CN105645393A - Preparing method for in-situ growth of graphene on graphite fibers - Google Patents
Preparing method for in-situ growth of graphene on graphite fibers Download PDFInfo
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- CN105645393A CN105645393A CN201610024032.4A CN201610024032A CN105645393A CN 105645393 A CN105645393 A CN 105645393A CN 201610024032 A CN201610024032 A CN 201610024032A CN 105645393 A CN105645393 A CN 105645393A
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a preparing method for in-situ growth of graphene on graphite fibers. The preparing method comprises the steps that in the preparing process, firstly, concentrated sulfuric acid with the concentration of 98% and hydrofluoric acid with the concentration of 35% are taken for preparing a mixed solvent of concentrated sulfuric acid and hydrofluoric acid; secondly, graphite fibers are added into the mixed solvent of concentrated sulfuric acid and hydrofluoric acid to prepare a solution containing graphite fibers, and sufficient stirring is carried out; thirdly, the solution with graphite fibers is put into a hydrothermal reaction kettle for a hydrothermal reaction, a solution obtained after the hydrothermal reaction is washed with deionized water, and graphene grown on graphite fibers in situ can be obtained after drying. Graphene, prepared through the method, grown on graphite fibers in situ is high in purity, is grown on the surfaces of graphite fibers in situ, and is not prone to agglomeration and good in dispersibility; in addition a second phase can be easily loaded on the surface of graphene, and thus the graphene can be easily applied to supercapacitors and lithium ion batteries.
Description
Technical field
The preparation method that the present invention relates to a kind of Graphene, is specifically related to a kind of preparation method of growth in situ Graphene on graphite fibre.
Background technology
Since Univ Manchester UK physicist An Deliegaimu in 2004 and the success of Constantine's Nuo Woxiao love are isolated Graphene from graphite and obtained Nobel Prize in physics, Graphene is just subject to research widely and pays close attention to. The electron mobility of Graphene is higher than the electron mobility of silicon and CNT, the resistivity of the resistivity ratio copper of Graphene and silver is low, there is again significantly high theoretical specific surface area, so that Graphene is with a wide range of applications in fields such as lithium ion battery, ultracapacitor, photocatalysis.
Prepare the predominantly organic tool stripping method of method of Graphene, vapour deposition process, electrochemical process and chemistry redox method at present. Wherein chemistry redox method is to prepare one of Graphene most common method on a large scale, being usually and utilizing chemical oxidation reaction is graphite oxide by graphite oxidation, then pass through ultrasonic stripping and then form graphene oxide, adding reducing agent reduction and can obtain Graphene. But chemistry redox method is commonly used strong oxidizer and reducing agent, these chemical substances easily affect the health of operator and easily cause the pollution of environment, easily there is irreversible reunion in the solution in the Graphene also with the synthesis of chemistry redox method, structure is destroyed and is had notable defect, thus causing that electric conductivity is greatly lowered, it is unfavorable for being applied in lithium ion battery and ultracapacitor.
Summary of the invention
Easily there is the problem of irreversible reunion in the Graphene in order to solve to utilize chemistry redox method to synthesize in prior art, the present invention provides a kind of preparation method of growth in situ Graphene on graphite fibre in the solution.
The present invention provides a kind of preparation method of growth in situ Graphene on graphite fibre, has the following steps:
The first step, takes the concentrated sulphuric acid that concentration is 98%, and concentration is the Fluohydric acid. of 35%, is the 1:5-5:1 mixed solvent configuring concentrated sulphuric acid and Fluohydric acid. according to the mass ratio of concentrated sulphuric acid and Fluohydric acid..
Second step, adds to graphite fibre and produces the solution containing graphite fibre in the mixed solvent of concentrated sulphuric acid and Fluohydric acid., and the solution containing graphite fibre is sufficiently stirred for.
3rd step, is placed in hydrothermal reaction kettle carries out hydro-thermal reaction by the solution containing graphite fibre after stirring.
4th step, filters the precipitate that the solution after hydro-thermal reaction completes obtains generating then the precipitate deionized water wash that will generate, and namely obtains the Graphene of growth in situ on graphite fibre after drying.
Preferably, in second step, taking magnetic agitation, mixing time is 2h to 4h.
Further preferably, mixing time is 4h.
Preferably, in the third step, the temperature of hydro-thermal reaction is 150 DEG C to 200 DEG C, and the hydro-thermal reaction time is 24h to 48h.
