CN108314025A - A kind of preparation method of bilayer graphene intercalation compound - Google Patents
A kind of preparation method of bilayer graphene intercalation compound Download PDFInfo
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- CN108314025A CN108314025A CN201810411872.5A CN201810411872A CN108314025A CN 108314025 A CN108314025 A CN 108314025A CN 201810411872 A CN201810411872 A CN 201810411872A CN 108314025 A CN108314025 A CN 108314025A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The present invention provides a kind of preparation method of bilayer graphene intercalation compound.Second order graphite intercalation compound is obtained using lodine chloride as intercalator, to second order graphite intercalation compound high-temperature process, lodine chloride decomposes generation gas stripping graphite flake layer and obtains the double-deck high-quality graphene material, using ferric trichloride etc. as intercalator, intercalation is carried out to the double-deck high-quality graphene with molte-salt synthesis, obtains bilayer graphene intercalation compound.The method of the present invention, using the controllable preparation of bilayer graphene, bilayer graphene intercalation compound is obtained, the presence of intercalator makes interlamellar spacing increase, intercalator also can allow the free carrier of lamella to migrate, to obtain the properties such as different electricity, calorifics and magnetics.Graphene intercalation compound based on bilayer graphene overcomes the too big disadvantage of traditional graphite intercalation compound size, can be applicable to the manufacture view of the devices such as novel micro nanometer electronics, transparent electrode, high frequency transistor.
Description
Technical field
The present invention relates to graphene intercalation compound preparation fields, and double-layer graphite is prepared using bilayer graphene and intercalator
Alkene intercalation compound.
Background technology
Graphite intercalation compound is that different atoms or molecule are inserted into graphite layers, one layer of new intercalation oxidant layer of formation
Composite material.The presence of intercalator makes graphite layers away from increase, while different intercalators can also allow the free current-carrying of graphite linings
Son migrates, to obtain having the compound of the properties such as different electricity, calorifics and magnetics.Graphite is made by chemical treatment
Intercalation compound, property is significantly better than graphite, has high temperature resistant, anti-thermal shock, anti-oxidation, corrosion-resistant, lubricity and sealing
Excellent performances or the functions such as property, be prepare novel conductive material, battery material, hydrogen storage material, effective catalyst, soft graphite,
The raw material of sealing material, application range have been expanded to metallurgy, oil, chemical industry, machinery, aerospace, atomic energy, novel energy
Equal fields.Traditional graphite intercalation compound is due to size, it is difficult to apply the manufacturing field in microelectronic component.Graphene
It is two dimensional crystal made of carbon atom is arranged with regular hexagon structural cycle.Graphene has great specific surface area, high
Visible light transmittance also has the good conductive and capacity of heat transmission and high intensity mechanical performance, has caused material science, partly led
The research agitation in the fields such as body technique, microelectric technique.Therefore, the graphene intercalation compound based on few layer graphene is ground
The manufacture view studied carefully in devices such as novel micro nanometer electronics, transparent electrode, high frequency transistors has broad prospects.
