CN108467031A - A kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type - Google Patents
A kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type Download PDFInfo
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- CN108467031A CN108467031A CN201810411856.6A CN201810411856A CN108467031A CN 108467031 A CN108467031 A CN 108467031A CN 201810411856 A CN201810411856 A CN 201810411856A CN 108467031 A CN108467031 A CN 108467031A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- 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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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention provides a kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type.Iodide Bromide and graphite Hybrid Heating are prepared into three rank graphite intercalation compounds, three rank graphite intercalation compounds is made to be chemically reacted in supercritical water, to efficiently prepare three atomic layer high-quality graphenes；With molte-salt synthesis by between anhydrous ferric trichloride insertion graphene layer, three layer graphene intercalation compound of p-type is obtained；Alternatively, by between metallic potassium insertion graphene layer, three layer graphene intercalation compound of N-shaped is obtained.N-shaped and three layer graphene intercalation compound of p-type prepared by the method for the present invention had both remained the good electricity of graphene, property optically and thermally etc., the new physicochemical characteristic such as superconducting characteristic, catalysis characteristics and optical characteristics is introduced again, and its nanometer grade thickness 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, superconductor, transparent electrode, high frequency transistor.
Description
Technical field
The present invention relates to graphene intercalation compound preparation fields, and p-type three is prepared using graphene and anhydrous ferric trichloride
Layer graphene intercalation compound；Three layer graphene intercalation compound of N-shaped is prepared using graphene and metallic potassium.
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 method for forming graphite intercalation compound using object atom or molecule come this body material of successively doped graphite
It is an important method of graphite chemical doping, wherein this kind of object atom or molecule are referred to as intercalator.The presence of intercalator
Make graphite layers away from increase, while different intercalators also can allow the free carrier of graphite linings to migrate, to be had
There is the compound of the properties such as different electricity, calorifics and magnetics.According to the type that carrier shifts, it is big that intercalator is divided into two
Class：Donor-type intercalator and acceptor type intercalator, wherein the former provides electronics to carbon atom, and the latter takes electricity by force from carbon atom
Son；N-shaped and p-type intercalation compound can be referred to as by being formed by intercalation compound.Graphite is by interlayer made of chemical treatment
Compound, property are significantly better than graphite, have high temperature resistant, anti-thermal shock, anti-oxidation, corrosion-resistant, lubricity and leakproofness etc. excellent
Benign energy or function, are to prepare novel conductive material, battery material, hydrogen storage material, effective catalyst, soft graphite, sealing material
The raw material of material, application range have been expanded to the necks such as metallurgy, oil, chemical industry, machinery, aerospace, atomic energy, novel energy
Domain.Traditional graphite intercalation compound is due to size, it is difficult to apply the manufacturing field in microelectronic component.Graphene is carbon
Two dimensional crystal made of atom is arranged with regular hexagon structural cycle.Graphene has great specific surface area, high visible
Light transmission rate also has the good conductive and capacity of heat transmission and high intensity mechanical performance, has caused material science, semiconductor skill
The research agitation in the fields such as art, microelectric technique.Multi-layer graphene intercalation compound with nanometer grade thickness both can be base
Plinth physical study provides good material, and will have better practical prospect in terms of micro-nano photoelectronics.Therefore, with few
Graphene intercalation compound based on layer graphene is studied in devices such as novel micro nanometer electronics, transparent electrode, high frequency transistors
Manufacture view have 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 has fusion method.Fusion method is that graphite and reactant Hybrid Heating are directly made insert
It is reacted with graphite under melting condition and compound between graphite layers is made, the method reaction speed is fast, and reaction is abundant, and it is low that some can be made
The compound between graphite layers sample of rank.Reaction system and process are simple to operation, are suitable for a large amount of synthesis.But how except after dereaction
The reactant being attached on compound between graphite layers, and obtain stage structure and gone back the problem of forming consistent compound between graphite layers
Have to be solved.Block-like CaC has been made using fused salt mixt method in Emery of France etc.6Sample, for the further research of the substance
Provide good condition.Graphite and the lithium calcium alloy of melting are in direct contact in experiment, anti-in the environment of 350 DEG C with pure argon
Ying Shitian, in reaction, that initially enter graphite layers is Li, exchange reaction occurs with the carry out Ca and Li of reaction, finally
Li is substituted completely.Preparing FeCl3What is used when-GIC is also molten-salt growth method, and reaction temperature is 400 DEG C, and the reaction time is 4 small
When, raw material proportioning C: FeCl3It is 1: 5, obtained product is pure second-order F eCl3Binary compound between graphite layers.Graphite intercalation chemical combination
Object is due to size, it is difficult to the manufacturing field in microelectronic component is applied, and graphene is with good performance, graphene is inserted
Layer compound research has great potentiality in the manufacture view of the devices such as novel micro nanometer electronics, transparent electrode, high frequency transistor.
