CN107399734A - A kind of high yield fluorinated graphene preparation method - Google Patents
A kind of high yield fluorinated graphene preparation method Download PDFInfo
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- CN107399734A CN107399734A CN201710675774.8A CN201710675774A CN107399734A CN 107399734 A CN107399734 A CN 107399734A CN 201710675774 A CN201710675774 A CN 201710675774A CN 107399734 A CN107399734 A CN 107399734A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 81
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 43
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 40
- 239000000138 intercalating agent Substances 0.000 claims abstract description 33
- 238000012856 packing Methods 0.000 claims abstract description 17
- 230000004044 response Effects 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical compound [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- -1 fluorographite Alkene Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 30
- 229960004424 carbon dioxide Drugs 0.000 description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 230000036772 blood pressure Effects 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 239000010410 layer Substances 0.000 description 12
- 230000002687 intercalation Effects 0.000 description 10
- 238000009830 intercalation Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of high yield fluorinated graphene preparation method, including：(1) according to weight than 1:(0.1~1) claim fluorographite and intercalator, mix and be sealed in built-in receptacle, be put into reactor, seal reactor, reactor vacuumizes；(2) liquefied carbon dioxide and it is injected into reactor, carbon dioxide reaches supercriticality, pressurize, then is depressured, and reactor pressure is down to normal pressure；(3) secondary booster, while enter supercritical carbon dioxide and circulate state, intercalator is gradually extracted out, then constant temperature circulating pulsing packing, is then depressurized to normal pressure；(4) 2~5 above-mentioned steps (3) are repeated, after the intercalator in question response kettle is extracted out, built-in receptacle is taken out, obtains fluorographite ene product.It has the following advantages that：The advantages that cost is cheap, green, pollution-free, yield is high, technique is simple, high-regularity, few layer of fluorinated graphene of high quality can be prepared.
Description
Technical field
The present invention relates to a kind of fluorinated graphene preparing technical field, more particularly to a kind of high yield fluorinated graphene to prepare
Method.
Background technology
In recent years, it is contemplated that C-F keys are highly stable, and sight is transferred to a kind of preparation of new Graphene derivative by people
With application field, i.e. fluorinated graphene field.Fluorinated graphene is by eliminating the electron cloud in graphene, and prevents electric current
Normality flows, but does not influence its stable carbon structure.Therefore fluorinated graphene is both most thin insulator, and a broad stopband
Semiconductor devices, have the mechanical performance suitable with graphene, chemically and thermally stable mechanical property.
Domestic and international fluorinated graphene technology of preparing mainly includes chemical reaction method, mechanical stripping method and liquid phase stripping method.(1)
Chemical reaction method：Utilize fluorination reagent such as F2、XeF2Fluorination synthesize fluorinated graphene, fluorination reagent used in the method has
Hypertoxicity and expensive, in addition chemical method harsh is required to experimental facilities, experiment condition, this strongly limits the extensive of this method
Using；(2) mechanical stripping method：Mechanical stripping is carried out using the fluorographite of high fluorine carbon ratio fluorinated graphene lamella, the method is made
Technique is simple, cost is low, but obtained fluorinated graphene size is smaller and carbon structure existing defects, regularity decline；(3) liquid phase
Stripping method：Hot intercalation is carried out to fluorographite using low boiling organic reagent or ionic liquid, aided in simple liquid phase ultrasound
The method of centrifugation separates few layer of fluorinated graphene, and compared to mechanical stripping method, liquid phase stripping is more gentle controllable, product
Appearance structure is more regular, and the method is to apply a kind of more method at present, but the yield that its ultrasound is peeled off is relatively low, can not obtain
Extensive utilization.
In recent years, supercritical carbon dioxide is gradually applied to the preparation of nano-powder as the remover of green, such as：
CN105645398A is disclosed to prepare the method for large scale fluorinated graphene by using overcritical using supercritical carbon dioxide
CO2As remover, various alcohols, surfactant are that dispersant produces fluorinated graphene, and disclosed yield is up to 61%.
However, it also has the following disadvantages a little：(1) it is difficult to the yield for improving individual layer or few layer fluorinated graphene in preparation process；(2) make
The fluorinated graphene F/C taken is small, and adulterates dispersant, is unfavorable for the follow-up utilization of product.
