CN109179395A - A kind of fluorinated graphene and preparation method thereof, application - Google Patents
A kind of fluorinated graphene and preparation method thereof, application Download PDFInfo
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- CN109179395A CN109179395A CN201811236756.0A CN201811236756A CN109179395A CN 109179395 A CN109179395 A CN 109179395A CN 201811236756 A CN201811236756 A CN 201811236756A CN 109179395 A CN109179395 A CN 109179395A
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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
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/02—Carbon; Graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/04—Elements
- C10M2201/041—Carbon; Graphite; Carbon black
- C10M2201/042—Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of fluorinated graphenes and preparation method thereof, application.A kind of preparation method of fluorinated graphene, including the following steps: make redox graphene and fluorization agent that fluorination reaction occur at 280~550 DEG C；The fluorization agent is F2With the mixed gas of inert gas, fluorine volumetric concentration is 1~10%, preferably 3~10%, preferably 3~8%, preferably 3~5% in mixed gas.Present invention F2It is fluorinated modified to redox graphene with the mixed gas of inert gas, safety, stability and the controllability of technique are improved, and high-purity F is effectively reduced2Corrosion to fluorizating apparatus solves the problems, such as that current process costs are high and fluorination quality is low.
Description
Technical field
The present invention relates to field of material technology, more particularly, to a kind of fluorinated graphene and preparation method thereof, application.
Background technique
A kind of derivative of the fluorinated graphene as graphene, is graphene fluorination or partially fluorinated product, it is combined
The feature performance benefit of graphene and fluorographite, such as high intensity, high Young's modulus, large specific surface area, excellent lubricity, dredge
The characteristics such as aqueous and abrasion resistance and band gap are wide.Different sizes, the number of plies, degree of fluorination and the fluorinated graphene of functional group, in light
, electricity, calorifics and interface etc. show different characteristics, thus can be widely applied to solid lubricant, antifouling anti-
The fields such as corrosion material, lithium fluorocarbon cell positive electrode material, super hydrophobic material and wear-resistant material, and in nano electron device, light
The fields such as electronic device have potential application.But it is constrained to quality, production capacity and the stabilization of graphene and fails
With suitable flaorination process, domestic at present there has been no being capable of scale, the stably and controllable enterprise for producing fluorinated graphene.
Preparing fluorinated graphene at present, there are mainly four types of technology paths:
First is that directly being reacted using strong fluorination reagent such as fluorine gas, xenon difluoride with graphene or reduced graphene.This side
Method is fast and effective, but cost of material is high, consersion unit requires harshness.
Second is that carrying out hydro-thermal reaction under high-temperature and high-pressure conditions using hydrogen fluoride and concentrated nitric acid and graphene oxide.This side
Method can prepare few layer of high quality fluorinated graphene, but material is stationary at high temperature, and mass transfer is insufficient, is conducive to graphite
The self assembly and aggregation of alkene are unfavorable for reacting for chemical reagent and graphene oxide, are difficult to prepare fluorine-containing more uniform fluorine
Graphite alkene.
Third is that although being reduced costs to fluorographite progress mechanical stripping or chemical stripping, this method, due to fluorination
Graphite polarizability is low, and liquid medium is difficult intercalation stripping, it is difficult to obtain few layer of fluorinated graphene of higher yields；And pass through strong oxygen
Agent is modified as melting KOH or NaOH pre-oxidizes fluorographite, can prepare single layer fluorinated graphene, but fluorinated graphene
It is easy defluorinate, causes degree of fluorination limited.
Fourth is that using supercritical CO2As remover, various alcohols, surfactant are that dispersing agent can prepare fluorographite
Alkene, this method is environmentally protective, simple and safe, but yield is lower, degree of fluorination is low and is unfavorable for the application of product containing dispersing agent
Development.
Therefore, how safe and stable, controllable and prepare with scale goes out a kind of fluorinated graphene, especially a kind of high quality
The fluorinated graphene of high degree of fluorination becomes current technology difficult point.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of fluorinated graphene, preparation method F2With inertia
The mixed gas of gas is fluorinated modified to redox graphene, improves safety, stability and the controllability of technique, and has
Effect reduces high-purity F2Corrosion to fluorizating apparatus solves the problems, such as that current process costs are high and fluorination quality is low.
The second object of the present invention is to provide a kind of fluorinated graphene, with the spherical structure of fold, sphere sizes
It is 0.5~10 μm, fluorine carbon ratio (degree of fluorination) is up to 0.5~1.2:1, and specific surface area is up to 350~520m2/ g, and organic molten
There is good dispersibility in agent, lubricant grease and resin matrix, can be applied to lithium fluorocarbon cell positive electrode material, lubrication material
The fields such as material, hydrophobic material and wear-resistant material.