Further preferably, hydrothermal temperature is 200 DEG C.
Further preferably, the hydro-thermal reaction time is 48h.
Preferably, graphite fibre is 1:50 with the mass ratio of concentrated sulphuric acid and the mixed solvent of Fluohydric acid..
Preferably, in the first step, the mass ratio of concentrated sulphuric acid and Fluohydric acid. is 1:1.
The present invention compared with prior art, has the advantages that
Above-mentioned a kind of preparation method of growth in situ Graphene on graphite fibre, graphite fibre is placed in the mixed solvent of concentrated sulphuric acid and Fluohydric acid. and carries out hydro-thermal reaction, the mixed solvent of concentrated sulphuric acid and Fluohydric acid. can deep-etching graphite fibre surface, form a large amount of sheet Graphene on graphite fibre surface. Provided by the invention on graphite fibre the preparation method of growth in situ Graphene compared with chemistry redox method, eliminate reduction process, preparation process is simple and convenient.
By the Graphene of growth in situ on graphite fibre that preparation method provided by the invention is made, have the advantage that
1, utilizing solvent of strong at graphite fibre sur-face peeling graphite, it does not have redox reaction, it does not have introducing impurity, compared with traditional chemistry redox method, the Graphene defect of generation is few, purity is high, the number of plies is few, good conductivity.
2, Graphene grows at graphite fibre surface in situ, it is not easy to reunite, and good dispersion, and the easy load regulation two-phase in surface are conducive to being applied in ultracapacitor and lithium ion battery.
Accompanying drawing explanation
Fig. 1 be in embodiment 1 on graphite fibre the Raman spectrogram of the Graphene of growth in situ.
Fig. 2 be in embodiment 1 on graphite fibre the scanning electron microscope (SEM) photograph of the Graphene of growth in situ.
Fig. 3 be in embodiment 1 on graphite fibre the transmission electron microscope picture of the Graphene of growth in situ; Wherein (a) is low power transmission electron microscope picture, and (b) is high power transmission electron microscope picture.
Detailed description of the invention
Below in conjunction with Fig. 1 to Fig. 3, the present invention is described in detail.
A kind of preparation method of growth in situ Graphene on graphite fibre described in following embodiment 1 to embodiment 5, the material related to has graphite fibre, concentrated sulphuric acid and Fluohydric acid.. The concentration of described concentrated sulphuric acid is 98%; The concentration of Fluohydric acid. is 35%; The S1 model graphite fibre powder produced by the source carbon graphite material company limited of Shenzhen's crystalline substance chosen by described graphite fibre.
Embodiment 1
(1) measure concentrated sulphuric acid and each 25g of Fluohydric acid., and concentrated sulphuric acid and Fluohydric acid. are poured in beaker, by concentrated sulphuric acid and Fluohydric acid. mix homogeneously and then configuration quality than the mixed solvent for 1:1.
(2) weigh 1g graphite fibre and graphite fibre be scattered in the concentrated sulphuric acid of 50g and the mixed solvent of Fluohydric acid., and then producing the solution containing graphite fibre.
(3) solution being added with containing graphite fibre is placed in magnetic stirring apparatus, is stirred by magnetic agitation 4h.
(4) being then placed in hydrothermal reaction kettle and react 48h by the solution containing graphene fiber after stirring, the reaction temperature in hydrothermal reaction kettle is 200 DEG C.
(5) finally the solution filtered after having reacted obtains the precipitate of generation, by precipitate deionized water wash, namely obtains the Graphene of growth in situ on graphite fibre after drying.
(6) by scanning electron microscope, transmission electron microscope and Raman spectrometer, the Graphene of growth in situ on graphite fibre of preparation is carried out observation analysis.
By scanning electron microscope, transmission electron microscope and Raman spectrometer, the Graphene of preparation is analyzed, as it is shown in figure 1, Raman spectrogram does not have the peak of other material, it is known that the Graphene purity of embodiment 1 preparation is high. As in figure 2 it is shown, the graphene uniform of preparation is distributed on graphite fibre, good dispersion. Shown in (b) in (a) in Fig. 3 and Fig. 3, the Graphene growth in situ of preparation is on graphite fibre, and Graphene is laminar structured and the number of plies is less, is rendered as fabulous crystalline structure.
