CN108178143A - A kind of fluorinated graphene material and preparation method and application - Google Patents
A kind of fluorinated graphene material and preparation method and application Download PDFInfo
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- CN108178143A CN108178143A CN201711363689.4A CN201711363689A CN108178143A CN 108178143 A CN108178143 A CN 108178143A CN 201711363689 A CN201711363689 A CN 201711363689A CN 108178143 A CN108178143 A CN 108178143A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
Abstract
The invention discloses a kind of fluorinated graphene materials and preparation method and application, belong to field of new materials.The preparation method, including：Graphene oxide solution with HF acid is mixed, carries out being refluxed reaction at 20 DEG C 80 DEG C, obtains mixed system；The mixed system that step 1 is obtained carries out hydro-thermal reaction, obtains suspension；It removes HF excessive in the suspension, be dried to obtain fluorinated graphene.Preparation method solvent provided by the invention is pollution-free, and fluorination reagent is HF solution relatively cheap and easy to get, and dosage is few, and integrated artistic difficulty is low, pollution is small, energy consumption is low；Obtained fluorinated graphene sheet of material is 28 layers, thinner thickness；The AlH coated with fluorinated graphene material prepared by this method3Or Al powder is applied in propulsion, can reduce AlH3In the sensitivity of propellant application and the efficiency of combustion of raising Al powder.
Description
Technical field
The present invention provides preparation method and the application of a kind of fluorinated graphene material, belongs to field of new materials.
Background technology
Graphene be one kind by carbon atom with sp2Hybridized orbit composition hexangle type is in the two-dimensional material of honeycomb lattice, only
One carbon atom thickness.In recent years since the unique structure of graphene assigns its many excellent physicochemical property, cause physics, change
, material, electronics, biology and mechanics field research boom, be also applied to all kinds of composite woods as excellent reinforced phase
In material.
The excellent physicochemical property that graphene has mainly includes the following：(1) excellent electric conductivity, electron-transport
Speed has reached the 1/300 of the light velocity, and carrier mobility is up to 2 × 105cm2/ (Vs), the 140 of electron mobility about in silicon
Times；Conductivity is up to 106S/m, current density are 100 times of copper.(2) heat of good thermal conductivity, under room temperature graphene
Conductance is in (4.84 ± 0.44) × 103To (5.30 ± 0.48) × 103Between W/ (mK), higher than carbon nanotube and diamond, it is
More than 10 times and the highest material of current thermal conductivity of the thermal conductivity of copper at room temperature；(3) good translucency, light transmittance reach
97.7%, it is the conductor material of a kind of " transparent "；(4) excellent mechanical property, it is 100 times higher than the hardness of steel, this is because stone
The black each carbon atom of alkene forms stable hexaplanar, tensile strength and elasticity by rigid σ keys and adjacent carbon atom
Modulus is respectively 125GPa and 1.1TPa, is intensity and the highest crystal structure of hardness in known materials；(5) huge specific surface
Product, theoretical value reach 2630m2/ g, 3.5g graphene can be paved with one piece of normal soccer field.Function based on above-mentioned brilliance is special
Property, graphene has great application prospect in new energy, pollution processing, microelectronic component, photoelectrocatalysis etc..
Fluorinated graphene is one kind of Graphene derivative.Research shows that：Compared to Teflon (Teflon), as two dimension
Teflon material --- the various excellent properties of fluorinated graphene be even more go even farther, such as good greasy property
And insulation performance, it plays a role available for manufacture electronic component or in surface field.The preparation of fluorinated graphene up to now
Mainly by two methods, one kind is ultrasound stripping fluorographite, and the usual lamella of fluorinated graphene that shortcoming is is thicker
And size is smaller, and solvent is difficult to detach, caused by pollute and also should not be underestimated.Another kind is to use fluorine gas or XeF2To graphite
Alkene is fluorinated, and shortcoming is expensive, higher to operation equipment requirement, and both fluorization agents have severe toxicity.
Invention content
Present invention solves the technical problem that it is：For problems of the prior art, a kind of fluorinated graphene material is provided
Material and preparation method and application, the preparation method technology difficulty is low, pollution is small, low energy consumption.
