CN108423661A - It is a kind of to derive the graphene that charcoal prepares the method for graphene and its prepares with mesophase pitch - Google Patents
It is a kind of to derive the graphene that charcoal prepares the method for graphene and its prepares with mesophase pitch Download PDFInfo
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- CN108423661A CN108423661A CN201810272424.1A CN201810272424A CN108423661A CN 108423661 A CN108423661 A CN 108423661A CN 201810272424 A CN201810272424 A CN 201810272424A CN 108423661 A CN108423661 A CN 108423661A
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- 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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Abstract
Deriving the graphene that charcoal prepares the method for graphene and its prepares using mesophase pitch the present invention relates to a kind of, above-mentioned preparation method is：Mesophase pitch derivative charcoal is handled into obtain pretreatment sample through high temperature carbonization；The pretreatment sample that processing obtains is immersed in inorganic fused salt system and obtains reaction product through high-temperature heat treatment, up to graphene after reaction product is separated off fused salt and is dried.Charcoal is derived as raw material using easily graphited mesophase pitch in the present invention, graphene is prepared using fused salt intercalation lift-off technology, has preparation method simple, easily operated, low production cost, the recyclable recycling of fused salt, and the advantages that cleanliness without any pollution；And the energy consumption in raw material high-temperature heat treatment process can also be substantially reduced less than the treatment temperature of 2000 DEG C of graphitization temperatures.
Description
Technical field
The invention belongs to technical field of graphene preparation more particularly to a kind of utilization mesophase pitch to derive charcoal and prepare graphite
The method of alkene and its graphene prepared.
Background technology
Graphene is the graphite flake of monoatomic thickness, has unique two dimensional crystal structure and excellent mechanics, calorifics, electricity
The physical properties such as, optics are widely used in the industries such as nano electron device, composite material, energy stores, gas sensing, are mesh
One hot spot of the area researches such as preceding material science, Condensed Matter Physics, chemical.
Nowadays method and the raw material for preparing graphene are varied, and most common preparation method is with high-crystallinity, Gao Shi
The natural graphite of inkization degree be raw material, aoxidized using chemical method (such as strong acid, nitration mixture), intercalation, stripping, first prepare oxidation stone
Black alkene restores processing and obtains graphene.The graphene quality that the technique obtains is general (such as size is smaller, and defect is more), system
Standby process is complex, and there are problem of environmental pollutions.
It is well known that mesophase pitch be the countless regular arrangement forms of condensed-nuclei aromatics molecule ordered structure (optics respectively to
It is anisotropic), have many advantages, such as that carbon yield is high, melting regulation and control are orientated, easy graphitization, is widely used in and prepares mesophase pitch coke, needle-shaped
Coke, high power graphite electrode, mesocarbon microspheres, Mesophase Pitch-based Carbon Fibers, high-performance foam charcoal and high heat conduction charcoal/charcoal
Composite material etc..These Carbon Materials derived from mesophase pitch are easy to be graphitized after high-temperature heat treatment, are formed regular
Orderly three-dimensional accumulation layered graphite structure, is highly suitable as preparing the precursor material of graphene.Meanwhile in high-temperature fusion
Under state, alkali metal chloride and fluoride smelt salt stability are good, and viscosity is relatively low, and Ion transfer and diffusion velocity are fast, very
It is easily accessible in Carbon Materials graphite microcrystal synusia and intercalation stripping is carried out to it.Derive charcoal using easily graphited mesophase pitch
(such as mesophase pitch coke, needle coke and Mesophase Pitch-based Carbon Fibers) are raw material, using fused salt ion insertion lift-off technology system
Standby graphene (or few layer graphene piece), may be implemented carbon-coating piece size and thickness control, the preparation method is simple, is easy to grasp
Make, production cost is low, and cleanliness without any pollution, has not yet to see correlative study and patent report.
