CN105645393B - A kind of preparation method of the growth in situ graphene on graphite fibre - Google Patents
A kind of preparation method of the growth in situ graphene on graphite fibre Download PDFInfo
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- CN105645393B CN105645393B CN201610024032.4A CN201610024032A CN105645393B CN 105645393 B CN105645393 B CN 105645393B CN 201610024032 A CN201610024032 A CN 201610024032A CN 105645393 B CN105645393 B CN 105645393B
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Abstract
A kind of preparation method of the growth in situ graphene on graphite fibre, during preparation, the concentrated sulfuric acid that concentration is 98% and the hydrofluoric acid that concentration is 35% is taken first, produces the mixed solvent of the concentrated sulfuric acid and hydrofluoric acid；Then the in the mixed solvent for graphite fibre being added to the concentrated sulfuric acid and hydrofluoric acid produces the solution containing graphite fibre, and is sufficiently stirred；Then, the solution added with graphite fibre is put into hydrothermal reaction kettle and carries out hydro-thermal reaction, the solution after hydro-thermal reaction is washed with deionized, the graphene of the growth in situ on graphite fibre is can obtain after drying.The graphene of growth in situ on graphite fibre prepared by the above method, purity is high, and graphene grows in graphite fibre surface in situ, it is less likely to occur to reunite, good dispersion, and the easy load regulation two-phase in surface, are advantageous to be applied in ultracapacitor and lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of graphene, and in particular to one kind growth in situ graphene on graphite fibre
Preparation method.
Background technology
Since Univ Manchester UK physicist An Deliegaimu in 2004 and Constantine's Nuo Woxiao loves
Success has isolated graphene since obtaining Nobel Prize in physics from graphite, and graphene is just widely studied and closed
Note.The electron mobility of graphene is higher than the electron mobility of silicon and CNT, the resistivity ratio copper of graphene and the electricity of silver
Resistance rate is low, has very high theoretical specific surface area again, so that graphene is in lithium ion battery, ultracapacitor, photocatalysis etc.
Field is with a wide range of applications.
The method for preparing graphene at present mainly has mechanical stripping method, vapour deposition process, electrochemical process and chemical oxidation also
Former method.Wherein chemistry redox method is to prepare one of the most frequently used method of graphene on a large scale, usually utilizes chemical oxidation
Graphite oxidation is graphite oxide by reaction, is then peeled off by ultrasound to form graphene oxide, adds reducing agent reduction
It can obtain graphene.But strong oxidizer and reducing agent are commonly used in chemistry redox method, the easy shadow of these chemical substances
Ring the health of operating personnel and easily cause the pollution of environment, the graphene synthesized also with chemistry redox method easily exists
Irreversible reunion occurs in solution, structure is destroyed and has notable defect, unfavorable so as to cause electric conductivity to be greatly lowered
In being applied in lithium ion battery and ultracapacitor.
The content of the invention
In order to solve in the prior art using chemistry redox method synthesis graphene easily in the solution occur can not
Inverse the problem of reuniting, the present invention provide a kind of preparation method of the growth in situ graphene on graphite fibre.
The present invention provides a kind of preparation method of the growth in situ graphene on graphite fibre, has the following steps：
The first step, the concentrated sulfuric acid that concentration is 98% is taken, concentration is 35% hydrofluoric acid, according to the matter of the concentrated sulfuric acid and hydrofluoric acid
Amount is than being 1:5-5:The mixed solvent of the 1 configuration concentrated sulfuric acid and hydrofluoric acid.
Second step, the in the mixed solvent that graphite fibre is added to the concentrated sulfuric acid and hydrofluoric acid are produced containing the molten of graphite fibre
Liquid, and the solution containing graphite fibre is sufficiently stirred.
3rd step, the solution containing graphite fibre after stirring is placed in hydrothermal reaction kettle and carries out hydro-thermal reaction.
4th step, the sediment that is generated of solution after the completion of hydro-thermal reaction is filtered, then the sediment of generation is spent
Ion water washing, the graphene of growth in situ on graphite fibre is obtained after drying.
Preferably, in second step, magnetic agitation is taken, mixing time is 2h to 4h.
Further preferably, mixing time 4h.
Preferably, in the third step, the temperature of hydro-thermal reaction be 150 DEG C to 200 DEG C, the hydro-thermal reaction time be 24h extremely
48h。
Further preferably, hydrothermal temperature is 200 DEG C.
Further preferably, the hydro-thermal reaction time 48h.