The reaction system and process of fusion method are simple to operation, are suitable for a large amount of synthesis, can be applicable to graphene intercalation compound and prepare neck
Domain.N-shaped and p-type graphene intercalation compound had not only remained the good electricity of graphene, property optically and thermally etc., but also
Introduce some new physicochemical characteristics, such as superconducting characteristic, catalysis characteristics and optical characteristics.Therefore it needs to prepare N-shaped and p-type
It is inclined to be applied to superconductor, electrode, hydrogen storage material, display, battery and optics for the effective ways of graphene intercalation compound
Shake the fields such as device.
Invention content
The present invention provides a kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type.
The present invention adopts the following technical scheme that：
A kind of preparation method of N-shaped and three layer graphene intercalation compound of p-type, includes the following steps：
(1) Iodide Bromide and graphite Hybrid Heating are prepared into three rank graphite intercalation compounds, makes three rank graphite intercalation compounds
Chemical reaction is carried out in supercritical water and generates gas stripping graphite flake layer, obtains three atomic layer high-quality graphene materials；
(2) it uses molte-salt synthesis by between anhydrous ferric trichloride insertion graphene layer, obtains three layer graphene intercalation chemical combination of p-type
Object；Between metallic potassium is inserted into graphene layer, three layer graphene intercalation compound of N-shaped is obtained.
Graphite in step (1) preferentially selects 10~10000 mesh expanded graphites, is secondly highly oriented pyrolytic graphite, scale
Graphite, micro crystal graphite or mixture.
The temperature of Iodide Bromide and graphite Hybrid Heating is about 100 DEG C in step (1), and the reaction time is 24~72h.
Supercritical water local environment asks that temperature is 374 DEG C or more in step (1), and pressure is 22.1MPa or more.
In step (2) anhydrous ferric trichloride be inserted into graphene layer between reaction temperature be 380~420 DEG C, the time be 12~
48h。
Reaction temperature is 180~220 DEG C between metallic potassium is inserted into graphene layer in step (2), and the time is 0.5~12h.
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) intercalator of diatomic layer can be loaded into graphene film by three layer graphene intercalation compounds prepared by the present invention
Between layer, the two-dimensional sheet structure with properties such as different electricity, calorifics and magnetics is prepared, it is good both to have remained graphene
Electricity, property optically and thermally etc., and introduce superconducting characteristic, catalysis characteristics and optical characteristics etc. new materialization is special
Property, and its nanometer grade thickness overcomes the too big disadvantage of traditional graphite intercalation compound size, can be applicable to novel micro nanometer
The manufacture view of the devices such as electronics, superconductor, transparent electrode, high frequency transistor.
Description of the drawings
Fig. 1 is the schematic diagram that the method for the present invention prepares graphene intercalation compound.
Fig. 2 is the TEM figures that the method for the present invention prepares three layer graphenes.
Fig. 3 is the TEM figures of p-type graphene intercalation compound prepared by the method for the present invention.
Fig. 4 is the TEM figures of N-shaped graphene intercalation compound prepared by the method for the present invention.
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 Iodide Bromide is uniformly mixed with 50mg expanded graphites, is packed into protection gas Ar gas, is enclosed within 50mL glass
It in bottle, is placed in 100 DEG C of oil bath environment, heats 12h, prepare three rank graphite intercalation compounds.
(2) graphite intercalation compound is taken out and is filtered from vial rapidly.
(3) all graphite intercalation compounds are put into quartz boat rapidly, quartz boat is put into argon gas protection atmosphere.
(4) quartz boat is heated to 800 DEG C, maintains 5min.
(5) reaction finishes, and takes out sample, and cleaning sample obtains graphene powder aggregation.
(6) by the anhydrous FeCl of 0.3g3It is uniformly mixed with 0.05g graphene powders, vacuum tightness is pacified in 20mL specification vacuum
In bottle.
(7) vacuum ampulla is put into Muffle furnace, 1h is warming up to 380 DEG C, maintains 12h.