The content of the invention
The invention provides a kind of high yield fluorinated graphene preparation method, which overcomes in background technology using overcritical
Carbon dioxide prepares the deficiency present in the method for large scale fluorinated graphene.
The present invention solves one of used technical scheme of its technical problem：
A kind of high yield fluorinated graphene preparation method, including：
(1), according to weight than 1:(0.1~1) fluorographite and intercalator, fluorographite and intercalator mixing and sealing are claimed
In built-in receptacle, the built-in receptacle of sealing is put into reactor, seals reactor, reactor vacuumizes；
(2), liquefied carbon dioxide and it is injected into reactor, carbon dioxide reaches supercriticality, pressurize, then is depressured,
Reactor pressure is set to be down to normal pressure；
(3), secondary booster, while enter supercritical carbon dioxide and circulate state, intercalator is gradually extracted out,
Then constant temperature circulating pulsing packing, then it is depressurized to normal pressure；
(4) 2~5 above-mentioned steps (3) are repeated, after the intercalator in question response kettle is extracted out, take out built-in receptacle,
Obtain fluorographite ene product.
Among one embodiment：The fluorine carbon ratio of the fluorographite ene product is 0.70~0.95.
Among one embodiment：The fluorine carbon ratio of the fluorographite ene product is 0.80~0.95.
Among one embodiment：Described intercalator is low boiling point organic solvent.
Among one embodiment：Described intercalator is acetonitrile, chloroform, 1-METHYLPYRROLIDONE and dimethylformamide
At least one of.
Among one embodiment：In described step (2)：Temperature of reaction kettle rises to 40~120 DEG C, and liquefied carbon dioxide simultaneously will
It is injected in reactor, and carbon dioxide reaches supercriticality, and reacting kettle inner pressure is in 8~20MPa, 30~120 points of pressurize
Clock, then be depressured, reactor pressure is down to normal pressure.
Among one embodiment：In described step (3)：Secondary booster, while supercritical carbon dioxide is entered recycle stream
Dynamic state, intercalator are gradually extracted out, and then constant temperature circulating pulsing packing 20~60 minutes, are then depressurized to normal pressure.
Among one embodiment：The built-in receptacle using filter membrane seal, with avoid the fluorinated graphene in built-in receptacle with
Gas disperses.
What the present invention solved the used technical scheme of its technical problem two is：
A kind of high yield fluorinated graphene preparation method, according to weight than 1:(0.1~1) fluorographite and intercalator are claimed,
Fluorographite and intercalator are mixed and are sealed in built-in receptacle, and the built-in receptacle of sealing is put into reactor, seal reactor；
Liquefied carbon dioxide gas is passed through into reactor, carbon dioxide reaches supercriticality, and to prepare fluorinated graphene, described inserts
Layer agent is at least one of acetonitrile, chloroform, 1-METHYLPYRROLIDONE and dimethylformamide.
Compared with background technology, it has the following advantages that the technical program：
The fluorographite and intercalator of the present invention is first sealed in built-in receptacle, is placed into reactor, seals reactor,
And -- -- pressurize -- is depressurized to normal pressure -- boosting -- constant temperature circulating pulsing packing -- drop to injection liquefied carbon dioxide using vacuumizing
Being depressed into normal pressure, -- -- constant temperature circulating pulsing packing -- be depressurized to normal pressure -- ... take out built-in receptacle -- obtains fluorographite for boosting
The technological process of ene product, thus can solve high-quality fluorinated graphene F/C present in background technology than it is small, yield rate is low,
There are the technical problems such as doping, and have the advantages that cost is cheap, green, pollution-free, yield is high, technique is simple, can make
For high-regularity, few layer of fluorinated graphene of high quality is gone out, be advantageous to fluorinated graphene Stability Analysis of Structures, wide scope is applicable.
The fluorographite and intercalator of the present invention is first sealed in built-in receptacle, is placed into reactor, seals reactor,
Fluorinated graphene can be avoided, and in fast pressure relief process, the product caused by big air motion outwards disperses, and then improves fluorographite
The yield rate of alkene.
Intercalator is low boiling point organic solvent, and at high temperature under high pressure, low boiling point organic solvent can effectively overcome fluorination stone
Van der Waals force between layer of ink, to fluorographite carry out solvent heat intercalation, while using supercritical carbon dioxide have extractant and
Dry effect, can be further by organic intercalation agent by circulating for supercritical carbon dioxide and multiple buck
Extract, reduce doping of the organic intercalation agent for fluorinated graphene.