Embodiment 2
(1) concentrated sulphuric acid 10g is measured, each 50g of Fluohydric acid., and concentrated sulphuric acid and Fluohydric acid. are poured in beaker, by concentrated sulphuric acid and Fluohydric acid. mix homogeneously and then configuration quality than the mixed solvent for 1:5, and from the mixed solvent of 60g, measure 50g.
(2) weigh 1g graphite fibre and graphite fibre be scattered in the concentrated sulphuric acid of 50g and the mixed solvent of Fluohydric acid., and then producing the solution containing graphite fibre.
(3) solution being added with containing graphite fibre is placed in magnetic stirring apparatus, is stirred by magnetic agitation 4h.
(4) being then placed in hydrothermal reaction kettle and react 48h by the solution containing graphene fiber after stirring, the reaction temperature in hydrothermal reaction kettle is 200 DEG C.
(5) finally the solution filtered after having reacted obtains the precipitate of generation, by precipitate deionized water wash, namely obtains the Graphene of growth in situ on graphite fibre after drying.
(6) by scanning electron microscope, transmission electron microscope and Raman spectrometer, the Graphene of growth in situ on graphite fibre of preparation is carried out observation analysis.
Learning by observing, in embodiment 2, the graphene uniform of preparation is distributed on graphite fibre, good dispersion, and purity is high. Compared with embodiment 1, graphene film length-width ratio is little, and quantity is few.
Embodiment 3
(1) concentrated sulphuric acid 50g is measured, each 10g of Fluohydric acid., and concentrated sulphuric acid and Fluohydric acid. are poured in beaker, by concentrated sulphuric acid and Fluohydric acid. mix homogeneously and then configuration quality than the mixed solvent for 5:1, and from the mixed solvent of 60g, measure 50g.
(2) weigh 1g graphite fibre and graphite fibre be scattered in the concentrated sulphuric acid of 50g and the mixed solvent of Fluohydric acid., and then producing the solution containing graphite fibre.
(3) solution being added with containing graphite fibre is placed in magnetic stirring apparatus, is stirred by magnetic agitation 4h.
(4) being then placed in hydrothermal reaction kettle and react 48h by the solution containing graphene fiber after stirring, the reaction temperature in hydrothermal reaction kettle is 200 DEG C.
(5) finally the solution filtered after having reacted obtains the precipitate of generation, by precipitate deionized water wash, namely obtains the Graphene of growth in situ on graphite fibre after drying.
(6) by scanning electron microscope, transmission electron microscope and Raman spectrometer, the Graphene of growth in situ on graphite fibre of preparation is carried out observation analysis.
Learning by observing, in embodiment 3, the graphene uniform of preparation is distributed on graphite fibre, good dispersion, and purity is high.But compared with embodiment 1, graphene film length-width ratio wants big, and the Graphene quantity produced is few.
Embodiment 4
(1) concentrated sulphuric acid 50g is measured, each 10g of Fluohydric acid., and concentrated sulphuric acid and Fluohydric acid. are poured in beaker, by concentrated sulphuric acid and Fluohydric acid. mix homogeneously and then configuration quality than the mixed solvent for 5:1, and from the mixed solvent of 60g, measure 50g.
(2) weigh 1g graphite fibre and graphite fibre be scattered in the concentrated sulphuric acid of 50g and the mixed solvent of Fluohydric acid., and then producing the solution containing graphite fibre.
(3) solution being added with containing graphite fibre is placed in magnetic stirring apparatus, is stirred by magnetic agitation 4h.
(4) being then placed in hydrothermal reaction kettle and react 24h by the solution containing graphene fiber after stirring, the reaction temperature in hydrothermal reaction kettle is 150 DEG C.
(5) finally the solution filtered after having reacted obtains the precipitate of generation, by precipitate deionized water wash, namely obtains the Graphene of growth in situ on graphite fibre after drying.
(6) by scanning electron microscope, transmission electron microscope and Raman spectrometer, the Graphene of growth in situ on graphite fibre of preparation is carried out observation analysis.
Learning by observing, in embodiment 4, the graphene uniform of preparation is distributed on graphite fibre, good dispersion, and purity is high. Compared with embodiment 3, graphene film length-width ratio is little, and quantity is few.
Embodiment 5
(1) concentrated sulphuric acid 50g is measured, each 10g of Fluohydric acid., and concentrated sulphuric acid and Fluohydric acid. are poured in beaker, by concentrated sulphuric acid and Fluohydric acid. mix homogeneously and then configuration quality than the mixed solvent for 5:1, and from the mixed solvent of 60g, measure 50g.