The preparation method of graphene intercalation compound can refer to the preparation method of graphite intercalation compound.Common graphite
The preparation method of intercalation compound mainly have fusion method, solvent-thermal method, dual chamber method, chemical method, electrochemical process, solid pressurization,
Explosion method and photochemical method etc..Dual chamber method is also known as vapor phase method or Vapor Transport, mainly utilizes insertion at a certain temperature
The steam of object is reacted with graphite and is made.The advantages of method is to be easier the structure and exponent number of control product, but lack
Point is that insert exists only in some carbon atomic layers of graphite surface, it is difficult to obtain the higher sample of quality, and react dress
Complexity is set, is needed especially customized, it is difficult to largely be synthesized, and the reaction time is long, reaction temperature is high, needs under vacuum
Operation.Certain metals or metal salt are dissolved in solvent and being reacted with graphite by solvent-thermal method, and common solvent has liquefied ammonia, SOCl2 to add
Organic solvent (such as benzene, naphthalene, tetrahydrofuran, dimethoxy-ethane).The method can be synthesized largely at normal temperatures, but react slow, rank
Structure is difficult to control, and easily generates ternary compound between graphite layers, and stability is poor.Fusion method is directly to mix graphite with reactant
Heating makes insert be reacted with graphite under melting condition and compound between graphite layers is made.The method reaction speed is fast, and reaction is filled
Point, the compound between graphite layers sample of some low orders can be made, reaction system and process are simple to operation, are suitable for a large amount of synthesis,
But how except the reactant being attached to after dereaction on compound between graphite layers, and obtain the stage structure graphite linings consistent with forming
Between compound the problem of it is also to be solved.Block-like CaC6 samples have been made using fused salt mixt method in Emery of France etc., for this
The further research of substance provides good condition.Graphite and the lithium calcium alloy of melting are in direct contact in experiment, 350 DEG C with
It is reacted ten days in the environment of pure argon, in reaction, that initially enter graphite layers is Li, is sent out with the carry out Ca and Li of reaction
Raw exchange reaction, finally substitutes Li completely.Preparing FeCl3What is used when-GIC is also molten-salt growth method, reaction temperature 400
DEG C, the reaction time is 4 hours, raw material proportioning C：FeCl3It is 1: 5, obtained product is pure second-order F eCl3Binary graphite layers
Close object.Chemical method can be described as liquid phase method again, and the insertion substance being in a liquid state is mixed with graphite, is reacted and generates graphite intercalation
Compound, in reaction temperature, time have a significant impact to the stage structure of product.This method equipment is simple, and reaction speed is also fast,
It is very effective to the synthesis of a large amount of samples, and the ratio for changing primitive reaction object graphite and insert can be utilized to reach desired
Stage structure and composition；Such as Br-GIC and H2SO4- GIC, the disadvantage is that the unstable products formed, if component is more in liquid phase, also
Unstable polynary graphite layers can be formed.Earliest expanded graphite, that is, graphite intercalation compound is exactly using the concentrated sulfuric acid as intercalation
Agent, be equipped with various oxidants reacted with natural flake graphite, depickling, washing, drying form.Electrochemical synthesis is mainly to be inserted into
The solution of object, including organic solution and inorganic solution or fuse salt are electrolyte, using the electrochemical system that graphite is formed as electrode,
General graphite and impressed current anode constitute anode chamber together, and some, which wraps up graphite with platinum net, makees anode, by adjusting electricity
The stage structure of control product is removed in position, electricity, is suitable for research intercalation thermodynamics.The method synthesis device is simple, and synthetic quantity is big, and
Product structure is stablized, which is that the stability of synthetic product is poorer than other methods, and high electricity in aqueous solution
Side reaction has been flowed down to occur and hardly result in single order compound.Bai Xinde etc. utilizes FeCl3、HCl、H2The mixed liquor of O carries out electrification
It learns intercalation and successfully obtains FeCl well4-GICs。
Above-mentioned several synthetic methods respectively have advantage and disadvantage, should require to select corresponding method according to preparing.Graphite intercalation
Object is closed due to size, it is difficult to the manufacturing field in microelectronic component is applied, and graphene is with good performance, graphene
Intercalation compound studies the manufacture view in devices such as novel micro nanometer electronics, transparent electrode, high frequency transistors with greatly latent
Power.The reaction system and process of fusion method are simple to operation, are suitable for a large amount of synthesis, can be applicable to the preparation of graphene intercalation compound
Field.
Invention content
The present invention provides a kind of preparation method of bilayer graphene intercalation compound.