Intercalator is at least one of acetonitrile, chloroform, 1-METHYLPYRROLIDONE and dimethylformamide, You Jirong
Agent low boiling point, at high temperature under high pressure, low boiling point organic solvent can effectively overcome fluorographite interlayer Van der Waals force, to being fluorinated stone
Ink carries out solvent heat intercalation, while has the function that extractant using supercritical carbon dioxide and dry, and passes through overcritical two
Circulate and the multiple buck of carbonoxide, further can extract organic intercalation agent, reduce organic intercalation agent
Doping for fluorinated graphene.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the apparatus structure schematic diagram that supercritical carbon dioxide of the present invention prepares fluorinated graphene：
Label declaration：Carbon dioxide steel cylinder -- 1, cool down tank arrangement -- 2, high-pressure pump -- 3, constant temperature and pressure reactor -- 4,
Organic solvent surge flask -- 5, vavuum pump -- 6.
Embodiment
In order to further illustrate the present invention, below in conjunction with accompanying drawing 1 to a kind of high yield fluorinated graphene provided by the invention
Preparation method is further described, but protection scope of the present invention is not limited to that.
A kind of high yield fluorinated graphene preparation method, including：
(1), according to weight than 1:(0.1~1) fluorographite and intercalator, fluorographite and intercalator mixing and sealing are claimed
In built-in receptacle, the built-in receptacle of sealing is put into reactor 4, seals reactor 4, reactor 4 vacuumizes；The present embodiment
Among：Described built-in receptacle uses PTFE containers, and PTFE is polytetrafluoroethylene (PTFE)；Described fluorographite and intercalator mixing and
After loading built-in receptacle, sealed using PTFE filter membranes；Lid lid is used to connect reactor to realize sealing；Reactor 4 uses constant temperature
Constant pressure reactor；The air in constant temperature and pressure reactor 4 is extracted out using vavuum pump 6 so that vacuum environment is kept in kettle.
(2), the temperature of reactor 4 rises to 40~120 DEG C, and liquefied carbon dioxide is simultaneously injected into reactor, carbon dioxide
Up to supercriticality, and reacting kettle inner pressure is in 8~20MPa, pressurize 30~120 minutes, then is depressured, and drops reactor pressure
To normal pressure.Among the present embodiment：CO2Enter cooling tank device 2 from carbon dioxide steel cylinder 1 to be liquefied, temperature of reaction kettle
For 40~120 DEG C, carbon dioxide is injected toward reactor 4 is interior using high-pressure pump 3, pressure is 8~20MPa in reactor 4, makes system
Reach supercriticality, at a constant temperature after static pressurize 30~120 minutes, by relief valve reduction of blood pressure in high-speed, make reactor pressure
It is down to normal pressure.
(3), secondary booster, while enter supercritical carbon dioxide and circulate state, intercalator is gradually extracted out,
Then constant temperature circulating pulsing packing 20~60 minutes, are then depressurized to normal pressure.Among the present embodiment：Secondary booster, open simultaneously
Intake valve and air outlet valve make supercritical carbon dioxide enter the state that circulates, and organic intercalation agent is gradually extracted out into organic
Solvent surge flask 5, constant temperature circulating pulsing packing after certain 20~60 minutes reduction of blood pressure in high-speed to normal pressure.
(4) 2~5 above-mentioned steps (3) are repeated, after the intercalator in question response kettle is extracted completely, built in taking-up
Container, obtain fluorographite ene product.Among the present embodiment：The fluorine carbon ratio (F/C) of the fluorographite ene product be 0.70~
0.95, the fluorine carbon ratio of preferably described fluorographite ene product is 0.80~0.95.
Among the present embodiment：Described intercalator is low boiling point organic solvent, and preferably, described intercalator is acetonitrile
(ACN), chloroform (CHCl3), at least one of 1-METHYLPYRROLIDONE (NMP) and dimethylformamide (DMF).This hair
Bright strong dissolving and high diffusivity ability using supercritical carbon dioxide, pass through CO2It is light that fluid molecule can carry organic intercalation agent
Ground enters fluorographite interlayer, has the function that intercalation, efficiently peels off fluorographite that can be realized by reduction of blood pressure in high-speed, makes its production
Fluorinated graphene of the product less than 10 layers reaches more than 65%, and the property of supercritical carbon dioxide has adjustability, by micro-
Temperature regulating or pressure can reach the purpose that regulation and control extent of exfoliation prepares few layer fluorinated graphene.