For achieving the above object, the present invention provides following technical solution：
A kind of preparation method of fluorinated graphene material, includes the following steps：
Step 1 mixes graphene oxide solution with HF acid, carries out being refluxed reaction at 20 DEG C -80 DEG C, be mixed
Zoarium system；
Step 2, the mixed system for obtaining step 1 carry out hydro-thermal reaction, obtain suspension；
Excessive HF, drying, obtain fluorinated graphene in step 3, the removal suspension.
In an alternative embodiment, the graphene oxide oxygen content described in step 1 is 30wt%-60wt%.
In an alternative embodiment, a concentration of 0.5mg/mL-5mg/mL of graphene oxide solution described in step 1 is described
The mass concentration of HF acid is 20%-40%, and the volume ratio of the graphene oxide solution and HF acid is 1:0.0125-0.25.
In an alternative embodiment, be refluxed reaction described in step 1, reaction temperature is 20 DEG C -80 DEG C, reaction
Time is 2h-60h, and when reaction passes through magnetic agitation, rotating speed 100r/min-600r/min.
In an alternative embodiment, the carry out hydro-thermal reaction described in step 2, reaction temperature is 100 DEG C -180 DEG C, during reaction
Between be 4h-30h.
In an alternative embodiment, heating rate is 3 DEG C/min-6 DEG C/min in step 2.
In an alternative embodiment, excessive HF in the removal suspension described in step 3, including：
The suspension is filtered, solvent is added in into filter residue and is cleaned and is filtered, until the filtered fluid of cleaning
PH value is in neutrality；Or
The suspension is centrifuged, removes supernatant, continues solubilizer and cleans and centrifuge, until supernatant pH value is
It is neutral.
In an alternative embodiment, the solvent described in step 3 includes one kind in deionized water, absolute ethyl alcohol, isopropanol
Or more than one combinations.
In an alternative embodiment, the drying described in step 3, including freeze-drying, vacuum drying or spray drying.
In an alternative embodiment, the drying time of the freeze-drying is 30h-80h；The drying temperature of the vacuum drying
It is 40 DEG C -80 DEG C to spend, and drying time is -48h for 24 hours；The drying temperature of the spray drying is 40 DEG C -80 DEG C.
Fluorinated graphene material prepared by above-mentioned preparation method.
Fluorinated graphene material prepared by above-mentioned preparation method is in cladding AlH3Or the application in Al powder.
The advantages of the present invention over the prior art are that：
Preparation method solvent provided by the invention is pollution-free, and fluorination reagent is HF solution relatively cheap and easy to get, and dosage
Seldom, integrated artistic difficulty is low, pollution is small, energy consumption is low；Obtained fluorinated graphene sheet of material is 10 layers hereinafter, meeting at present
In the world to the requirement of grapheme material, thinner thickness；The AlH coated with fluorinated graphene material prepared by this method3Or Al
Powder is applied in propulsion, can reduce AlH3In the sensitivity of propellant application and the efficiency of combustion of raising Al powder.
Description of the drawings
Fig. 1 is the fluorinated graphene material microscopic appearance figure that the embodiment of the present invention 2 provides；
Fig. 2 is the fluorinated graphene material microscopic appearance figure that the embodiment of the present invention 5 provides；
Fig. 3 is that the fluorinated graphene that the embodiment of the present invention 3 provides coats AlH3Scanning electron microscope (SEM) figure；
Fig. 4 is scanning electron microscope (SEM) figure that the fluorinated graphene that the embodiment of the present invention 8 provides coats Al powder.
Specific embodiment
The present invention is described in further detail in the following with reference to the drawings and specific embodiments.
An embodiment of the present invention provides a kind of preparation methods of fluorinated graphene material, include the following steps：
Step 1 mixes graphene oxide solution with HF acid, carries out being refluxed reaction at 20 DEG C -80 DEG C, be mixed
Zoarium system；
Wherein, the graphene oxide solution can be for commodity graphene oxide solution or by commodity high activity Graphene powder
The graphene oxide solution that end is formulated, the present invention do not limit；The preferred oxygen content of graphene oxide is 30wt%-
60wt%；
The preferred 0.5mg/mL-5mg/mL of concentration of the graphene oxide solution, the mass concentration of the HF acid are preferred
20%-40%, the graphene oxide solution and the volume ratio preferably 1 of HF acid:0.0125-0.25；Raw material uses proportioning at this time
Meet atom economy, fluorinated graphene product lamella is relatively thin.