In order to achieve the goal above, the present invention provides following technical schemes:
A kind of preparation method of fluorinated graphene, including the following steps:
Make redox graphene and fluorization agent that fluorination reaction occur at 280~550 DEG C；
The fluorization agent is F2With the mixed gas of inert gas, fluorine volumetric concentration is 1~10% in mixed gas, preferably
3~10%, preferably 3~8%, preferably 3~5%；The preferred N of inert gas2Or Ar2。
Compared with prior art, invention achieves following technical effects:
(1) the preferable low defect graphene oxide of the preferred lamellar structure of preparation method of the present invention is raw material, also by control
The reduced graphene of the spherical structure of fold can be obtained in original process condition, reduced graphene activity with higher, to mention
The reaction efficiency of high graphene and fluorization agent reduces fluorination reaction temperature.
(2) the preparation method of the present invention flaorination process more mature using the art, and combine reduced graphene material
Expect the preferred F of characteristic2/ inert gas mixed gas is fluorination reagent, improves safety, stability and the controllability of technique, and
High-purity F is effectively reduced2Corrosion to fluorizating apparatus.
In addition, using F2With N2Or Ar2Mixed gas be fluorization agent, need within specified temperatures with reduction-oxidation graphite
Alkene reaction could obtain certain degree of fluorination, the fluorination performances such as structure and specific surface area.Meanwhile in 280~550 DEG C of ranges
Interior to control reasonable temperature and reaction time, adjustable degree of fluorination is fluorinated the performances such as structure and specific surface area, such as
280 DEG C, 300 DEG C, 320 DEG C, 350 DEG C, 380 DEG C, 400 DEG C, 420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 550 DEG C etc..Wherein, it mixes
F in gas2Content fluorination result is also had a major impact, being investigated can obtain preferable degree of fluorination and ratio 1~10%
Surface area, can select arbitrary ratio within this range, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%,
10% etc..
Due in graphene oxide containing combining water and oxygen, under high temperature with F2There are the security risks of explosion when reaction；And
Physical method preparation graphene sheet layer it is thicker and active lower, can not high efficiency obtain the fluorographite of high fluorine content high-quality
Alkene.Therefore, selective reduction graphene oxide of the present invention is matched with this flaorination process, is accomplished scale production.
In principle, any type of redox graphene is suitable for F2With the fluorization agent of inert gas and 280~
550 DEG C of fluorination temperature, including it is commercially available and homemade.However fault of construction and degree of oxidation due to graphene oxide and
The structure of redox graphene and reducing degree difference, so that the materialization activity on reaction raw materials surface is different, and then cause most
Fluorination efficiency, degree of fluorination, the fluorination performances such as structure and specific surface area of whole material are different.
In order to obtain more excellent degree of fluorination, fluorination structure and specific surface area etc., the present invention filters out preferable oxygen
The process conditions such as the type and reduction process of graphite alkenes type and redox graphene, and pretreatment, fluorination,
It is specific as follows.
Preferably, the temperature of the fluorination reaction is: with the heating rate of 5~15 DEG C/min, 280~550 DEG C are warming up to,
Then 3~50 hours are kept the temperature.
If heating rate is too fast, fluorination reaction is insufficient, reduces quality of graphene；If heating rate is excessively slow, fluorine
Change overlong time, increases unnecessary fluorination cost.It is preferred through investigating with the heating rate of 5~15 DEG C/min, such as 5 DEG C/
Min, 8 DEG C/min, 10 DEG C/min, 12 DEG C/min, 15 DEG C/min etc..
It is highly preferred that heating rate is 10~15 DEG C/min, the outlet temperature preferably 350 after heating when the fluorination reaction
~450 DEG C.
Preferably, the redox graphene is that low defect graphene oxide powder is made through reducing process, described low
Defect graphene oxide powder is one of LDGO2211 powder, LDGO2111 powder, LDGO2311 powder or a variety of.
The model of the above low defect graphene oxide powder refers both to high star new carbon Changzhou Co., Ltd production.
Or the redox graphene directlyed adopt with flowering structure:
Preferably, the redox graphene is the spherical structure of fold, and piece diameter is having a size of 0.05~20 μm, the number of plies
3~5 layers；Carbon content is preferably 75~95wt.%, and oxygen content is preferably 3~20wt.%, and ash content is less than 1wt.%.
The redox graphene of structure activity with higher, so that improves graphene and fluorization agent reacts effect
Rate reduces fluorination reaction temperature and reaction time.
