CN106744888A - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN106744888A CN106744888A CN201710033158.2A CN201710033158A CN106744888A CN 106744888 A CN106744888 A CN 106744888A CN 201710033158 A CN201710033158 A CN 201710033158A CN 106744888 A CN106744888 A CN 106744888A
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- preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The present invention relates to a kind of preparation method of Graphene, it is comprised the following steps：20~50mg graphite powders and 20 40 mg aluminum fluoride powder are added to the dispersion liquid formation mixed system that 10~30ml is dissolved with amine compound；The mixed system is shaken, is washed, be centrifuged and obtain graphene solution；Wherein, the amine compound includes imidazoles, methylimidazole, alanine, glycine, threonine, lauryl amine, hexamethylene diamine and octamethylenediamine.This preparation method has the advantages that considerable yield, preparation process is simple, products obtained therefrom good properties.
Description
Technical field
The invention belongs to field of nano material preparation, and in particular to a kind of preparation method of Graphene.
Background technology
Graphene is a kind of novel charcoal material, it be it is a kind of be the single layer of carbon atom facestock separated from graphite material
Material, this two-dimentional graphite crystal film strength is 100 times of steel.Graphene has the mechanical strength of superelevation, good conduction
The electrical properties of heat conductivility and uniqueness, thus be with a wide range of applications.
The method for preparing Graphene at present mainly has mechanical stripping method, epitaxial growth method, oxidation-reduction method and chemical gaseous phase
Sedimentation.The amount for preparing Graphene using mechanical stripping method and epitaxial growth method is relatively low, and in uneven thickness；Oxidation-reduction method master
It is divided into oxidation thermal reduction and oxidation chemistry reduction, oxidation thermal reduction prepares Graphene and often requires that temperature higher, consumes energy
Than larger, and chemical reduction method prepares Graphene often using chemical reagent such as hydrazines, and these reagents have certain toxicity, to human body
There is harm with environment；It is higher to production equipment requirement with process for preparing graphenes by chemical vapour deposition.
The content of the invention
In order to solve the above problems, the invention provides a kind of yield it is considerable, preparation condition is less demanding, preparation technology is simple
Single, the Graphene production technology of products obtained therefrom good properties.
For above-mentioned technical problem, the technical scheme that proposes is the present invention：
A kind of preparation method of Graphene, comprises the following steps：
20~50mg graphite powders and 20~40mg aluminum fluoride powder are added to the dispersion that 10~30ml is dissolved with amine compound
Liquid forms mixed system；
The mixed system is shaken, is washed, be centrifuged and obtain graphene solution；
Wherein, the amine compound include imidazoles, methylimidazole, alanine, glycine, threonine, lauryl amine, hexamethylene diamine and
Octamethylenediamine.
Further, the preparation process of the dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive oligomer of phenylamine,
The relative molecular weight of the oligomer of phenylamine is 600-2000；
The oligomer of phenylamine includes any one in aniline tripolymer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Use weak base or/and weak acid pH value conditioning agent regulating step（2）In the pH value of solution for preparing, make its PH 11~
Between 12；
（4）By step（3）The solution for obtaining carries out ultrasound at least 30min, you can obtain dispersion liquid.
Further, the step（3）Middle weak base or/and weak acid pH value conditioning agent are ammoniacal liquor, acetic acid and tetramethyl hydrogen-oxygen
Change one or more in ammonium.
Further, the Graphene is in the dispersion liquid, under inert gas shielding, under the conditions of 50~70 DEG C,
Shaken.
Further, the concussion time be at least 24h.
Further, the 500~8000rpm of centrifugal rotational speed, is centrifuged 10~30min；After the completion of centrifugation, it is isolated on
Clear liquid is graphene dispersing solution.
Further, the concussion of the mixed system uses ultrasonic oscillation.
Further, the method for described ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h,
Ultrasonic vibration 4h, then stops 12h again, is so recycled to the ultrasonic vibration time and adds and be 24h.
The graphene preparation method that the present invention is provided mixes by by graphite with aluminum fluoride, is heated in inert gas, fluorine
It is organic by small molecule again that change aluminium molecule just can be plugged into the prepared aluminum fluoride intercalation thing of graphite layers under relatively low reaction temperature
Thing part replaces interlayer aluminum fluoride molecule, under heating decomposes organic matter, and then allows graphite expansion to peel off, so as to graphite is obtained
Alkene；And the oligomer of phenylamine that be with the addition of in dispersion liquid can form π-π compounds with Graphene, you can graphite is substantially improved
Decentralization of the alkene in decentralized medium, dispersion stabilization and redispersibility energy, unique physical also without detriment to Graphene, chemically
Can, and it is simple to operate, implement beneficial to scale.