Embodiment one
A kind of high yield fluorinated graphene preparation method, including：
(1) a certain amount of fluorographite (F/C=0.90) and ACN solvents are mixed, fluorographite and ACN weight ratio are
1：0.1, PTFE containers are poured into, with PTFE filter membrane good seals, are put into reactor, seal reactor 4, reactor 4 vacuumizes.
(2) temperature of reactor is risen to 120 DEG C, injects liquefaction CO using high-pressure pump2, reactor pressure rises to 16MPa,
Static pressurize 90min at a constant temperature, by relief valve reduction of blood pressure in high-speed, makes reactor pressure be down to normal pressure.
(3) reacting kettle inner pressure is risen into 16MPa again, while open intake valve and air outlet valve to make supercritical carbon dioxide
Into the state that circulates, ACN solvents are gradually extracted out, and reduction of blood pressure in high-speed is to normal pressure after constant temperature circulating pulsing packing 60min.
(4) above-mentioned (3) process is repeated 3 times, makes system after 3 boostings, circulate the process of pulsing packing, reduction of blood pressure in high-speed,
PTFE containers are taken out, obtain fluorographite ene product.Characterized by testing, fluorinated graphene of the product less than 10 layers accounts for 71%.
Embodiment two
A kind of high yield fluorinated graphene preparation method, including：
(1) by a certain amount of fluorographite (F/C=0.95) and CHCl3Solvent mixes, fluorographite and CHCl3Weight
Than for 1：0.5, PTFE containers are poured into, with PTFE filter membrane good seals, are put into reactor, seal reactor 4, reactor 4 is taken out very
It is empty.
(2) temperature of reactor is risen to 100 DEG C, injects liquefaction CO using high-pressure pump2, reactor pressure rises to 12MPa,
Static pressurize 120min at a constant temperature, by relief valve reduction of blood pressure in high-speed, makes reactor pressure be down to normal pressure.
(3) reacting kettle inner pressure is risen into 12MPa again, while open intake valve and air outlet valve to make supercritical carbon dioxide
Into the state that circulates, CHCl3Solvent is gradually extracted out, and reduction of blood pressure in high-speed is to normal pressure after constant temperature circulating pulsing packing 40min.
(4) above-mentioned (3) process is repeated 5 times, makes system after 5 boostings, circulate the process of pulsing packing, reduction of blood pressure in high-speed,
PTFE containers are taken out, obtain fluorographite ene product.Characterized by testing, fluorinated graphene of the product less than 10 layers accounts for 86%.
Embodiment three
A kind of high yield fluorinated graphene preparation method, including：
(1) a certain amount of fluorographite (F/C=0.85) and nmp solvent are mixed, fluorographite and NMP weight ratio are
1：0.7, PTFE containers are poured into, with PTFE filter membrane good seals, are put into reactor, seal reactor 4, reactor 4 vacuumizes.
(2) temperature of reactor is risen to 60 DEG C, injects liquefaction CO using high-pressure pump2, reactor pressure rises to 20MPa,
Static pressurize 60min at a constant temperature, by relief valve reduction of blood pressure in high-speed, makes reactor pressure be down to normal pressure.
(3) reacting kettle inner pressure is risen into 20MPa again, while open intake valve and air outlet valve to make supercritical carbon dioxide
Into the state that circulates, nmp solvent is gradually extracted out, and reduction of blood pressure in high-speed is to normal pressure after constant temperature circulating pulsing packing 20min.
(4) above-mentioned (3) process is repeated 2 times, makes system after 2 boostings, circulate the process of pulsing packing, reduction of blood pressure in high-speed,
PTFE containers are taken out, obtain fluorographite ene product.Characterized by testing, fluorinated graphene of the product less than 10 layers accounts for 76%.
Example IV
A kind of high yield fluorinated graphene preparation method, including：
(1) a certain amount of fluorographite (F/C=0.80) and DMF solvent are mixed, fluorographite and DMF weight ratio are
1：1, PTFE containers are poured into, with PTFE filter membrane good seals, are put into reactor, seal reactor 4, reactor 4 vacuumizes.