Preferably, the reducing process are as follows: under 0.1Mpa vacuum condition, be warming up to the heating rate of 5~15 DEG C/min
200~1200 DEG C, and insulation reaction 2~20 hours；
It is highly preferred that the reducing process are as follows: under 0.1Mpa vacuum condition, heated up with the heating rate of 10~15 DEG C/min
To 500~800 DEG C, and insulation reaction 2~20 hours.
Before being fluorinated redox graphene, fluorinated impurity is unfavorable for by vacuum removal of impurities removal, it is specific as follows.
Preferably, the redox graphene further includes vacuum removal of impurities: vacuum degree 0.1Mpa or less item before fluorination
Under part, 100~250 DEG C are warming up to the heating rate of 5~15 DEG C/min, and keep the temperature 0.5~5 hour；
It is highly preferred that the process of the vacuum removal of impurities are as follows: under vacuum degree 0.1Mpa the following conditions, with 10~15 DEG C/min's
Heating rate is warming up to 100~200 DEG C, and keeps the temperature 0.5~5 hour.
To sum up, compared with prior art, invention achieves following technical effects:
(1) present invention uses F2The mixed gas of/inert gas is fluorinated modified to redox graphene, improves technique
Safety, stability and controllability, and high-purity F is effectively reduced2Corrosion to fluorizating apparatus；
(2) present invention is had found by investigating influence of the characteristic of redox graphene to fluorination result with fold class ball
When the redox graphene of shape structure is raw material, preferable fluorination effect can be obtained, therefore filtered out preferable oxidation stone
Black alkenes type and reducing process condition etc.；
(3) the fluorinated graphene degree of fluorination with higher prepared by the present invention, the fluorination structure and higher of rule
Specific surface area (have the spherical structure of fold, sphere sizes be 0.5~10 μm, fluorine carbon ratio is up to 0.5~1.2:1, specific surface
Product is up to 350~520m2/ g), therefore there is good dispersibility in organic solvent, lubricant grease and resin matrix, it can answer
For lithium fluorocarbon cell positive electrode material, lubriation material, hydrophobic material, wear-resistant material or other fields leaved for development.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the shape appearance figure of present invention preparation gained reduced graphene；
Fig. 2 is the shape appearance figure of present invention preparation gained fluorinated graphene；
Fig. 3 is the XPS map of present invention preparation gained fluorinated graphene；
Fig. 4 is the FT-IR map of present invention preparation gained fluorinated graphene；
Fig. 5 is the XRD spectrum of present invention preparation gained fluorinated graphene.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 600 DEG C, and insulation reaction 2 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 3% F2/N2Mixed gas is warming up to 350 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 2
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 800 DEG C, and insulation reaction 2 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 1% F2/N2Mixed gas is warming up to 300 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 3
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 600 DEG C, and insulation reaction 5 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through, 5% F2/N2Mixed gas is warming up to 450 DEG C with the rate of 10 DEG C/min, and insulation reaction 30 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 4
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 1000 DEG C, and insulation reaction 5 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 2 hours progress edulcoration purifications
Reason；It is passed through 10% F2/N2Mixed gas is warming up to 450 DEG C with the rate of 15 DEG C/min, and insulation reaction 30 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 5
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 5 DEG C/min of program are warming up to 800 DEG C, and insulation reaction 2 hours, terminate program naturally cool to room temperature to get
To the spherical reduced graphene of fold.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 10 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 8% F2/N2Mixed gas is warming up to 350 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 6
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 600 DEG C, and insulation reaction 10 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
Embodiment 7
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 200 DEG C, and insulation reaction 20 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
Embodiment 8
The preparation of reduced graphene: weighing in 100g LDGO2211 powder merging quartz tube furnace, closed to be evacuated to
0.1Mpa, setting 10 DEG C/min of program are warming up to 1200 DEG C, and insulation reaction 2 hours, terminate program and naturally cool to room temperature, i.e.,
Obtain the spherical reduced graphene of fold.
Embodiment 9
Reduced graphene is the same as embodiment 1.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 10% F2/N2Mixed gas is warming up to 350 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 10
Reduced graphene is the same as embodiment 1.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 5% F2/N2Mixed gas is warming up to 350 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 11
Reduced graphene is the same as embodiment 1.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 3% F2/N2Mixed gas is warming up to 350 DEG C with the rate of 5 DEG C/min, insulation reaction 20 hours, naturally cools to
Room temperature to get arrive fluorinated graphene.
Embodiment 12
Reduced graphene is the same as embodiment 1.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 3% F2/N2Mixed gas is warming up to 280 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Embodiment 13
Reduced graphene is the same as embodiment 1.
