CN109160507A - The magnanimity preparation method of fluorinated graphene - Google Patents
The magnanimity preparation method of fluorinated graphene Download PDFInfo
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- CN109160507A CN109160507A CN201811223796.1A CN201811223796A CN109160507A CN 109160507 A CN109160507 A CN 109160507A CN 201811223796 A CN201811223796 A CN 201811223796A CN 109160507 A CN109160507 A CN 109160507A
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- fluorinated graphene
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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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/10—Carbon fluorides, e.g. [CF]nor [C2F]n
Abstract
The present invention provides a kind of magnanimity preparation method of fluorinated graphene, after cationic surfactant and organic intercalation agent processing, ultrasound removing, the fluorinated graphene of single layer or few layer is can be obtained using cheap fluorographite as raw material in the present invention.The preparation method simple process, reaction is mild, and easily controllable, raw material is cheap and easy to get, and yield is high, is suitable for extensive macroblock quantization industrial production application.
Description
Technical field
The invention belongs to field of new materials, are related to a kind of magnanimity preparation method of fluorinated graphene.
Background technique
A kind of new derivatives of the fluorinated graphene as grapheme material, had both maintained the high-intensity performance of graphene,
Because the introducing of fluorine atom is brought, surface can be reduced, hydrophobicity enhances and novel interface and the physical chemistry such as Bandgap extension again
Performance.Especially compared with the graphene of zero band gap, the controllable introducing of fluorine realizes its electronic structure by conductor, semiconductor to absolutely
The transition and transformation of edge body, the broadening of band gap is so that fluorinated graphene shows more excellent photoelectric properties and bigger reality
Border application possibility.These excellent characteristics of fluorinated graphene have it in fields such as lubricant, electronic optical devices
Huge application potential.Continuous development prepares scientific research and skill of the new method for fluorinated graphene field of fluorinated graphene
Art application has great significance.
The preparation method of fluorinated graphene mainly has graphene fluorination and two kinds of mechanical stripping fluorographite at present.Former
It is the F using graphene as raw material2Or XeF2For fluorination reagent, graphene is exposed to F2Or XeF2Atmosphere in fluorination reaction occurs
It realizes, since this method is higher to reaction atmosphere and equipment requirement, expensive, reaction is not easy to control easily to cause danger,
And fluorization agent has severe toxicity, it is difficult to realize industrialization；Second method carries out it using fluorographite as raw material, by various means
Removing obtains fluorinated graphene, and the method that Withers seminar is by mechanically pulling off removes fluorographite to obtain fluorographite
Alkene, it is clear that the method is not used to large scale preparation fluorinated graphene, and Zboril seminar is using the very strong sulfolane of polarity
Solvent liquid phase ultrasound removing fluorographite obtains fluorinated graphene, the disadvantage of this method is that having used the stronger ring of toxicity
Fourth sulfone.Since the application prospect of fluorinated graphene is boundless, it is non-to find easy, environmentally friendly, economic magnanimity preparation method
It is often urgent.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of magnanimity preparation method of fluorinated graphene,
A kind of method that simple and effective magnanimity prepares fluorinated graphene.
This invention takes following technical solutions: a kind of magnanimity preparation method of fluorinated graphene, with cheap fluorination stone
Ink is raw material, and after cationic surfactant and organic intercalation agent processing, ultrasound removing, single layer or few layer can be obtained
Fluorinated graphene, comprising the following steps:
Step 1: cationic surfactant being placed in a beaker, solvent, the ratio of cationic surfactant and solvent is added
For 1g:30 ~ 200mL, the mixed solution for stirring 10 ~ 30min at room temperature is spare；
Step 2: taking fluorographite powder that organic intercalation agent is added, the ratio of fluorographite powder and organic intercalation agent is
The mixed solution prepared in step 1,1 ~ 8h of water bath with thermostatic control at 25 ~ 70 DEG C is added in 1g:50 ~ 300mL；
Step 3: the resulting mixed liquor of natural cooling step 2 at room temperature is placed in ultrasound 20min ~ 10h in ultrasonic vibration washer,
Obtain fluorinated graphene dispersion liquid；
Step 4: the resulting fluorinated graphene dispersion liquid of step 3 being centrifuged, supernatant liquid is collected, by washing, taking out
It filters, be dried to obtain fluorinated graphene.
Preparation method simple process of the present invention, reaction is mild, and easily controllable, raw material is cheap and easy to get, and yield is high, is suitable for big
Scale magnanimity industrialized production.
