CN108946706A - A method of fluorinated graphene film is prepared by Fluorine source of fluorine gas - Google Patents
A method of fluorinated graphene film is prepared by Fluorine source of fluorine gas Download PDFInfo
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- CN108946706A CN108946706A CN201710353047.XA CN201710353047A CN108946706A CN 108946706 A CN108946706 A CN 108946706A CN 201710353047 A CN201710353047 A CN 201710353047A CN 108946706 A CN108946706 A CN 108946706A
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- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
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Abstract
The present invention discloses a kind of method for preparing fluorinated graphene film as Fluorine source using fluorine gas, graphene oxide dispersion is carried out with crystalline flake graphite, and graphene oxide film is prepared with this, it is reacted in fluorine gas and nitrogen mixed gas, obtains fluorinated graphene film product.Operation of the present invention is simple, and raw material sources are wide, at low cost, and yield is high, and post-processes simply, and fluorinated graphene film is made in single step reaction.The fluorinated graphene film of acquisition has fine thermal stability, and chemical stability, can use should be in the fields such as high quality barrier material and lithium ion battery.
Description
Technical field
The present invention relates to the preparation method of fluorinated graphene film, a kind of specifically prepared using fluorine gas as Fluorine source is fluorinated
The method of graphene film.
Background technique
Fluorinated graphene is a kind of derived material of graphene, and graphene is zero energy gap semiconductor material of one kind, in electricity
On application sometimes will receive some limitations, it is on nanobelt or right to be limited in electronics to open energy band generally
The double-layer structure of graphene carries out some modifications, graphene is chemically modified be one of propagation energy band method.When
When oxygen atom, hydrogen atom or fluorine atom pass through covalent bond in conjunction with the carbon atom in graphene, wide forbidden band is formd.Fluorine is former
Son has been connected on each individually carbon atom, this can eliminate electron cloud, is also possible to prevent the normality flowing of electric current, but this is not
It will affect complete graphite framework in microstructure.In pervious work, they mainly bias toward hydrogen atom rather than fluorine is former
Son, but find that the hydrogenation graphene generated is unstable at high temperature, and fluorinated graphene is a kind of high mechanical strength, calorifics and change
Learn the stable compound of performance.The birth of this novel substance will have an immense impact on to electronic application, it will improve electron mass,
Fluorinated graphene may be used as tunnel obstacle, or as high quality barrier material, be applied in organic electronic product.It prepares
Fluorinated graphene film there is certain mechanical strength to be used directly for battery electrode.
Although had in the past it is some with gas be Fluorine source preparation fluorinated graphene fluorine carbon ratio it is higher, temperature requirement is very
Height consumes energy larger, does not meet present energy-saving and environment-friendly requirement.Therefore preparing fluorinated graphene with lower temperature seems especially heavy
It wants.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide prepare fluorinated graphene film by Fluorine source of fluorine gas
Method, for low yield in current fluorinated graphene membrane preparation method, energy consumption is high, disadvantage of preparation process complexity, and yield reaches
To tens milligrams even several grams of fluorinated graphene film, to meet the needs of to fluorinated graphene film.
Technical purpose of the invention is achieved by following technical proposals:
A method of fluorinated graphene film being prepared by Fluorine source of fluorine gas, is carried out as steps described below:
Step 1, graphene oxide dispersion is placed in mold and gives drying, prepare graphene oxide film；
Step 2, the graphene oxide film prepared by step 1 is placed in reaction kettle and is passed through by percentage by volume 20-
40% fluorine gas and 60-80% nitrogen composition mixed gas, be warming up at 40-120 DEG C and react 1-4h, vacuum drying is
Product fluorinated graphene film can be obtained.
In step 1, graphene oxide dispersion is prepared by hummers method, and goes water to be deployed into concentration by centrifugation
For 2-20mg/ml graphene oxide dispersion, solvent is distilled water.
In step 1,2-5 mass parts of crystalline flake graphite of 100-150 mesh are selected, each mass parts are 1g, are passed through
Hummers method prepares graphene oxide dispersion.
In step 1, dry at least 2 hours, preferably 4-6 hours under 50-60 degrees Celsius, it is thin to prepare graphene oxide
Film.
In step 2, the mixed gas of the fluorine gas of percentage by volume 20-30% and 60-70% nitrogen composition is selected,
It is warming up at 80-120 DEG C and reacts 1-4h.
In step 2,10-12 hours dry under vacuum condition, 50-60 degrees Celsius.
Compared with prior art, operation of the present invention is simple, and raw material sources are wide, at low cost, and yield is high, and post-processes letter
Single, fluorinated graphene film is made in single step reaction on the basis of graphene oxide film；(2) the fluorinated graphene film tool obtained
There is fine thermal stability, chemical stability, can use should be in the fields such as high quality barrier material and lithium ion battery, and it is very good to have
Application prospect.