The preparation method that the present invention is provided has the following advantages that：
（1）Operating process is simple, easily-controllable, and post processing is simple, graphene suspension, dispersion fissility is good, uniform particle sizes, can
The performance of stable existence and Graphene is uninfluenced；
（2）Harmfulness to environment and people is small；
（3）It is prepared by proper scaleization；
（4）It is easy to store and transports, the stabilization resting period is room temperature condition lower more than three months；
（5）It is simply mixed in decentralized medium by by the dispersion liquid and Graphene, you can Graphene is substantially improved and is situated between in dispersion
Decentralization, dispersion stabilization and redispersibility energy in matter, unique physical, chemical property also without detriment to Graphene, and operation
Simply, implement beneficial to scale.
Specific embodiment
Embodiment 1
A kind of preparation method of Graphene, comprises the following steps：
20mg graphite powders and 20mg aluminum fluoride powder are added to the dispersion liquid formation mixture that 20ml is dissolved with amine compound
System；Under the protection of inert gas, under the conditions of 50 DEG C, ultrasonic vibration 24h is carried out to mixed system, after washing, centrifugal rotational speed
It is 500rpm, 25min is centrifuged；After the completion of centrifugation, isolated supernatant is graphene dispersing solution；
The method of ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, Ran Houting
Only 12h, being so recycled to the ultrasonic vibration time adds and is 24h.
Wherein, the amine compound include imidazoles, methylimidazole, alanine, glycine, threonine, lauryl amine, oneself two
Amine and octamethylenediamine.
The thickness of obtained Graphene is 1.05nm, and the square resistance of Graphene is 4 Ω sq-1。
The preparation process of dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive relative molecular weight for the aniline of 600-2000 is oligomeric
Thing,
The oligomer of phenylamine includes any one in aniline tripolymer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Use weak base or/and weak acid pH value conditioning agent regulating step（2）In the pH value of solution for preparing, make its PH 11, it is weak
Alkali or/and weak acid pH value conditioning agent are one or more in ammoniacal liquor, acetic acid and TMAH；
（4）By step（3）The solution for obtaining carries out ultrasonic 30min, you can obtain dispersion liquid.
Embodiment 2
30mg graphite powders and 40mg aluminum fluoride powder are added to the dispersion liquid formation mixture that 30ml is dissolved with amine compound
System；Under the protection of inert gas, under the conditions of 60 DEG C, ultrasonic vibration 24h is carried out to mixed system, after washing, set centrifugation
Rotating speed is 5000rpm, and 30min is centrifuged；After the completion of centrifugation, isolated supernatant is graphene dispersing solution；
The method of ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, Ran Houting
Only 12h, being so recycled to the ultrasonic vibration time adds and is 24h.
Wherein, the amine compound include imidazoles, methylimidazole, alanine, glycine, threonine, lauryl amine, oneself two
Amine and octamethylenediamine.
The thickness of obtained Graphene is 1.12nm, and the square resistance of Graphene is 5 Ω sq-1。
The preparation process of dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive relative molecular weight for the aniline of 600-2000 is oligomeric
Thing,
The oligomer of phenylamine includes any one in aniline tripolymer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Use weak base or/and weak acid pH value conditioning agent regulating step（2）In the pH value of solution for preparing, make its PH be 11, it is weak
Alkali or/and weak acid pH value conditioning agent are one or more in ammoniacal liquor, acetic acid and TMAH；
（4）By step（3）The solution for obtaining carries out ultrasonic 40min, you can obtain dispersion liquid.
Embodiment 3
50mg graphite powders and 30mg aluminum fluoride powder are added to the dispersion liquid formation mixture that 10ml is dissolved with amine compound
System；Under the protection of inert gas, under the conditions of 70 DEG C, ultrasonic vibration 24h is carried out to mixed system, after washing, set centrifugation
Rotating speed is 8000rpm, and 10min is centrifuged；After the completion of centrifugation, isolated supernatant is graphene dispersing solution；
The method of ultrasonic vibration process is：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, Ran Houting
Only 12h, being so recycled to the ultrasonic vibration time adds and is 24h.
Wherein, the amine compound include imidazoles, methylimidazole, alanine, glycine, threonine, lauryl amine, oneself two
Amine and octamethylenediamine.