The present invention adopts the following technical scheme that：
A kind of preparation method of bilayer graphene intercalation compound, includes the following steps：
(1) second order graphite intercalation compound is obtained using lodine chloride as intercalator, it is high to second order graphite intercalation compound
Temperature processing, lodine chloride decompose generation gas stripping graphite flake layer and obtain the double-deck high-quality graphene material；
(2) using ferric trichloride etc. as intercalator, intercalation is carried out to the double-deck high-quality graphene with molte-salt synthesis, is obtained
To bilayer graphene intercalation compound.
Intercalator of the lodine chloride as second order graphite intercalation compound in step (1).
Graphite in step (1) preferentially selects 10~150 mesh expanded graphites, is secondly highly oriented pyrolytic graphite, scale stone
Ink, micro crystal graphite or mixture.
Lodine chloride and the temperature of graphite Hybrid Heating are about 160 DEG C in step (1).
The intercalator of graphite intercalation compound is metal or metal halide, specially potassium, sodium, lithium, potassium sodium in step (2)
Alloy, lodine chloride, aluminium chloride, nickel chloride, antimony chloride, iron chloride or antimony fluoride.
The temperature of molte-salt synthesis is 380~420 DEG C in step (2).
The present invention has following advantage：
(1) step used in the present invention is simple, and equipment requirement is not high, is suitable for industry or laboratory operation.
(2) a kind of preparation method of bilayer graphene intercalation compound is proposed in the present invention, it can be by monoatomic layer
Intercalator is loaded between bilayer graphene, prepares two had with properties such as the different electricity of graphene, calorifics and magnetics
Lamellar structure is tieed up, the fields such as novel micro nanometer electronics, transparent electrode, high frequency transistor are can be applicable to.
Description of the drawings
Fig. 1 is the schematic diagram that the method for the present invention prepares bilayer graphene intercalation compound.
Fig. 2 is the TEM figures that the method for the present invention prepares bilayer graphene.
Fig. 3 is the TEM figures that the method for the present invention prepares bilayer graphene intercalation compound.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) 30g lodine chlorides are uniformly mixed with 50mg expanded graphites, are packed into protection gas Ar gas, are enclosed within 50mL glass
In bottle.
(2) it is placed in 160 DEG C of oil bath environment, heats 48h, prepare second order graphite intercalation compound.
(3) graphite intercalation compound is taken out and is filtered from vial rapidly.
(4) all graphite intercalation compounds are put into quartz boat rapidly, quartz boat is put into argon gas protection atmosphere.
(5) quartz boat is heated to 800 DEG C, maintains 5min.
(6) reaction finishes, and takes out sample, and cleaning sample obtains bilayer graphene powder aggregates.
(7) by the anhydrous FeCl of 0.3g3It is uniformly mixed with 0.05g bilayer graphene powder, vacuum tightness is true in 20mL specifications
In empty ampulla.
(8) vacuum ampulla is put into Muffle furnace, 1h is warming up to 380 DEG C, maintains 12h.
(9) product is dissolved in dilute hydrochloric acid solution, filters drying, obtains bilayer graphene intercalation compound.
Fig. 2 is the TEM figures that the present embodiment prepares bilayer graphene.
Fig. 3 is the TEM figures that the present embodiment prepares bilayer graphene intercalation compound.
Embodiment 2
(1) 30g lodine chlorides are uniformly mixed with 50mg high temperature directional thermal decomposition graphite, are packed into protection gas Ar gas, are enclosed within
In 50mL vials.
(2) it is placed in 160 DEG C of oil bath environment, heats 48h, prepare second order graphite intercalation compound.
(3) graphite intercalation compound is taken out and is filtered from vial rapidly.
(4) all graphite intercalation compounds are put into quartz boat rapidly, quartz boat is put into argon gas protection atmosphere.
(5) quartz boat is heated to 800 DEG C, maintains 5min.
(6) reaction finishes, and takes out sample, and cleaning sample obtains bilayer graphene powder aggregates.
(7) by the anhydrous FeCl of 0.3g3It is uniformly mixed with 0.05g bilayer graphene powder, vacuum tightness is true in 20mL specifications
In empty ampulla.