Described is refluxed reaction, and preferred reactant temperature is 20 DEG C -80 DEG C, reaction time 2h-60h, more preferably
Reaction temperature is 45 DEG C -60 DEG C, reaction time 20h-30h；Reaction system can be made to consume energy in the case where ensureing fluorination rate higher strip part
It is relatively low.It can be flowed back during reaction by condensing unit, by magnetic agitation, the preferred 100-600r/min of rotating speed；
Step 2, the mixed system for obtaining step 1 carry out hydro-thermal reaction, obtain suspension；
Specifically, hydro-thermal reaction preferable reaction temperature is 100 DEG C -180 DEG C, reaction time 4h-30h；More preferably reaction
Temperature is 120 DEG C -160 DEG C, reaction time 8h-16h；The reaction temperature and under the time ensures the fluorination of fluorographite ene product
Rate simultaneously, can remove part oxygen-containing functional group.Heating rate preferably 3 DEG C/min-6 DEG C/min.
Step 3 removes HF excessive in the suspension, is dried to obtain fluorinated graphene.
Wherein, in the embodiment of the present invention, excessive HF, can include in the removal suspension：To described outstanding
Turbid is filtered, and solvent is added in into filter residue and is cleaned and is filtered, until the filtered fluid pH value of cleaning is in neutrality；It is or right
The suspension is centrifuged, and removes supernatant, is continued solubilizer and is cleaned and centrifuge, until supernatant pH value is neutrality；At it
It can also be combined in his embodiment by the two or other modes remove extra HF, the present invention does not limit.The solvent includes
One or more kinds of combinations in deionized water, absolute ethyl alcohol, isopropanol；
The drying, including freeze-drying, vacuum drying or spray drying.The drying time of the freeze-drying is preferred
30h-80h；The preferred drying temperature of vacuum drying is 40 DEG C -80 DEG C, and drying time is -48h for 24 hours；The spray drying
Preferably 40 DEG C -80 DEG C of drying temperature.
The color of target product of the embodiment of the present invention is black or grey, and state is powdered or fluffy spongy or other
The solid of irregular shape；The fluorinated volume of target product is 8wt%-55.06wt%, and the piece number of plies is 2-6 layers, is slightly soluble in water, can
It is dissolved in part organic solvent.
The embodiment of the present invention additionally provides the above method and prepares fluorinated graphene material.
The embodiment of the present invention additionally provides the fluorinated graphene material of above method preparation in cladding AlH3Or in Al powder
Using.
Specifically, by AlH3(or Al powder) is configured to suspension A, fluorinated graphene is configured to dispersion liquid B, A is mixed with B
Afterwards plus surfactant and non-solvent D carry out self assembly；Dispersion solvent used is tetrahydrofuran, isopropanol in wherein suspension A
Or one or more kinds of combinations in ethyl acetate equal solvent；AlH3The mass fraction of (or Al powder) in suspension A is preferred
0.5-4%；The preferred water of dispersion liquid B solvent for use, tetrahydrofuran, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO) or N- methyl pyrroles
One or more kinds of combinations in pyrrolidone, the preferred 0.2mg/ml- of concentration of the fluorinated graphene material in dispersion liquid B
10mg/ml；The volume ratio of suspension A and dispersion liquid B are preferably (0.5-2)：1；The preferred dodecyl sodium sulfate of surfactant, ovum
One or more kinds of combinations in phosphatide or alkyl dimethyl tertiary amide, the preferred AlH of additive amount of surfactant3(or Al powder)
The 0.01%-0.02% of quality；One or more kinds of combinations in the preferred toluene of non-solvent D, hexamethylene or atoleine, it is non-
The preferred suspension A of volume of solvent D and 1-3 times of dispersion liquid B total volumes.
The AlH of fluorinated graphene material cladding provided in an embodiment of the present invention3Or Al powder, when being applied to propellant, energy
The efficiency of combustion of aluminium powder is enough improved, reduces AlH3Sensitivity.
It is below specific embodiments of the present invention, each embodiment is raw materials used, reagent is commercial product.
Embodiment 1
Step 1：By graphene oxide (oxygen content 40%) aqueous solution of a concentration of 2mg/mL of 30mL, 1.5mL concentration is added in
In the HF acid of 30wt%, to add in magneton after mixing, loading onto reflux condensate device, react for 24 hours, mixed at 40 DEG C
System, during reaction, magnetic agitation, magneton rotating speed is 300r/min.