The cationic surfactant is dodecyldimethylamine yl pyridines ammonium bromide, dialkyl ethanolamine ester methyl sulphur
One of sour ammonium methyl, dimethyl diallyl ammonium chloride, cetyl trimethylammonium bromide, vinyl pyrrolidone are more
Kind mixture；
The organic intercalation agent be N-Methyl pyrrolidone, N, N- dimethylformamide, N, N- dimethyl acetamide,
N- methylacetamide, pyrroles, pyridine, one of 1,3- dimethyl -2- imidazo alkanone or a variety of mixtures.
The solvent is one of methylene chloride, isopropanol, ethyl alcohol or more than one combinations.
Ultrasonic power in the step 3 is 30 ~ 250W.
Fluorinated graphene dispersion liquid is centrifuged in the step 4, revolving speed control 3500 ~
12000rpm, 6 ~ 20min of time.
Drying in the step 4 is at least one of freeze-drying, vacuum drying, spray drying.
The beneficial effects of the present invention are:
(1) using fluorographite cheap and easy to get as raw material, fluorinated graphene is prepared by ultrasonic removing, preparation process is simple, nothing
Special or complicated consersion unit is needed, cost is lower；
(2) preparation step is few, and controllability is good, and high production efficiency, the period is short, is suitable for large-scale industrial production；
(3) the fluorinated graphene product purity prepared is high, for fluorinated graphene deeper into research to provide good preparation basic,
It can be widely used for the fields such as high temperature corrosion-resisting coating, nano electron device, lithium ion battery and electro-catalysis simultaneously.
Detailed description of the invention
Fig. 1 is the TEM figure of fluorinated graphene prepared by embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
0.2g cetyl trimethylammonium bromide is placed in 100mL beaker, 20mL isopropanol is added, stirs 10min at room temperature
Obtain mixed solution；
0.2g fluorographite powder is taken, 50mLN- methyl pyrrolidone is added, above-mentioned cetyl trimethyl bromine is added after stirring
Change ammonium mixed solution, the water bath with thermostatic control 2h at 50 DEG C；
It at room temperature after natural cooling, is placed in ultrasonic vibration washer, 150W power ultrasound 2h；
The fluorinated graphene dispersion liquid obtained after ultrasound removing is centrifuged, is centrifuged 15min under the conditions of 12000rmp,
Supernatant liquor is collected, is filtered, is repeatedly washed using ethyl alcohol, freeze-drying obtains target product fluorinated graphene.
Fig. 1 is the TEM of fluorinated graphene manufactured in the present embodiment.
Embodiment 2
0.3g dodecyldimethylamine yl pyridines ammonium bromide is placed in 100mL beaker, 50mL methylene chloride is added, stirs at room temperature
10min；
0.5g fluorographite powder is taken, 100mLN- methyl pyrrolidone is added, dodecyldimethylamine yl pyridines bromine is added after stirring
Change ammonium mixed solution, the water bath with thermostatic control 2h at 30 DEG C；
It at room temperature after natural cooling, is placed in ultrasonic vibration washer, 150W power ultrasound 6h；
The fluorinated graphene dispersion liquid obtained after ultrasound removing is centrifuged, is centrifuged 10min under the conditions of 12000rmp,
Supernatant liquor is collected, is filtered, is repeatedly washed using ethyl alcohol, freeze-drying obtains target product fluorinated graphene.
Embodiment 3
0.4g cetyl trimethylammonium bromide is placed in 100mL beaker, 30mL ethyl alcohol is added, stirs 10min at room temperature；
0.1g fluorographite powder is taken, 50mL N is added, cetyl trimethyl bromine is added in N- dimethyl acetamide after stirring
Change ammonium mixed solution, the water bath with thermostatic control 2h at 60 DEG C；
It at room temperature after natural cooling, is placed in ultrasonic vibration washer, 200W power ultrasound 4h；
The fluorinated graphene dispersion liquid obtained after ultrasound removing is centrifuged, is centrifuged 15min under the conditions of 10000rmp,
Supernatant liquor is collected, is filtered, is repeatedly washed using ethyl alcohol, freeze-drying obtains target product fluorinated graphene.
Embodiment 4
0.2g vinyl pyrrolidone is placed in 100mL beaker, 10mL isopropanol is added, stirs 10min at room temperature；
1g fluorographite powder is taken, 300mLN- methyl pyrrolidone is added, it is molten that vinyl pyrrolidone mixing is added after stirring
Liquid, the water bath with thermostatic control 3h at 60 DEG C；
It at room temperature after natural cooling, is placed in ultrasonic vibration washer, 150W power ultrasound 10h；To what is obtained after ultrasound removing
Fluorinated graphene dispersion liquid is centrifuged, and 20min is centrifuged under the conditions of 8000rmp, collects supernatant liquor, is filtered,
It is repeatedly washed using ethyl alcohol, vacuum drying obtains target product fluorinated graphene.