Detailed description of the invention
Fig. 1 is the stereoscan photograph for the fluorinated graphene film that the present invention is prepared.
Fig. 2 is the EDS energy spectrum diagram for the fluorinated graphene film that the present invention is prepared.
Fig. 3 is the battery performance test figure for the fluorinated graphene film that the present invention is prepared.
Specific embodiment
Technical solution of the present invention is illustrated below by way of specific embodiment.100 mesh crystalline flake graphite 3g are selected to carry out
Hummers method prepares graphene oxide dispersion.
Example 1
(1) it takes crystalline flake graphite to prepare graphene oxide dispersion by hummers method, goes water to be deployed into dispersion liquid centrifugation
Concentration is 2mg/ml graphene oxide dispersion.
(2) the dispersion liquid 10ml in (1) is added in Teflon mould, die horizontal is put into drying box 50 and is taken the photograph
It is 6 hours dry under family name's degree, graphene oxide film is made.
(3) graphene oxide film prepared in (2) is taken out 47.7mg to be put into the reaction kettle of 5L, is passed through 20%F2、
80%N2Mixed gas, react 4h at 120 DEG C.
(4) film obtained in (3) is placed in a vacuum drying oven under 50 degrees Celsius dry 12h, obtains fluorinated graphene
Film product 51.6mg.
Example 2
(1) it takes crystalline flake graphite to prepare graphene oxide dispersion by hummers method, goes water to be deployed into dispersion liquid centrifugation
Concentration is 2mg/ml graphene oxide dispersion.
(2) the dispersion liquid 10ml in (1) is added in Teflon mould, die horizontal is put into drying box 60 and is taken the photograph
It is 4 hours dry under family name's degree, graphene oxide film is made.
(3) graphene oxide film prepared in (2) is taken out 43.1mg to be put into the reaction kettle of 5L, is passed through 20%F2、
80%N2Mixed gas, react 4h at 80 DEG C.
(4) film obtained in (3) is placed in a vacuum drying oven under 50 degrees Celsius dry 12h, obtains fluorinated graphene
Film product 45.3mg.
Example 3
(1) it takes crystalline flake graphite to prepare graphene oxide dispersion by hummers method, goes water to be deployed into dispersion liquid centrifugation
Concentration is 2mg/ml graphene oxide dispersion.
(2) the dispersion liquid 10ml in (1) is added in Teflon mould, die horizontal is put into drying box 60 and is taken the photograph
It is 2 hours dry under family name's degree, graphene oxide film is made.
(3) graphene oxide film prepared in (2) is taken out 27.1mg to be put into the reaction kettle of 5L, is passed through 30%F2、
70%N2Mixed gas, react 4h at 40 DEG C.
(4) film obtained in (3) is placed in a vacuum drying oven under 60 degrees Celsius dry 12h, obtains fluorinated graphene
Film product 28.7mg.
Example 4
(1) it takes crystalline flake graphite to prepare graphene oxide dispersion by hummers method, goes water to be deployed into dispersion liquid centrifugation
Concentration is 20mg/ml graphene oxide dispersion.
(2) the dispersion liquid 10ml in (1) is added in Teflon mould, die horizontal is put into drying box 60 and is taken the photograph
It is 5 hours dry under family name's degree, graphene oxide film is made.
(3) graphene oxide film prepared in (2) is taken out 46.8mg to be put into the reaction kettle of 5L, is passed through 20%F2、
80%N2Mixed gas, react 4h at 120 DEG C.
(4) film obtained in (3) is placed in a vacuum drying oven under 60 degrees Celsius dry 10h, obtains fluorinated graphene
Film product 49.7mg.
Example 5
(1) it takes crystalline flake graphite to prepare graphene oxide dispersion by hummers method, goes water to be deployed into dispersion liquid centrifugation
Concentration is 20mg/ml graphene oxide dispersion.
(2) the dispersion liquid 30ml in (1) is added in Teflon mould, die horizontal is put into drying box 55 and is taken the photograph
It is 5 hours dry under family name's degree, graphene oxide film is made.
(3) graphene oxide film prepared in (2) is taken out 29.8mg to be put into the reaction kettle of 5L, is passed through 40%F2、
60%N2Mixed gas, react 3h at 120 DEG C.
(4) film obtained in (3) is placed in a vacuum drying oven under 60 degrees Celsius dry 12h, obtains fluorinated graphene
Film product 33.4mg.
Product prepared in the above embodiments is characterized, and pattern shows film；It is more that there are contents in component
The peak value of fluorine element, oxygen is weakened, or even is disappeared, and illustrates that graphene oxide is sufficiently reacted in mixed atmosphere, and pattern is not
It changes, keeps original shape substantially.