The preparation of fluorinated graphene: the reduced graphene 30g of the spherical structure of above-mentioned fold is taken to imported into closed fluorination
In reaction kettle, under 0.1Mpa vacuum condition, 200 DEG C are warming up to 5 DEG C/min rate, is kept the temperature at 3 hours progress edulcoration purifications
Reason；It is passed through 3% F2/N2Mixed gas is warming up to 550 DEG C with the rate of 10 DEG C/min, and insulation reaction 20 hours, natural cooling
To room temperature to get arrive fluorinated graphene.
Comparative example
Other graphenes: using market company physical method graphene, and graphene performance indicator is as follows: carbon content is
99.5wt.%, ash content are less than 0.5wt.%, and piece diameter size is 5~10 μm, and piece diameter is with a thickness of 1~3nm.
The preparation of fluorinated graphene is the same as embodiment 1.
The characteristic of 1 to 8 gained reduced graphene of comparing embodiment, the results are shown in Table 1.
Table 1
Compare the performance of fluorinated graphene obtained by different fluorination conditions, as a result such as table 2.
Table 2
In addition, the present invention has also listed the shape appearance figure of reduced graphene prepared by embodiment 1 and fluorinated graphene, point
Not not as illustrated in fig. 1 and 2；XPS map such as Fig. 3 of fluorinated graphene, FT-IR map such as Fig. 4, XRD spectrum such as Fig. 5.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of preparation method of fluorinated graphene, characterized in that it comprises the following steps:
Make redox graphene and fluorization agent that fluorination reaction occur at 280~550 DEG C；
The fluorization agent is F2With the mixed gas of inert gas, in mixed gas fluorine volumetric concentration be 1~10%, preferably 3~
10%, preferably 3~8%, preferably 3~5%；The preferred N of inert gas2Or Ar2。
2. preparation method according to claim 1, which is characterized in that the temperature of the fluorination reaction is: with 5~15 DEG C/
The heating rate of min is warming up to 280~550 DEG C, then keeps the temperature 3~50 hours.
3. preparation method according to claim 2, which is characterized in that heating rate is 10~15 when the fluorination reaction
DEG C/min, preferably 350~450 DEG C of the outlet temperature after heating.
4. preparation method according to claim 1, which is characterized in that the redox graphene is that low defect aoxidizes stone
Black alkene powder through reducing process be made, the low defect graphene oxide powder be LDGO2211 powder, LDGO2111 powder and
One of LDGO2311 powder is a variety of.
5. preparation method according to claim 1, which is characterized in that the redox graphene is the spherical knot of fold
Structure, for piece diameter having a size of 0.05~20 μm, the number of plies is 3~5 layers；Carbon content is preferably 75~95wt.%, and oxygen content is preferably 3~
20wt.%, ash content are less than 1wt.%.
6. the preparation method according to claim 4, which is characterized in that the reducing process are as follows: 0.1Mpa or less vacuum item
Under part, 200~1200 DEG C, and insulation reaction 2~20 hours are warming up to the heating rate of 5~15 DEG C/min；
Preferably, the reducing process are as follows: under 0.1Mpa or less vacuum condition, be warming up to the heating rate of 10~15 DEG C/min
500~800 DEG C, and insulation reaction 2~20 hours.
7. preparation method according to claim 1, which is characterized in that the redox graphene also wraps before fluorination
It includes vacuum removal of impurities: under the conditions of vacuum degree 0.1Mpa, being warming up to 100~250 DEG C with the heating rate of 5~15 DEG C/min, and keep the temperature
0.5~5 hour；
Preferably, the process of the vacuum removal of impurities are as follows: under the conditions of vacuum degree 0.1Mpa, with the heating rate liter of 10~15 DEG C/min
Temperature keeps the temperature 0.5~5 hour to 100~200 DEG C.
8. a kind of fluorinated graphene, which is characterized in that be made using the described in any item preparation methods of claim 1-7.
9. fluorinated graphene according to claim 8, which is characterized in that fluorine carbon ratio is 0.5~1.2:1, and specific surface area is
350~520m2/g。
10. the application of fluorinated graphene described in claim 8 or 9, which is characterized in that be used to prepare lithium fluorocarbon cell positive electrode
Material, lubriation material, hydrophobic material and wear-resistant material.