Invention content
The existing above problem is prepared for existing graphene, is now provided and a kind of being derived charcoal using mesophase pitch and prepare
The method of graphene and its graphene (or few layer graphene piece) prepared.
Specific technical solution is as follows：
The first aspect of the invention is to provide a kind of method preparing graphene with mesophase pitch derivative charcoal, has this
The feature of sample, includes the following steps：
1) mesophase pitch derivative charcoal, is handled into obtain pretreatment sample through high temperature carbonization；
2), the pretreatment sample that processing obtains in step 1) is immersed in inorganic fused salt system and is obtained instead through high-temperature heat treatment
Product is answered, up to graphene after reaction product is separated off fused salt and is dried.
Above-mentioned method, also has the feature that, mesophase pitch described in step 1) derives charcoal and dripped selected from interphase
One kind in green coke, needle coke, Mesophase Pitch-based Carbon Fibers or the band-like Carbon fibe of intermediate phase pitch-based.
The Mesophase Pitch-based Carbon Fibers provided in the present invention have splitting phenomena, and its diameter is generally higher than 20 μm.
Above-mentioned method, also has the feature that, mesophase pitch described in step 1) derives the granularity or length of charcoal
For 0.5-3cm.
The mesophase pitch that the mode that shearing or crushing can be used in the present invention obtains above-mentioned granularity or length is 0.5-3cm
Derivative charcoal.
Above-mentioned method, also has the feature that, treatment temperature is 1500-1900 in the processing of step 1) high temperature carbonization
DEG C, processing time 1-3h.
Above-mentioned method, also has the feature that, inorganic fused salt system described in step 2) is by KF, LiCl, KCl system
At, wherein the mass ratio of LiCl and KCl is 1:1.2, KF mass contents are 1-7% in the inorganic fused salt system.
The dosage of inorganic fused salt system, which is subject to just, in the present invention did not had mesophase pitch to derive charcoal.
Above-mentioned method, also has the feature that, treatment temperature is 600-900 DEG C in step 2) high-temperature heat treatment, place
The reason time is 3-7h.
Above-mentioned method, also has the feature that, fused salt is separated off using washing separation method in step 2).
Above-mentioned method, also has the feature that, washing separation method is：By reaction product successively in ultrasonic vibration condition
Lower washing is simultaneously filtered 2-6 times.
Above-mentioned method, also has the feature that, drying temperature is 40-80 DEG C in step 2), drying time 4-
10h。
The second aspect of the invention is to provide a kind of graphene prepared using the above method.
The advantageous effect of said program is：
(1) it is raw material to derive charcoal using easily graphited mesophase pitch in the present invention, and by it in less than 2000 DEG C stones
It is preferably converted into the Carbon Materials of graphite-like structure at a temperature of inkization, so that follow-up intercalation stripping prepares graphene, ensures simultaneously
Graphene layer chip size is sufficiently large inside Carbon Materials；And it can also be substantially reduced less than the treatment temperature of 2000 DEG C of graphitization temperatures
Energy consumption in raw material high-temperature heat treatment process；
(2) graphene is prepared using fused salt intercalation lift-off technology in the present invention, has preparation method simple, it is easily operated,
Low production cost, the recyclable recycling of fused salt, and the advantages that cleanliness without any pollution；
(3) preferable using graphene quality prepared by preparation method of the present invention, synusia size is 100-10000 μm2, layer
Number is layer 1-7, and can realize synusia size, layer according to precursor material size, charing process condition and the fused salt extent of reaction
Several controllableization.
Description of the drawings
Fig. 1 is the transmission electron microscope image of the graphene prepared in the embodiment of the present invention 1.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of not making creative work it is all its
His embodiment, shall fall within the protection scope of the present invention.
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
The invention will be further described in the following with reference to the drawings and specific embodiments, but not as limiting to the invention.