(2) temperature of reactor is risen to 40 DEG C, injects liquefaction CO using high-pressure pump2, reactor pressure rises to 8MPa,
Static pressurize 30min, by relief valve reduction of blood pressure in high-speed, makes reactor pressure be down to normal pressure under constant temperature.
(3) reacting kettle inner pressure is risen into 8MPa again, while open intake valve and air outlet valve to make supercritical carbon dioxide
Into the state that circulates, DMF solvent is gradually extracted out, and reduction of blood pressure in high-speed is to normal pressure after constant temperature circulating pulsing packing 50min.
(4) above-mentioned (3) process is repeated 4 times, makes system after 4 boostings, circulate the process of pulsing packing, reduction of blood pressure in high-speed,
PTFE containers are taken out, obtain fluorographite ene product.Characterized by testing, fluorinated graphene of the product less than 10 layers accounts for 63%.
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still it belong in the range of the present invention covers.
Claims (9)
- A kind of 1. high yield fluorinated graphene preparation method, it is characterised in that：Including：(1), according to weight than 1:(0.1~1) fluorographite and intercalator are claimed, fluorographite and intercalator are mixed and be sealed in interior Put in container, the built-in receptacle of sealing is put into reactor, seal reactor, reactor vacuumizes；(2), liquefied carbon dioxide and it is injected into reactor, carbon dioxide reaches supercriticality, pressurize, then is depressured, and makes anti- Kettle pressure is answered to be down to normal pressure；(3), secondary booster, while enter supercritical carbon dioxide and circulate state, intercalator is gradually extracted out, then Constant temperature circulating pulsing packing, is then depressurized to normal pressure；(4) 2~5 above-mentioned steps (3) are repeated, after the intercalator in question response kettle is extracted out, built-in receptacle is taken out, obtains Fluorographite ene product.
- A kind of 2. high yield fluorinated graphene preparation method according to claim 1, it is characterised in that：The fluorographite The fluorine carbon ratio of ene product is 0.70~0.95.
- A kind of 3. high yield fluorinated graphene preparation method according to claim 2, it is characterised in that：The fluorographite The fluorine carbon ratio of ene product is 0.80~0.95.
- A kind of 4. high yield fluorinated graphene preparation method according to claim 1 or 2 or 3, it is characterised in that：Described Intercalator is low boiling point organic solvent.
- A kind of 5. high yield fluorinated graphene preparation method according to claim 1 or 2 or 3, it is characterised in that：Described Intercalator is at least one of acetonitrile, chloroform, 1-METHYLPYRROLIDONE and dimethylformamide.
- A kind of 6. high yield fluorinated graphene preparation method according to claim 1 or 2 or 3, it is characterised in that：Described In step (2)：Temperature of reaction kettle rises to 40~120 DEG C, and liquefied carbon dioxide is simultaneously injected into reactor, and carbon dioxide reaches super Critical condition, and reacting kettle inner pressure is in 8~20MPa, pressurize 30~120 minutes, then be depressured, reactor pressure is down to often Pressure.
- A kind of 7. high yield fluorinated graphene preparation method according to claim 1 or 2 or 3, it is characterised in that：Described In step (3)：Secondary booster, while enter supercritical carbon dioxide and circulate state, intercalator is gradually extracted out, is connect Constant temperature circulating pulsing packing 20~60 minutes, be then depressurized to normal pressure.
- A kind of 8. high yield fluorinated graphene preparation method according to claim 1 or 2 or 3, it is characterised in that：In described Put container to seal using filter membrane, to avoid the fluorinated graphene in built-in receptacle from dispersing with gas.
- A kind of 9. high yield fluorinated graphene preparation method, it is characterised in that：According to weight than 1:(0.1~1) fluorographite is claimed And intercalator, fluorographite and intercalator are mixed and be sealed in built-in receptacle, the built-in receptacle of sealing is put into reactor, close Seal reactor；Liquefied carbon dioxide gas is passed through into reactor, carbon dioxide reaches supercriticality, to prepare fluorographite Alkene, described intercalator are at least one of acetonitrile, chloroform, 1-METHYLPYRROLIDONE and dimethylformamide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN113772666A (en) * | 2021-10-25 | 2021-12-10 | 大连元晶科技有限公司 | Method for preparing oil-soluble fluorinated graphene by stripping with supercritical carbon dioxide |
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