Step 2：Reaction gained mixed system is transferred in 50mL reaction kettles, 120 are warming up to the rate of 3 DEG C/min
DEG C, 8h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is filtered using Buchner funnel, suction filtration finishes, and adds again into filter residue
Water is cleaned and is filtered, until the filtered fluid pH value of cleaning is in neutrality.Filter cake adds a small amount of moisture to dissipate and is transferred in surface plate, is put into
Freeze-drying 30h is carried out in freeze drier.Obtained sample is the loose spongy solid of grey.
After tested, sample fluorine content is as a result shown as 25.00wt%, and the piece number of plies is about 4 layers.
Embodiment 2
Step 1：By the graphene oxide water solution (oxygen content 60%) of a concentration of 2mg/mL of 60mL, it is a concentration of to add in 3mL
In the HF acid of 40wt%, magneton is added in after mixing, loads onto reflux condensate device, reacted at 40 DEG C for 24 hours, obtain mixture
System, during reaction, magnetic agitation, magneton rotating speed is 500r/min.
Step 2：Reaction gained mixed system is transferred in 100mL reaction kettles, 120 are warming up to the rate of 3 DEG C/min
DEG C, 8h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：Suspension obtained by step 2 is put into centrifuge and is centrifuged, removes supernatant liquor, continue plus go from
Sub- water cleaning is precipitated and is centrifuged, and repeatedly until supernatant liquor pH value is neutrality, lower sediment is transferred in beaker, is put into true
It is dried for 24 hours at empty 80 DEG C of baking oven.Obtained sample is the irregular solid of black.
After tested, sample fluorine content is as a result shown as 21.62wt%, and the piece number of plies is about 6 layers.
Embodiment 3
Step 1：The graphene oxide solid powder that 120mg oxygen contents are 40% is taken, 60mL water is added in and is configured to 2mg/mL
Graphene oxide solution, the HF acid of 3mL a concentration of 40wt% is added in into the graphene oxide solution being configured to, is uniformly mixed
After add in magneton, load onto reflux condensate device, reacted at 40 DEG C for 24 hours, obtain mixed system, during reaction, magnetic agitation, magneton
Rotating speed is 400r/min.
Step 2：Reaction gained mixed system is transferred in 100mL reaction kettles, 180 are warming up to the rate of 6 DEG C/min
DEG C, 4h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is filtered using Buchner funnel, suction filtration finishes, and adds again into filter residue
Enter washes of absolute alcohol and filter, repeatedly after plus water clean and surveys its pH value, until clean filtered fluid pH value be in neutrality.
Filter cake adds a small amount of moisture to dissipate and is transferred in surface plate, is put into freeze drier and carries out freeze-drying 50h.Obtained sample is
Black spongy solid.
After tested, sample fluorine content is as a result shown as 16.45wt%, and the piece number of plies is about 6 layers, and microscopic appearance is referring to Fig. 1.
Embodiment 4
Step 1：By graphene oxide (oxygen content 40%) aqueous solution of a concentration of 5mg/mL of 30mL, it is a concentration of to add in 3mL
In the HF acid of 40wt%, magneton is added in after mixing, loads onto reflux condensate device, react 60h at 50 DEG C, obtain mixture
System, during reaction, magnetic agitation, magneton rotating speed is 600r/min.
Step 2：Reaction gained mixed system is transferred in 50mL reaction kettles, 140 are warming up to the rate of 4 DEG C/min
DEG C, 8h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：After suspension obtained by step 2 is centrifuged using centrifuge, supernatant liquid is outwelled, is added in appropriate different
Propyl alcohol is cleaned and is centrifuged, repeatedly after, again plus water and test its pH value.Cleaning to pH value is in neutrality.Precipitation is sprayed
Mist is dried, and temperature is set as 40 DEG C.Obtained sample is black powder solid.
After tested, sample fluorine content is as a result shown as 55.06wt%, and the piece number of plies is about 2 layers.
Embodiment 5
Step 1：Will in graphene oxide (oxygen content 60%) aqueous solution of a concentration of 2mg/mL of 30mL add in 30mL go from
Sub- water is diluted to the graphene oxide water solution of 1mg/mL, and a concentration of 40wt% of 3mL are then added dropwise into the aqueous solution after dilution
HF acid, add in magneton after mixing, load onto reflux condensate device, react 30h at 20 DEG C, obtain mixed system, react
When, magnetic agitation, magneton rotating speed is 300r/min.