It weighs PVDF to be added in NMP, is configured to the solution that concentration is 50mg/ml.It is measured respectively for 8:1:1 in mass ratio
FC sample (fluorinated graphene film), acetylene black, PVDF prepare cell positive material.NMP ultrasonic disperse Cheng Jun is added dropwise thereto
Even pulp solution.It is placed in baking oven and is dried using ethyl alcohol cleaning aluminium foil, by scattered pulp solution even application in aluminium
On foil, 60 DEG C of baking 12h in convection oven are placed in, are subsequently placed at 60 DEG C of vacuum drying 12h in vacuum oven.It takes out, uses
Mass difference method determines the amount of active material, carries out battery assembly.The electrolyte group used becomes 1M NaPF6EC (ethylene carbonate
Ester): DMC (dimethyl carbonate), the mixed liquor of the two volume ratio 1:1, that is, the electrolyte group used become 1M NaPF6Solution,
The solution is the mixed solution of ethylene carbonate and dimethyl carbonate, and the two volume ratio is 1:1.The electrode slice prepared is put
Enter in glove box.First stainless steel elastic slice is placed in the negative cover of battery, gasket is placed, is then placed in metal lithium sheet, is added dropwise
Electrolyte is put into diaphragm after standing, places into electrode slice and a few drop electrolyte are added dropwise again, finally sealed with sealing machine.Assembly
Good battery is stood for 24 hours at room temperature, is allowed electrolyte sufficiently to infiltrate positive and negative pole material, is then carried out related chemical property again
Test.Battery is connected on LAND battery test system, after standing 10min, carries out constant current discharge performance test, test
Discharge current be 10mAg-1, final discharging voltage 1.5V, test result is as shown in the picture.
The technological parameter that content is recorded according to the present invention is adjusted, and the preparation of fluorinated graphene film can be achieved, and
Show the performance almost the same with above-described embodiment.Illustrative description has been done to the present invention above, it should explanation,
In the case where not departing from core of the invention, any simple deformation, modification or other skilled in the art can not be spent
The equivalent replacement of expense creative work each falls within protection scope of the present invention.
Claims (5)
1. a kind of method for preparing fluorinated graphene film as Fluorine source using fluorine gas, which is characterized in that carry out as steps described below:
Step 1, graphene oxide dispersion is placed in mold and gives drying, prepare graphene oxide film；
Step 2, the graphene oxide film prepared by step 1 is placed in reaction kettle and is passed through by percentage by volume 20-40%
Fluorine gas and 60-80% nitrogen composition mixed gas, be warming up at 40-120 DEG C and react 1-4h, vacuum drying can be obtained
Product fluorinated graphene film.
2. a kind of method for preparing fluorinated graphene film as Fluorine source using fluorine gas according to claim 1, which is characterized in that
In step 1, graphene oxide dispersion is prepared by hummers method, and going water to be deployed into concentration by centrifugation is 2-20mg/
Ml graphene oxide dispersion, solvent are distilled water.
3. a kind of method for preparing fluorinated graphene film as Fluorine source using fluorine gas according to claim 1, which is characterized in that
In step 1, dry at least 2 hours, preferably 4-6 hours under 50-60 degrees Celsius, to prepare graphene oxide film.
4. a kind of method for preparing fluorinated graphene film as Fluorine source using fluorine gas according to claim 1, which is characterized in that
In step 2, the mixed gas for selecting the fluorine gas of percentage by volume 20-30% and 60-70% nitrogen composition, is warming up to
1-4h is reacted at 80-120 DEG C.
5. a kind of method for preparing fluorinated graphene film as Fluorine source using fluorine gas according to claim 1, which is characterized in that
In step 2,10-12 hours dry under vacuum condition, 50-60 degrees Celsius.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108927191A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | Fluorine-containing graphite-phase nitrogen carbide photochemical catalyst and preparation method thereof |
| CN111533122A (en) * | 2020-03-31 | 2020-08-14 | 四川大学 | Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof |
| CN113353924A (en) * | 2021-07-29 | 2021-09-07 | 西南科技大学 | Preparation method and application of fluorinated graphene photo-thermal conversion film for laser ignition |
| CN115465857A (en) * | 2022-09-15 | 2022-12-13 | 贵州梅岭电源有限公司 | Conductive fluorinated graphene nanoribbon material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108927191A (en) * | 2017-05-22 | 2018-12-04 | 天津大学 | Fluorine-containing graphite-phase nitrogen carbide photochemical catalyst and preparation method thereof |
| CN108927191B (en) * | 2017-05-22 | 2021-05-28 | 天津大学 | Fluorine-containing graphite phase nitrogen carbide photocatalyst and preparation method thereof |
| CN111533122A (en) * | 2020-03-31 | 2020-08-14 | 四川大学 | Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof |
| CN113353924A (en) * | 2021-07-29 | 2021-09-07 | 西南科技大学 | Preparation method and application of fluorinated graphene photo-thermal conversion film for laser ignition |
| CN115465857A (en) * | 2022-09-15 | 2022-12-13 | 贵州梅岭电源有限公司 | Conductive fluorinated graphene nanoribbon material and preparation method thereof |
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