(8) product is dissolved in dilute hydrochloric acid solution, filters drying, obtains three layer graphene intercalation compound of p-type.
Fig. 2 is the TEM figures that the present embodiment prepares three layer graphenes.
Fig. 3 is the TEM figures that the present embodiment prepares p-type graphene intercalation compound.
Embodiment 2
(1) 30g Iodide Bromide is uniformly mixed with 50mg expanded graphites, is packed into protection gas Ar gas, is enclosed within 50mL glass
It in bottle, is placed in 100 DEG C of oil bath environment, heats 12h, prepare three rank graphite intercalation compounds.
(2) graphite intercalation compound is taken out and is filtered from vial rapidly.
(3) all graphite intercalation compounds are put into quartz boat rapidly, quartz boat is put into argon gas protection atmosphere.
(4) quartz boat is heated to 800 DEG C, maintains 5min.
(5) reaction finishes, and takes out sample, and cleaning sample obtains graphene powder aggregation.
(6) 0.5g metallic potassiums are uniformly mixed with 0.05g graphene powders, vacuum tightness is in 20mL specification vacuum ampullas
In.
(7) vacuum ampulla being put into Muffle furnace, 1h is warming up to 180 DEG C, maintains 4h, between metallic potassium is inserted into graphene layer,
Obtain three layer graphene intercalation compound of N-shaped.
(8) product is dissolved in tetrahydrofuran solution, for use.
Fig. 4 is the TEM figures of N-shaped graphene intercalation compound prepared by the method for the present invention.
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 three layer graphene intercalation compound of N-shaped and p-type, includes the following steps：
(1) Iodide Bromide and graphite Hybrid Heating are prepared into three rank graphite intercalation compounds, makes three rank graphite intercalation compounds super
Chemical reaction is carried out in critical and generates gas stripping graphite flake layer, obtains three atomic layer high-quality graphene materials；
(2) it uses molte-salt synthesis by between anhydrous ferric trichloride insertion graphene layer, obtains three layer graphene intercalation compound of p-type；
Between metallic potassium is inserted into graphene layer, three layer graphene intercalation compound of N-shaped is obtained.
2. preparation method according to claim 1, which is characterized in that the graphite preferentially selection 10~10000 in step (1)
Secondly mesh expanded graphite is highly oriented pyrolytic graphite, crystalline flake graphite, micro crystal graphite or mixture.
3. preparation method according to claim 1, which is characterized in that the Iodide Bromide in step (1) and graphite Hybrid Heating
Temperature be about 100 DEG C, the reaction time be 24~72h.
4. preparation method according to claim 1, which is characterized in that the supercritical water local environment in step (1) asks temperature
Degree is 374 DEG C or more, and pressure is 22.1MPa or more.
5. preparation method according to claim 1, which is characterized in that anhydrous ferric trichloride is inserted into graphene in step (2)
Interlayer reaction temperature is 380~420 DEG C, and the time is 12~48h.
6. preparation method according to claim 1, which is characterized in that the metallic potassium in step (2) is inserted between graphene layer
Reaction temperature is 180~220 DEG C, and the time is 0.5~12h.
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Cited By (3)
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| CN108862259A (en) * | 2018-08-13 | 2018-11-23 | 深圳天元羲王材料科技有限公司 | A kind of graphene production method and device |
| CN109750316A (en) * | 2018-09-12 | 2019-05-14 | 东莞理工学院 | Electrochemistry formated ammonia catalyst based on graphene quantum dot and preparation method thereof |
| CN112441579A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Method for intercalation of graphite, graphite intercalation material prepared by the method and oxidation method of hydrocarbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108862259A (en) * | 2018-08-13 | 2018-11-23 | 深圳天元羲王材料科技有限公司 | A kind of graphene production method and device |
| CN108862259B (en) * | 2018-08-13 | 2022-04-01 | 深圳天元羲王材料科技有限公司 | Graphene production method and device |
| CN109750316A (en) * | 2018-09-12 | 2019-05-14 | 东莞理工学院 | Electrochemistry formated ammonia catalyst based on graphene quantum dot and preparation method thereof |
| CN112441579A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Method for intercalation of graphite, graphite intercalation material prepared by the method and oxidation method of hydrocarbon |
| CN112441579B (en) * | 2019-08-30 | 2022-11-15 | 中国石油化工股份有限公司 | Method for intercalation of graphite, graphite intercalation material prepared by the method and oxidation method of hydrocarbon |
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Application publication date: 20180831 |