Preferably, graphite fibre and the mass ratio of the concentrated sulfuric acid and the mixed solvent of hydrofluoric acid are 1:50.
Preferably, in the first step, the mass ratio of the concentrated sulfuric acid and hydrofluoric acid is 1:1.
The present invention compared with prior art, has the advantages that：
A kind of preparation method of above-mentioned growth in situ graphene on graphite fibre, the concentrated sulfuric acid and hydrogen are placed in by graphite fibre
The in the mixed solvent of fluoric acid carries out hydro-thermal reaction, the mixed solvent of the concentrated sulfuric acid and hydrofluoric acid can deep-etching graphite fibre surface,
A large amount of sheet graphenes are formed on graphite fibre surface.The system of the growth in situ graphene provided by the invention on graphite fibre
Preparation Method eliminates reduction process compared with chemistry redox method, and preparation process is simple and convenient.
By made of preparation method provided by the invention on graphite fibre growth in situ graphene, have it is following excellent
Point：
1st, without redox reaction, impurity is not introduced in graphite fibre sur-face peeling graphite using solvent of strong, with
Traditional chemistry redox method is compared, and the graphene defect of generation is few, and purity is high, the number of plies is few, good conductivity.
2nd, graphene grows in graphite fibre surface in situ, it is not easy to reunite, good dispersion, and surface is easily born
The second phase is carried, is advantageous to be applied in ultracapacitor and lithium ion battery.
Brief description of the drawings
Fig. 1 is the Raman spectrogram of the graphene of growth in situ on graphite fibre in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the graphene of growth in situ on graphite fibre in embodiment 1.
Fig. 3 is the transmission electron microscope picture of the graphene of growth in situ on graphite fibre in embodiment 1；Wherein (a) is low power
Transmission electron microscope picture, (b) are high power transmission electron microscope picture.
Embodiment
With reference to Fig. 1 to Fig. 3, the present invention is described in detail.
Following embodiments 1 relate to a kind of preparation method of growth in situ graphene on graphite fibre described in embodiment 5
And material have graphite fibre, the concentrated sulfuric acid and hydrofluoric acid.The concentration of the concentrated sulfuric acid is 98%；The concentration of hydrofluoric acid is 35%；
The graphite fibre chooses the S1 model graphite fibre powder produced by the source carbon graphite material Co., Ltd of Shenzhen's crystalline substance.
Embodiment 1
(1) concentrated sulfuric acid and each 25g of hydrofluoric acid are measured, and the concentrated sulfuric acid and hydrofluoric acid are poured into beaker, by the concentrated sulfuric acid and hydrogen
Fluoric acid is well mixed and then configuration quality ratio is 1:1 mixed solvent.
(2) 1g graphite fibres are weighed and graphite fibre is scattered in the 50g concentrated sulfuric acid and the in the mixed solvent of hydrofluoric acid, are entered
And produce the solution containing graphite fibre.
(3) it will be placed in magnetic stirring apparatus added with the solution containing graphite fibre, stirred by magnetic agitation 4h.
(4) then the solution containing graphene fiber after stirring is placed in hydrothermal reaction kettle and reacts 48h, hydro-thermal reaction
Reaction temperature in kettle is 200 DEG C.
(5) sediment that the solution after the completion of finally filtering reaction is generated, sediment is washed with deionized, done
The graphene of the growth in situ on graphite fibre is produced after dry.
(6) stone of growth in situ on graphite fibre by ESEM, transmission electron microscope and Raman spectrometer to preparation
Black alkene carries out observation analysis.
The graphene of preparation is analyzed by ESEM, transmission electron microscope and Raman spectrometer, as shown in figure 1, drawing
There is no the peak of other materials in graceful spectrogram, it is known that graphene purity prepared by embodiment 1 is high.As shown in Fig. 2 the graphite prepared
Alkene is evenly distributed on graphite fibre, good dispersion.As shown in (b) in (a) in Fig. 3 and Fig. 3, the graphene of preparation is in situ
It is grown on graphite fibre, graphene is that the laminar structured and number of plies is less, is rendered as fabulous crystalline structure.
Embodiment 2
(1) concentrated sulfuric acid 10g, each 50g of hydrofluoric acid are measured, and the concentrated sulfuric acid and hydrofluoric acid are poured into beaker, by the concentrated sulfuric acid and
Hydrofluoric acid is well mixed and then configuration quality ratio is 1:5 mixed solvent, and measure 50g from 60g in the mixed solvent.
(2) 1g graphite fibres are weighed and graphite fibre is scattered in the 50g concentrated sulfuric acid and the in the mixed solvent of hydrofluoric acid, are entered
And produce the solution containing graphite fibre.