(8) vacuum ampulla is put into Muffle furnace, 1h is warming up to 380 DEG C, maintains 12h.
(9) product is dissolved in dilute hydrochloric acid solution, filters drying, obtains bilayer graphene intercalation compound.
Embodiment 3
(1) 30g lodine chlorides are uniformly mixed with 50mg expanded graphites, are packed into protection gas Ar gas, are enclosed within 50mL glass
In bottle.
(2) it is placed in 160 DEG C of oil bath environment, heats 48h, prepare second order graphite intercalation compound.
(3) graphite intercalation compound is taken out and is filtered from vial rapidly.
(4) all graphite intercalation compounds are put into quartz boat rapidly, quartz boat is put into argon gas protection atmosphere.
(5) quartz boat is heated to 1000 DEG C, maintains 5min.
(6) reaction finishes, and takes out sample, and cleaning sample obtains bilayer graphene powder aggregates.
(7) by the anhydrous FeCl of 0.6g3It is uniformly mixed with 0.1g bilayer graphene powder, vacuum tightness is in 20mL specification vacuum
In ampulla.
(8) vacuum ampulla is put into Muffle furnace, 0.5h is warming up to 380 DEG C, maintains 12h.
(9) product is dissolved in dilute hydrochloric acid solution, filters drying, obtains bilayer graphene intercalation compound.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (6)
1. a kind of preparation method of bilayer graphene intercalation compound, includes the following steps：
(1) second order graphite intercalation compound is obtained using lodine chloride as intercalator, at second order graphite intercalation compound high temperature
Reason, lodine chloride decompose generation gas stripping graphite flake layer and obtain the double-deck high-quality graphene material；
(2) using ferric trichloride etc. as intercalator, intercalation is carried out to the double-deck high-quality graphene with molte-salt synthesis, is obtained double
Layer graphene intercalation compound.
2. preparation method according to claim 1, which is characterized in that the lodine chloride in step (1) is inserted as second order graphite
The intercalator of layer compound.
3. preparation method according to claim 1, which is characterized in that the graphite in step (1) preferentially selects 10~150 mesh
Secondly expanded graphite is highly oriented pyrolytic graphite, crystalline flake graphite, micro crystal graphite or mixture.
4. preparation method according to claim 1, which is characterized in that the lodine chloride in step (1) and graphite Hybrid Heating
Temperature be about 160 DEG C.
5. preparation method according to claim 1, which is characterized in that the intercalator of graphite intercalation compound in step (2)
It is metal or metal halide, specially potassium, sodium, lithium, sodium-potassium eutectic, lodine chloride, aluminium chloride, nickel chloride, antimony chloride, iron chloride
Or antimony fluoride.
6. preparation method according to claim 1, which is characterized in that in step (2) temperature of molte-salt synthesis be 380~
420℃。
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| CN112723353A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Graphite intercalation compound and preparation method and application thereof |
| CN112919451A (en) * | 2021-02-04 | 2021-06-08 | 四川大学 | Biomass graphene for treating organic pollutants as well as preparation method and application of biomass graphene |
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| CN109012496B (en) * | 2018-09-29 | 2021-06-04 | 盐城师范学院 | Method for preparing diamond film by shock wave method |
| CN112723353A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Graphite intercalation compound and preparation method and application thereof |
| CN112723353B (en) * | 2019-10-29 | 2022-09-27 | 中国石油化工股份有限公司 | Graphite intercalation compound and preparation method and application thereof |
| CN112919451A (en) * | 2021-02-04 | 2021-06-08 | 四川大学 | Biomass graphene for treating organic pollutants as well as preparation method and application of biomass graphene |
| CN112919451B (en) * | 2021-02-04 | 2023-01-31 | 四川大学 | Biomass graphene for treating organic pollutants as well as preparation method and application of biomass graphene |
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Application publication date: 20180724 |