The thickness of obtained Graphene is 0.82nm, and the square resistance of Graphene is 1.5 Ω sq-1。
The preparation process of dispersion liquid is as follows：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive relative molecular weight for the aniline of 600-2000 is oligomeric
Thing,
The oligomer of phenylamine includes any one in aniline tripolymer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Use weak base or/and weak acid pH value conditioning agent regulating step（2）In the pH value of solution for preparing, make its PH be 11, it is weak
Alkali or/and weak acid pH value conditioning agent are one or more in ammoniacal liquor, acetic acid and TMAH；
（4）By step（3）The solution for obtaining carries out ultrasonic 70min, you can obtain dispersion liquid.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof equivalent thereof.
Claims (8)
1. a kind of preparation method of Graphene, it is characterised in that comprise the following steps：
20~50mg graphite powders and 20~40mg aluminum fluoride powder are added to the dispersion that 10~30ml is dissolved with amine compound
Liquid forms mixed system；
The mixed system is shaken, is washed, be centrifuged and obtain graphene solution；
Wherein, the amine compound include imidazoles, methylimidazole, alanine, glycine, threonine, lauryl amine, hexamethylene diamine and
Octamethylenediamine.
2. the preparation method of Graphene according to claim 1, it is characterised in that the preparation process of the dispersion liquid is such as
Under：
（1）Isopropanol and DMF are mixed, its matched proportion density is：Isopropanol：N, N- dimethyl formyl
Amine is 5：1；
（2）Take step（1）Solution 50ml, add 2g to have electroactive oligomer of phenylamine,
The relative molecular weight of the oligomer of phenylamine is 600-2000；
The oligomer of phenylamine includes any one in aniline tripolymer, Tetraaniline, aniline pentamer, the aggressiveness of aniline six
Or two or more combinations；
（3）Use weak base or/and weak acid pH value conditioning agent regulating step（2）In the pH value of solution for preparing, make its PH 11~
Between 12；
（4）By step（3）The solution for obtaining carries out ultrasound at least 30min, you can obtain dispersion liquid.
3. the preparation method of Graphene according to claim 2, it is characterised in that the step（3）Middle weak base or/and weak
Sour pH value conditioning agent is one or more in ammoniacal liquor, acetic acid and TMAH.
4. the preparation method of Graphene according to claim 1, it is characterised in that the Graphene is in the dispersion liquid
In, under inert gas shielding, under the conditions of 50~70 DEG C, shaken.
5. the preparation method of Graphene according to claim 1, it is characterised in that the concussion time is at least 24h.
6. the preparation method of Graphene according to claim 1, it is characterised in that the centrifugal rotational speed 500~
8000rpm, is centrifuged 10~30min；After the completion of centrifugation, isolated supernatant is graphene dispersing solution.
7. the preparation method of Graphene according to claim 1, it is characterised in that the concussion of the mixed system is using super
Sound wave shock.
8. the preparation method of Graphene according to claim 7, it is characterised in that the method for described ultrasonic vibration process
For：Power 100W, after ultrasonic vibration 4h, stops, after 12h, then ultrasonic vibration 4h, then stop 12h, so it is recycled to ultrasonic shake
The time of swinging adds and is 24h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102021202367A1 (en) | 2020-12-15 | 2022-06-15 | Robert Bosch Gesellschaft mit beschränkter Haftung | Method of manufacturing an electrically conductive carbon conductor with carbon structure shapes |
| DE102021207914A1 (en) | 2020-12-15 | 2022-06-15 | Robert Bosch Gesellschaft mit beschränkter Haftung | Method for producing an electrically conductive strand of conductors with at least one carbon conductor |
| WO2022128497A1 (en) | 2020-12-15 | 2022-06-23 | Robert Bosch Gmbh | Method for producing an electrically conductive carbon conductor with carbon structural forms |
| WO2022128495A1 (en) | 2020-12-15 | 2022-06-23 | Robert Bosch Gmbh | Method for producing an electrically conductive conductor strand having at least one carbon conductor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102021202367A1 (en) | 2020-12-15 | 2022-06-15 | Robert Bosch Gesellschaft mit beschränkter Haftung | Method of manufacturing an electrically conductive carbon conductor with carbon structure shapes |
| DE102021207914A1 (en) | 2020-12-15 | 2022-06-15 | Robert Bosch Gesellschaft mit beschränkter Haftung | Method for producing an electrically conductive strand of conductors with at least one carbon conductor |
| WO2022128497A1 (en) | 2020-12-15 | 2022-06-23 | Robert Bosch Gmbh | Method for producing an electrically conductive carbon conductor with carbon structural forms |
| WO2022128495A1 (en) | 2020-12-15 | 2022-06-23 | Robert Bosch Gmbh | Method for producing an electrically conductive conductor strand having at least one carbon conductor |
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Application publication date: 20170531 |