Embodiment 1
A kind of graphene, preparation method include the following steps：
1) it is 1-2cm that mesophase pitch coke powder, which, is broken to granule size, then by the mesophase pitch coke after crushing 1500
Through high temperature carbonization 1h at DEG C, pretreatment sample is obtained；
2), the pretreatment sample that processing obtains in step 1) is immersed in LiCl-KCl-KF inorganic fused salt systems, then at
High-temperature heat treatment 3h, obtains reaction product at 600 DEG C, reaction product is washed under the conditions of ultrasonic vibration successively and filter 2 times with
It is separated off fused salt, up to graphene after 40 DEG C of dry 4h；
Wherein, inorganic fused salt system is made of KF, LiCl, KCl in step 2), and the mass ratio of LiCl and KCl are 1:1.2
KF mass contents are 4% in inorganic fused salt system；
Graphene synusia size manufactured in the present embodiment is 1000-5000 μm2, the number of plies is layer 1-7.As shown in Figure 1, this reality
Apply in example that made graphene film size is larger, thin, transparent, thickness is more uniform, and defect is few.
Embodiment 2
A kind of graphene, preparation method include the following steps：
1), by needle coke be crushed to granule size be 2-3cm, then by the needle coke after crushing at 1700 DEG C through pyrocarbon
Change 2h, obtains pretreatment sample；
2), the pretreatment sample that processing obtains in step 1) is immersed in LiCl-KCl-KF inorganic fused salt systems, then at
High-temperature heat treatment 4h, obtains reaction product at 750 DEG C, reaction product is washed under the conditions of ultrasonic vibration successively and filter 4 times with
It is separated off fused salt, up to graphene after 60 DEG C of dry 6h；
Wherein, inorganic fused salt system is made of KF, LiCl, KCl in step 2), and the mass ratio of LiCl and KCl are 1:1.2
KF mass contents are 4% in inorganic fused salt system；
Graphene synusia size manufactured in the present embodiment is 5000-10000 μm2, the number of plies is 1-4 layers.
Embodiment 3
A kind of graphene, preparation method include the following steps：
1) it is 0.5-1cm that Mesophase Pitch-based Carbon Fibers, which, are cut into length, then the mesophase pitch that will be obtained after shearing
Based carbon fiber, through high temperature carbonization 2.5h, obtains pretreatment sample at 1800 DEG C；
2), the pretreatment sample that processing obtains in step 1) is immersed in LiCl-KCl-KF inorganic fused salt systems, then at
High-temperature heat treatment 6h, obtains reaction product at 830 DEG C, reaction product is washed under the conditions of ultrasonic vibration successively and filter 6 times with
It is separated off fused salt, up to graphene after 65 DEG C of dry 8h；
Wherein, inorganic fused salt system is made of KF, LiCl, KCl in step 2), and the mass ratio of LiCl and KCl are 1:1.2
KF mass contents are 5% in inorganic fused salt system；
Graphene synusia size manufactured in the present embodiment is 100-1000 μm2, the number of plies is 1-5 layers.
Embodiment 4
A kind of graphene, preparation method include the following steps：
1) it is 0.5-2cm that the band-like Carbon fibe of intermediate phase pitch-based, which, is cut into length, then the interphase that will be obtained after shearing
The band-like Carbon fibe of asphaltic base, through high temperature carbonization 3h, obtains pretreatment sample at 1900 DEG C；
2), the pretreatment sample that processing obtains in step 1) is immersed in 7gLiCl-KCl-KF inorganic fused salt systems, then
High-temperature heat treatment 7h, obtains reaction product at 900 DEG C, and reaction product is washed under the conditions of ultrasonic vibration successively and is filtered 6 times
To be separated off fused salt, up to graphene after 80 DEG C of dry 10h；
Wherein, inorganic fused salt system is made of KF, LiCl, KCl in step 2), and the mass ratio of LiCl and KCl are 1:1.2
KF mass contents are 7% in inorganic fused salt system；
Graphene synusia size manufactured in the present embodiment is 100-1000 μm2, the number of plies is 1-3 layers.
