohol, formic acid, acetic acid, in water or dilute hydrochloric acid, reaction
Severe degree is not distinguished significantly, but can slightly be slowed down with acid reduction.
Embodiment 5:
(1) graphite powder and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 8:1, it is folding
Roll-in, until graphite powder and lithium metal, which are placed in inert atmosphere after evenly mixing after placing 48 hours, becomes golden yellow to said mixture
Color；
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into flask, water is slowly introducing into flask
Steam is further expanded after vapor and volume after the raw lithium hydroxide of intercalation metal slow reaction, is about taken out after 2h；
(3) above-mentioned product is put into formic acid (analysis is pure), intercalation reacts with formic acid, and composite material expansion exists
30s in formic acid.Solution is cleaned repeatedly after solution is ultrasonically treated one hour after the reaction was completed, filters isolated graphite
Alkene material.
Embodiment 6:
(1) expanded graphite and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 10:1, repeatedly
Rolling is folded, is become until expanded graphite and lithium metal are placed in inert atmosphere after evenly mixing after placing 48 hours to said mixture
At golden yellow；
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into flask, argon is slowly introducing into flask
Gas-acetic acid gaseous mixture (acetic acid is brought into Ar, estimates the total charge volume ratio of acetic acid Zhan between 1%~10%), it is to be mixed
Acetic acid is further expanded with volume after the raw lithium acetate of intercalation metal slow reaction in gas；
(3) into the water by above-mentioned product, intercalation reacts with water, and composite material expansion is in water after about 1min
In.Solution is cleaned repeatedly after solution is ultrasonically treated one hour after the reaction was completed, filters isolated grapheme material.
Embodiment 7:
(1) expanded graphite and lithium metal are mixed in inert environments argon gas with the ratio of mass ratio 10:1, repeatedly
Rolling is folded, is become until expanded graphite and lithium metal are placed in inert atmosphere after evenly mixing after placing 48 hours to said mixture
At golden yellow；
(2) above-mentioned golden yellow composite material is taken out from inert environments, is put into flask, argon is slowly introducing into flask
Gas-ethyl alcohol gaseous mixture (the total charge volume ratio of acetic acid Zhan be 1%~10% between), ethyl alcohol and intercalation metal are slow in gas to be mixed
Volume further expands after reacting raw lithium ethoxide；
(3) into the water by above-mentioned product, intercalation reacts with water, and composite material expansion is in water.It has reacted
Solution is cleaned repeatedly after being ultrasonically treated solution one hour after, filters isolated grapheme material.
Above embodiment be only a specific embodiment of the invention is described, not to the scope of the present invention into
Row limits, and those skilled in the art can also do numerous modifications and variations on the basis of existing technology, set not departing from the present invention
Under the premise of meter spirit, all variations and modifications that this field ordinary engineering and technical personnel makes technical solution of the present invention,
It should fall within the scope of protection determined by the claims of the present invention.
Claims (9)
1. a kind of method that alkali metal intercalation prepares graphene, which comprises the following steps:
(1) in inert environments, graphite-like raw material and alkali metal are mixed, obtain graphite-alkali metal mixing material, and
It is stood in inert environments, makes graphite that metal intercalation reaction occur, until composite material becomes golden yellow by black；
(2) resulting composite material is put into the liquid medium that can be reacted and is reacted, remove intercalation object, passed through
Concussion, cleaning, separation, obtain graphene.
2. the method that alkali metal intercalation prepares graphene according to claim 1, which is characterized in that the alkali metal is lithium,
Sodium, one or more of potassium；The graphite type material is natural or artificial graphite, specially graphite paper, graphite
One of powder, crystalline flake graphite, expanded graphite, spherical graphite, highly oriented pyrolytic graphite are a variety of.
3. the method that alkali metal intercalation prepares graphene according to claim 1, which is characterized in that stone described in step (1)
The mass ratio of black class material and alkali metal is 1~10:1.
4. the method that alkali metal intercalation prepares graphene according to claim 1, which is characterized in that in step (1), graphite-like
Material and alkali metal mixing after folding roll-in to be uniformly mixed；Or heating alkali metal is melted after be added graphite type material stir
It mixes uniformly mixed.
5. the method that alkali metal intercalation prepares graphene according to claim 1, which is characterized in that described lazy in step (1)
Property environment be argon atmosphere and/or helium atmosphere, stand in inert environments to sample and become golden yellow, time of repose is in 10h
More than.
6. the method that alkali metal intercalation prepares graphene according to claim 1, which is characterized in that described in step (2)
Liquid medium is one of water, methanol, ethyl alcohol, propyl alcohol, n-butanol, ethylene glycol, formic acid, acetic acid, propionic acid, hydrochloric acid or a variety of.
7. the method that any one alkali metal intercalation prepares graphene according to claim 1~6, which is characterized in that step (1)
Afterwards, it is operated:
Golden yellow composite material obtained is transferred in non-inert environment and is handled, is taken off completely to above-mentioned golden yellow；It is described
Non-inert environment be air, nitrogen, carbon dioxide, ammonia, vapor, argon gas-organic acid gaseous mixture, argon gas-Organic Alcohol is mixed
Close one of gas or a variety of.
8. the method that alkali metal intercalation prepares graphene according to claim 7, which is characterized in that after step (1), grasped
Make: composite material obtained being placed in the vessel, Xiang Suoshu container is slowly introducing vapor, argon gas-acetic acid gaseous mixture, argon
One of gas-ethyl alcohol gaseous mixture, the golden yellow to the composite material are taken off completely, are taken out composite material, are carried out step
(2)。
9. the graphene that any one of claim 1~8 the method is prepared.
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| CN201810312337.4A CN110357081A (en) | 2018-04-09 | 2018-04-09 | A kind of method that alkali metal intercalation prepares graphene |
| PCT/CN2018/085135 WO2019196144A1 (en) | 2018-04-09 | 2018-04-28 | Method for preparing graphene by intercalation of alkali metal |
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| CN114408916A (en) * | 2021-12-16 | 2022-04-29 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103626165A (en) * | 2012-08-28 | 2014-03-12 | 海洋王照明科技股份有限公司 | Graphene preparation method |
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| CN104003372A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Graphene material and preparation method thereof |
| CN107416809A (en) * | 2017-06-01 | 2017-12-01 | 黄凯 | A kind of method for preparing graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102815694A (en) * | 2012-03-13 | 2012-12-12 | 华东理工大学 | Graphene preparation method, and graphene prepared through using method |
| CN103626165A (en) * | 2012-08-28 | 2014-03-12 | 海洋王照明科技股份有限公司 | Graphene preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114408916A (en) * | 2021-12-16 | 2022-04-29 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method thereof |
| WO2023109192A1 (en) * | 2021-12-16 | 2023-06-22 | 广东邦普循环科技有限公司 | Expanded graphite and preparation method therefor |
| GB2617006A (en) * | 2021-12-16 | 2023-09-27 | Guangdong Brunp Recycling Technology Co Ltd | Expanded graphite and preparation method therefor |
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Application publication date: 20191022 |