(2) weigh 1g graphite fibre and graphite fibre be scattered in the concentrated sulphuric acid of 50g and the mixed solvent of Fluohydric acid., and then producing the solution containing graphite fibre.
(3) solution being added with containing graphite fibre is placed in magnetic stirring apparatus, is stirred by magnetic agitation 2h.
(4) being then placed in hydrothermal reaction kettle and react 48h by the solution containing graphene fiber after stirring, the reaction temperature in hydrothermal reaction kettle is 200 DEG C.
(5) finally the solution filtered after having reacted obtains the precipitate of generation, by precipitate deionized water wash, namely obtains the Graphene of growth in situ on graphite fibre after drying.
(6) by scanning electron microscope, transmission electron microscope and Raman spectrometer, the Graphene of growth in situ on graphite fibre of preparation is carried out observation analysis.
Learning by observing, in embodiment 5, the graphene uniform of preparation is distributed on graphite fibre, good dispersion, and purity is high. Compared with embodiment 3, graphene film length-width ratio is little, and quantity is few.
The Graphene of growth in situ on graphite fibre of above-described embodiment 1 to embodiment 5 preparation, graphene uniform is distributed on graphite fibre, good dispersion, and the purity of Graphene is high. Graphene is laminar structured and the number of plies is less, is rendered as fabulous crystalline structure.
Certainly, described above is not limitation of the present invention, and the present invention is also not limited to the example above, the change made in the essential scope of the present invention of those skilled in the art, remodeling, interpolation or replacement, also should belong to protection scope of the present invention.
Claims (8)
1. the preparation method of growth in situ Graphene on graphite fibre, it is characterised in that have the following steps:
The first step, takes the concentrated sulphuric acid that concentration is 98%, and concentration is the Fluohydric acid. of 35%, is the 1:5-5:1 mixed solvent producing concentrated sulphuric acid and Fluohydric acid. according to the mass ratio of concentrated sulphuric acid and Fluohydric acid.;
Second step, adds to graphite fibre and produces the solution containing graphite fibre in the mixed solvent of concentrated sulphuric acid and Fluohydric acid., and the solution containing graphite fibre is sufficiently stirred for;
3rd step, is placed in hydrothermal reaction kettle carries out hydro-thermal reaction by the solution containing graphite fibre after stirring;
4th step, filters the precipitate that the solution after hydro-thermal reaction completes obtains generating then the precipitate deionized water wash that will generate, and namely obtains the Graphene of growth in situ on graphite fibre after drying.
2. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 1, it is characterised in that in second step, taking magnetic agitation, mixing time is 2h to 4h.
3. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 2, it is characterised in that mixing time is 4h.
4. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 1, it is characterised in that in the 3rd step, hydrothermal temperature is 150 DEG C to 200 DEG C, and the hydro-thermal reaction time is 24h to 48h.
5. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 4, it is characterised in that hydrothermal temperature is 200 DEG C.
6. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 4, it is characterised in that the hydro-thermal reaction time is 48h.
7. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 1, it is characterised in that the mass ratio of graphite fibre and mixed solvent is 1:50.
8. a kind of preparation method of growth in situ Graphene on graphite fibre as claimed in claim 1, it is characterised in that in the first step, the mass ratio of concentrated sulphuric acid and Fluohydric acid. is 1:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108365201A (en) * | 2018-02-12 | 2018-08-03 | 梁天俐 | A kind of TiO2Carbon-based graphene composite material and its preparation method and application |
| CN109112822A (en) * | 2018-07-23 | 2019-01-01 | 河南工业大学 | A method of preparing carbon fiber growth in situ graphene composite carrier |
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| 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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- 2016-01-14 CN CN201610024032.4A patent/CN105645393B/en not_active Expired - Fee Related
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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108365201A (en) * | 2018-02-12 | 2018-08-03 | 梁天俐 | A kind of TiO2Carbon-based graphene composite material and its preparation method and application |
| CN108365201B (en) * | 2018-02-12 | 2020-09-25 | 梁天俐 | TiO 22-carbon-based graphene composite material and preparation method and application thereof |
| CN109112822A (en) * | 2018-07-23 | 2019-01-01 | 河南工业大学 | A method of preparing carbon fiber growth in situ graphene composite carrier |
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