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Cited By (12)
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| CN109679758A (en) * | 2019-01-21 | 2019-04-26 | 江苏捷达油品有限公司 | A kind of environment-friendly water-based diamond wire silicon wafer circulation cutting liquid of the clean type of low COD and application |
| CN110862700A (en) * | 2019-12-03 | 2020-03-06 | 祁娟 | Preparation method of oil-water amphiphilic powder and powder prepared by same |
| CN110961078A (en) * | 2019-11-28 | 2020-04-07 | 河海大学 | Application of fluorinated graphene material, solid-phase micro-extraction probe and adsorption extraction stirring rod based on fluorinated graphene extraction coating |
| CN111474221A (en) * | 2020-02-17 | 2020-07-31 | 中国农业科学院油料作物研究所 | Electrochemical sensor based on gold nanocage/fluorinated graphene and application |
| CN111533122A (en) * | 2020-03-31 | 2020-08-14 | 四川大学 | Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof |
| CN112624098A (en) * | 2021-01-20 | 2021-04-09 | 湖北卓熙氟化股份有限公司 | Preparation method and application of fluorinated graphene with high fluorocarbon ratio |
| CN112661146A (en) * | 2020-12-23 | 2021-04-16 | 湘潭大学 | Preparation method of laminated fluorinated graphene for positive electrode of lithium battery |
| CN113871615A (en) * | 2021-08-31 | 2021-12-31 | 兰州大学 | Fluorinated graphene electrode active material and preparation method and application thereof |
| CN114657002A (en) * | 2022-04-02 | 2022-06-24 | 北京交通大学 | Modification method of graphene lubricating oil based on fluorine ion doping |
| CN115261105A (en) * | 2022-09-15 | 2022-11-01 | 汉能（青岛）润滑科技有限公司 | Preparation method of anti-wear energy-saving lubricating oil |
| CN115403431A (en) * | 2022-08-25 | 2022-11-29 | 四川大学 | Gas-phase fluorinated modified aluminum powder and preparation method thereof |
| CN116354667A (en) * | 2023-03-28 | 2023-06-30 | 广西建宏水泥制品有限公司 | Sound insulation mortar with low water absorption rate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109679758B (en) * | 2019-01-21 | 2021-10-01 | 江苏捷达油品有限公司 | Low-COD clean type environment-friendly water-based diamond wire silicon wafer circulating cutting fluid and application |
| CN109679758A (en) * | 2019-01-21 | 2019-04-26 | 江苏捷达油品有限公司 | A kind of environment-friendly water-based diamond wire silicon wafer circulation cutting liquid of the clean type of low COD and application |
| CN110961078A (en) * | 2019-11-28 | 2020-04-07 | 河海大学 | Application of fluorinated graphene material, solid-phase micro-extraction probe and adsorption extraction stirring rod based on fluorinated graphene extraction coating |
| CN110862700A (en) * | 2019-12-03 | 2020-03-06 | 祁娟 | Preparation method of oil-water amphiphilic powder and powder prepared by same |
| CN111474221A (en) * | 2020-02-17 | 2020-07-31 | 中国农业科学院油料作物研究所 | Electrochemical sensor based on gold nanocage/fluorinated graphene and application |
| CN111474221B (en) * | 2020-02-17 | 2022-11-25 | 中国农业科学院油料作物研究所 | Electrochemical sensor based on gold nanocage/fluorinated graphene and application |
| CN111533122A (en) * | 2020-03-31 | 2020-08-14 | 四川大学 | Fluorinated graphene macroscopic assembly, graphene macroscopic assembly and preparation method thereof |
| CN112661146A (en) * | 2020-12-23 | 2021-04-16 | 湘潭大学 | Preparation method of laminated fluorinated graphene for positive electrode of lithium battery |
| CN112661146B (en) * | 2020-12-23 | 2022-07-05 | 湘潭大学 | Preparation method of laminated fluorinated graphene for positive electrode of lithium battery |
| CN112624098A (en) * | 2021-01-20 | 2021-04-09 | 湖北卓熙氟化股份有限公司 | Preparation method and application of fluorinated graphene with high fluorocarbon ratio |
| 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 |
| CN114657002A (en) * | 2022-04-02 | 2022-06-24 | 北京交通大学 | Modification method of graphene lubricating oil based on fluorine ion doping |
| CN115403431A (en) * | 2022-08-25 | 2022-11-29 | 四川大学 | Gas-phase fluorinated modified aluminum powder and preparation method thereof |
| CN115261105A (en) * | 2022-09-15 | 2022-11-01 | 汉能（青岛）润滑科技有限公司 | Preparation method of anti-wear energy-saving lubricating oil |
| CN116354667A (en) * | 2023-03-28 | 2023-06-30 | 广西建宏水泥制品有限公司 | Sound insulation mortar with low water absorption rate and preparation method thereof |
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