(3) it will be placed in magnetic stirring apparatus added with the solution containing graphite fibre, stirred by magnetic agitation 4h.
(4) then the solution containing graphene fiber after stirring is placed in hydrothermal reaction kettle and reacts 48h, hydro-thermal reaction
Reaction temperature in kettle is 200 DEG C.
(5) sediment that the solution after the completion of finally filtering reaction is generated, sediment is washed with deionized, done
The graphene of the growth in situ on graphite fibre is produced after dry.
(6) stone of growth in situ on graphite fibre by ESEM, transmission electron microscope and Raman spectrometer to preparation
Black alkene carries out observation analysis.
Learn that the graphene uniform prepared in embodiment 2 is distributed on graphite fibre, good dispersion, purity by observation
It is high.Compared with Example 1, graphene film length-width ratio is small, and quantity is few.
Embodiment 3
(1) concentrated sulfuric acid 50g, each 10g of hydrofluoric acid are measured, and the concentrated sulfuric acid and hydrofluoric acid are poured into beaker, by the concentrated sulfuric acid and
Hydrofluoric acid is well mixed and then configuration quality ratio is 5:1 mixed solvent, and measure 50g from 60g in the mixed solvent.
(2) 1g graphite fibres are weighed and graphite fibre is scattered in the 50g concentrated sulfuric acid and the in the mixed solvent of hydrofluoric acid, are entered
And produce the solution containing graphite fibre.
(3) it will be placed in magnetic stirring apparatus added with the solution containing graphite fibre, stirred by magnetic agitation 4h.
(4) then the solution containing graphene fiber after stirring is placed in hydrothermal reaction kettle and reacts 48h, hydro-thermal reaction
Reaction temperature in kettle is 200 DEG C.
(5) sediment that the solution after the completion of finally filtering reaction is generated, sediment is washed with deionized, done
The graphene of the growth in situ on graphite fibre is produced after dry.
(6) stone of growth in situ on graphite fibre by ESEM, transmission electron microscope and Raman spectrometer to preparation
Black alkene carries out observation analysis.
Learn that the graphene uniform prepared in embodiment 3 is distributed on graphite fibre, good dispersion, purity by observation
It is high.But compared with Example 1, graphene film length-width ratio is big, and caused graphene quantity is few.
Embodiment 4
(1) concentrated sulfuric acid 50g, each 10g of hydrofluoric acid are measured, and the concentrated sulfuric acid and hydrofluoric acid are poured into beaker, by the concentrated sulfuric acid and
Hydrofluoric acid is well mixed and then configuration quality ratio is 5:1 mixed solvent, and measure 50g from 60g in the mixed solvent.
(2) 1g graphite fibres are weighed and graphite fibre is scattered in the 50g concentrated sulfuric acid and the in the mixed solvent of hydrofluoric acid, are entered
And produce the solution containing graphite fibre.
(3) it will be placed in magnetic stirring apparatus added with the solution containing graphite fibre, stirred by magnetic agitation 4h.
(4) then the solution containing graphene fiber after stirring is placed in hydrothermal reaction kettle and reacts 24h, hydro-thermal reaction
Reaction temperature in kettle is 150 DEG C.
(5) sediment that the solution after the completion of finally filtering reaction is generated, sediment is washed with deionized, done
The graphene of the growth in situ on graphite fibre is produced after dry.
(6) stone of growth in situ on graphite fibre by ESEM, transmission electron microscope and Raman spectrometer to preparation
Black alkene carries out observation analysis.
Learn that the graphene uniform prepared in embodiment 4 is distributed on graphite fibre, good dispersion, purity by observation
It is high.Compared with Example 3, graphene film length-width ratio is small, and quantity is few.
Embodiment 5
(1) concentrated sulfuric acid 50g, each 10g of hydrofluoric acid are measured, and the concentrated sulfuric acid and hydrofluoric acid are poured into beaker, by the concentrated sulfuric acid and
Hydrofluoric acid is well mixed and then configuration quality ratio is 5:1 mixed solvent, and measure 50g from 60g in the mixed solvent.
(2) 1g graphite fibres are weighed and graphite fibre is scattered in the 50g concentrated sulfuric acid and the in the mixed solvent of hydrofluoric acid, are entered
And produce the solution containing graphite fibre.
(3) it will be placed in magnetic stirring apparatus added with the solution containing graphite fibre, stirred by magnetic agitation 2h.