Claims (7)
1. a kind of magnanimity preparation method of fluorinated graphene, which is characterized in that using cheap fluorographite as raw material, by sun from
After sub- surfactant and organic intercalation agent processing, ultrasound removing, the fluorinated graphene of single layer or few layer can be obtained, including
Following steps:
Step 1: cationic surfactant being placed in a beaker, solvent, the ratio of cationic surfactant and solvent is added
For 1g:30 ~ 200mL, the mixed solution for stirring 10 ~ 30min at room temperature is spare；
Step 2: taking fluorographite powder, be added organic intercalation agent, the ratio of fluorographite powder and organic intercalation agent is
The mixed solution prepared in step 1,1 ~ 8h of water bath with thermostatic control at 25 ~ 70 DEG C is added in 1g:50 ~ 300mL；
Step 3: the resulting mixed liquor of natural cooling step 2 at room temperature is placed in ultrasound 20min ~ 10h in ultrasonic vibration washer,
Obtain fluorinated graphene dispersion liquid；
Step 4: the resulting fluorinated graphene dispersion liquid of step 3 being centrifuged, supernatant liquid is collected, by washing, taking out
It filters, be dried to obtain fluorinated graphene.
2. the magnanimity preparation method of fluorinated graphene as described in claim 1, which is characterized in that the cationic surface is living
Property agent be dodecyldimethylamine yl pyridines ammonium bromide, dialkyl ethanolamine ester methyl sulfate methyl ammonium, dimethyl diallyl chlorine
Change one of ammonium, cetyl trimethylammonium bromide, vinyl pyrrolidone or a variety of mixtures.
3. the magnanimity preparation method of fluorinated graphene as described in claim 1, which is characterized in that the solvent is dichloromethane
One of alkane, isopropanol, ethyl alcohol or more than one combinations.
4. the magnanimity preparation method of fluorinated graphene as described in claim 1, which is characterized in that the organic intercalation agent
Are as follows: N-Methyl pyrrolidone, N, N- dimethylformamide, N, N- dimethyl acetamide, N- methylacetamide, pyrroles, pyrrole
Pyridine, one of 1,3- dimethyl -2- imidazo alkanone or a variety of mixtures.
5. the magnanimity preparation method of fluorinated graphene as described in claim 1, which is characterized in that the ultrasonic power is 30
~250W。
6. the magnanimity preparation method of fluorinated graphene as described in claim 1, which is characterized in that pair in the step 4
Fluorinated graphene dispersion liquid is centrifuged, and revolving speed is controlled in 3500 ~ 12000rpm, 6 ~ 20min of time.
7. the magnanimity preparation method of fluorinated graphene as described in claim 1 or 6, which is characterized in that in the step 4
Dry is at least one of freeze-drying, vacuum drying, spray drying.
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Cited By (4)
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| CN111171483A (en) * | 2020-02-21 | 2020-05-19 | 广州机械科学研究院有限公司 | Wear-resistant self-lubricating sealing composite material |
| CN111533122A (en) * | 2020-03-31 | 2020-08-14 | 四川大学 | Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof |
| CN111690453A (en) * | 2020-06-30 | 2020-09-22 | 中国人民解放军陆军勤务学院 | Polyurea-based lubricating grease containing fluorographene and preparation method thereof |
| CN113871615A (en) * | 2021-08-31 | 2021-12-31 | 兰州大学 | Fluorinated graphene electrode active material and preparation method and application thereof |
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| CN107200319A (en) * | 2017-07-19 | 2017-09-26 | 西安交通大学 | One kettle way liquid phase peels off the method for being prepared on a large scale high-quality graphene |
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| CN104843680A (en) * | 2015-04-03 | 2015-08-19 | 北京理工大学 | Method for batch preparation of graphene from microcrystalline graphite |
| CN107200319A (en) * | 2017-07-19 | 2017-09-26 | 西安交通大学 | One kettle way liquid phase peels off the method for being prepared on a large scale high-quality graphene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171483A (en) * | 2020-02-21 | 2020-05-19 | 广州机械科学研究院有限公司 | Wear-resistant self-lubricating sealing composite material |
| CN111533122A (en) * | 2020-03-31 | 2020-08-14 | 四川大学 | Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof |
| CN111690453A (en) * | 2020-06-30 | 2020-09-22 | 中国人民解放军陆军勤务学院 | Polyurea-based lubricating grease containing fluorographene and preparation method thereof |
| CN113871615A (en) * | 2021-08-31 | 2021-12-31 | 兰州大学 | Fluorinated graphene electrode active material and preparation method and application thereof |
| CN113871615B (en) * | 2021-08-31 | 2024-03-15 | 兰州大学 | Fluorinated graphene electrode active material and preparation method and application thereof |
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