It these are only preferred embodiments of the present invention, be not intended to limit the implementation manners and the protection scope of the present invention, it is right
For those skilled in the art, it should can appreciate that and all be replaced with being equal made by description of the invention and diagramatic content
It changes and obviously changes obtained scheme, should all be included within the scope of the present invention.
Claims (10)
1. a kind of deriving the method that charcoal prepares graphene with mesophase pitch, which is characterized in that include the following steps：
1) mesophase pitch derivative charcoal, is handled into obtain pretreatment sample through high temperature carbonization；
2), the pretreatment sample that processing obtains in step 1) is immersed in inorganic fused salt system must react production through high-temperature heat treatment
Object, up to graphene after reaction product is separated off fused salt and is dried.
2. according to the method described in claim 1, which is characterized in that mesophase pitch described in step 1) derives charcoal in
Between one kind in asphalt phase coke, needle coke, Mesophase Pitch-based Carbon Fibers or the band-like Carbon fibe of intermediate phase pitch-based.
3. according to the method described in claim 1, which is characterized in that mesophase pitch described in step 1) derives the granularity of charcoal
Or length is 0.5-3cm.
4. according to the method described in claim 1, which is characterized in that treatment temperature is in the processing of step 1) high temperature carbonization
1500-1900 DEG C, processing time 1-3h.
5. according to the method described in claim 1, which is characterized in that inorganic fused salt system described in step 2) by KF, LiCl,
KCl is made, wherein the mass ratio of LiCl and KCl is 1:1.2, KF mass contents are 1-7% in the inorganic fused salt system.
6. according to the method described in claim 1, which is characterized in that treatment temperature is 600- in step 2) high-temperature heat treatment
900 DEG C, processing time 3-7h.
7. according to the method described in claim 1, which is characterized in that use washing separation method to be separated off in step 2) molten
Salt.
8. according to the method described in claim 7, which is characterized in that washing separation method is：By reaction product successively in ultrasound
It washes and filters 2-6 times under the conditions of concussion.
9. according to the method described in claim 1, which is characterized in that drying temperature is 40-80 DEG C in step 2), drying time
For 4-10h.
10. a kind of graphene prepared according to any one of claim 1-9 the methods.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111013626A (en) * | 2019-12-18 | 2020-04-17 | 中钢集团鞍山热能研究院有限公司 | Monoatomic metal graphene catalyst based on needle coke and preparation method thereof |
| CN115417401A (en) * | 2022-05-12 | 2022-12-02 | 太原理工大学 | Method for preparing graphene by recoverable low-temperature molten salt |
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| CN106315540A (en) * | 2015-06-18 | 2017-01-11 | 北京化工大学 | Method for preparing graphene quantum dot from asphalt |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103588195A (en) * | 2013-11-01 | 2014-02-19 | 天津大学 | Preparation method of graphene |
| CN104291327A (en) * | 2014-09-24 | 2015-01-21 | 北京化工大学常州先进材料研究院 | Method for preparing graphene by peeling graphite in electrochemical manner by using molten salt |
| CN104876213A (en) * | 2015-05-04 | 2015-09-02 | 北京化工大学 | Graphene material and preparation method of electrode material of graphene material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013626A (en) * | 2019-12-18 | 2020-04-17 | 中钢集团鞍山热能研究院有限公司 | Monoatomic metal graphene catalyst based on needle coke and preparation method thereof |
| CN111013626B (en) * | 2019-12-18 | 2023-04-28 | 中钢集团鞍山热能研究院有限公司 | Single-atom metal graphene catalyst based on needle coke and preparation method thereof |
| CN115417401A (en) * | 2022-05-12 | 2022-12-02 | 太原理工大学 | Method for preparing graphene by recoverable low-temperature molten salt |
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Application publication date: 20180821 |