(4) then the solution containing graphene fiber after stirring is placed in hydrothermal reaction kettle and reacts 48h, hydro-thermal reaction
Reaction temperature in kettle is 200 DEG C.
(5) sediment that the solution after the completion of finally filtering reaction is generated, sediment is washed with deionized, done
The graphene of the growth in situ on graphite fibre is produced after dry.
(6) stone of growth in situ on graphite fibre by ESEM, transmission electron microscope and Raman spectrometer to preparation
Black alkene carries out observation analysis.
Learn that the graphene uniform prepared in embodiment 5 is distributed on graphite fibre, good dispersion, purity by observation
It is high.Compared with Example 3, graphene film length-width ratio is small, and quantity is few.
The graphene of growth in situ on graphite fibre prepared by above-described embodiment 1 to embodiment 5, graphene uniform distribution
On graphite fibre, good dispersion, and the purity of graphene is high.Graphene is that the laminar structured and number of plies is less, is rendered as pole
Good crystalline structure.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above, this technology neck
The variations, modifications, additions or substitutions that the technical staff in domain is made in the essential scope of the present invention, it should also belong to the present invention's
Protection domain.
Claims (7)
1. a kind of preparation method of the growth in situ graphene on graphite fibre, it is characterised in that have the following steps：
The first step, the concentrated sulfuric acid that concentration is 98% is taken, concentration is 35% hydrofluoric acid, according to the concentrated sulfuric acid and the mass ratio of hydrofluoric acid
For 1:5-5:1 produces the mixed solvent of the concentrated sulfuric acid and hydrofluoric acid；
Second step, the in the mixed solvent that graphite fibre is added to the concentrated sulfuric acid and hydrofluoric acid produce the solution containing graphite fibre,
And the solution containing graphite fibre is sufficiently stirred；
3rd step, the solution containing graphite fibre after stirring is placed in hydrothermal reaction kettle and carries out hydro-thermal reaction；Hydro-thermal reaction
Temperature is 150 DEG C to 200 DEG C, and the hydro-thermal reaction time is 24h to 48h；
4th step, filter the sediment that is generated of solution after the completion of hydro-thermal reaction, then the sediment deionization by generation
Water washing, the graphene of growth in situ on graphite fibre is obtained after drying.
A kind of 2. preparation method of the growth in situ graphene on graphite fibre as claimed in claim 1, it is characterised in that
In second step, magnetic agitation is taken, mixing time is 2h to 4h.
3. a kind of preparation method of the growth in situ graphene on graphite fibre as claimed in claim 2, it is characterised in that stir
It is 4h to mix the time.
A kind of 4. preparation method of the growth in situ graphene on graphite fibre as claimed in claim 1, it is characterised in that water
Thermal response temperature is 200 DEG C.
A kind of 5. preparation method of the growth in situ graphene on graphite fibre as claimed in claim 1, it is characterised in that water
The thermal response time is 48h.
A kind of 6. preparation method of the growth in situ graphene on graphite fibre as claimed in claim 1, it is characterised in that stone
The mass ratio of black fiber and mixed solvent is 1:50.
A kind of 7. preparation method of the growth in situ graphene on graphite fibre as claimed in claim 1, it is characterised in that the
In one step, the mass ratio of the concentrated sulfuric acid and hydrofluoric acid is 1:1.
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| CN109112822B (en) * | 2018-07-23 | 2021-01-22 | 河南工业大学 | Method for preparing carbon fiber in-situ growth graphene composite carrier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462889A (en) * | 2009-01-16 | 2009-06-24 | 南开大学 | Graphene and carbon fiber composite material, and preparation thereof |
| CN103614902A (en) * | 2013-11-20 | 2014-03-05 | 上海应用技术学院 | Preparation method of graphene/carbon fiber composite |
| CN104310371A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for growing carbon nano tube in situ on surface of fiber |
| CN104532548A (en) * | 2015-01-29 | 2015-04-22 | 中国兵器工业集团第五三研究所 | In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462889A (en) * | 2009-01-16 | 2009-06-24 | 南开大学 | Graphene and carbon fiber composite material, and preparation thereof |
| CN103614902A (en) * | 2013-11-20 | 2014-03-05 | 上海应用技术学院 | Preparation method of graphene/carbon fiber composite |
| CN104310371A (en) * | 2014-09-30 | 2015-01-28 | 张映波 | Method for growing carbon nano tube in situ on surface of fiber |
| CN104532548A (en) * | 2015-01-29 | 2015-04-22 | 中国兵器工业集团第五三研究所 | In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface |
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