Step 2：Reaction gained mixed system is transferred in 50mL reaction kettles, 170 are warming up to the rate of 5 DEG C/min
DEG C, it maintains for 24 hours, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is filtered using Buchner funnel, suction filtration finishes, and is added in into filter residue different
Propyl alcohol is cleaned and is filtered, and finally plus water surveys its pH value, until cleaning solution pH value is in neutrality.Filter residue is transferred in surface plate, is put
Enter in vacuum drying oven and dry, temperature is 40 DEG C, time 48h.Obtained sample is the irregular blocks of solid of black.
After tested, sample fluorine content is as a result shown as 15.50wt%, and the piece number of plies is about 4 layers, and microscopic appearance is referring to Fig. 2.
Embodiment 6
Step 1：It takes 200mg, the graphene oxide solid powder that oxygen content is 60%, adds in 40mL water and be configured to 5mg/mL
Graphene oxide solution, the HF acid of 10mL a concentration of 20wt% is added dropwise into the graphene oxide solution of configuration, is uniformly mixed
After add in magneton, load onto reflux condensate device, react 2h at 60 DEG C, obtain mixed system, during reaction, magnetic agitation, magneton
Rotating speed is 500r/min.
Step 2：Reaction gained mixed system is transferred in 100mL reaction kettles, 170 are warming up to the rate of 5 DEG C/min
DEG C, 2h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is centrifuged using centrifuge, centrifugation finishes, added in into precipitation go from
Sub- water cleans and continues to centrifuge, and repeatedly tests pH value, until cleaning solution pH value is in neutrality.Precipitation is spray-dried,
Temperature is 60 DEG C.Obtained sample is black powder solid.
After tested, sample fluorine content is as a result shown as 11.02wt%, and the piece number of plies is about 4 layers.
Embodiment 7
Step 1：It is dense by 0.75mL is added dropwise in graphene oxide (oxygen content 40%) aqueous solution of a concentration of 2mg/mL of 30mL
The HF for 30wt% is spent, adds in magneton after mixing, loads onto reflux condensate device, 3h is reacted at 40 DEG C, obtains mixture
System, during reaction, magnetic agitation, magneton rotating speed is 100r/min.
Step 2：Reaction gained mixed system is transferred in 50mL reaction kettles, 100 are warming up to the rate of 3 DEG C/min
DEG C, 20h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is filtered using Buchner funnel, suction filtration finishes, and adds again into filter residue
Water cleans, until cleaning solution pH value is in neutrality.Filter residue is transferred in beaker, is put into vacuum drying oven, the dry 36h at 60 DEG C.
Obtained sample is the irregular solid of black.
After tested, sample fluorine content is as a result shown as 8.35wt%, and the piece number of plies is about 5 layers.
Embodiment 8
Step 1：Will in graphene oxide (oxygen content 30%) aqueous solution of a concentration of 2mg/mL of 30mL add in 30mL go from
Sub- water is diluted to the graphene oxide water solution of 1mg/mL, and a concentration of 40wt% of 4mL are then added dropwise into the solution that dilution obtains
HF acid, add in magneton after mixing, load onto reflux condensate device, react 30h at 30 DEG C, obtain mixed system, react
When, magnetic agitation, magneton rotating speed is 300r/min.
Step 2：Reaction gained mixed system is transferred in 50mL reaction kettles, 120 are warming up to the rate of 4 DEG C/min
DEG C, 8h is maintained, reaction finishes cooled to room temperature, obtains suspension.
Step 3：After being centrifuged using centrifuge to the suspension obtained by step 2, add absolute ethyl alcohol again into precipitation
Clean and centrifuge, repeatedly after plus water survey its pH value, until cleaning solution pH value is in neutrality.Turn to precipitation plus a small amount of water and together
It moves in surface plate, is put into freeze dryer and carries out freeze-drying 60h, obtained sample is black spongy solid.
After tested, sample fluorine content is as a result shown as 29.45wt%, and the piece number of plies is about 3 layers.
Embodiment 9
Step 1：It takes 60mg, the graphene oxide solid powder that oxygen content is 30%, adds in 60mL water and be configured to 1mg/mL
Graphene oxide solution, the HF acid of 1.5mL a concentration of 40wt% is added dropwise into the graphene oxide solution being configured, mixing is equal
Magneton is added in after even, reflux condensate device is loaded onto, reacts 3h at 40 DEG C, obtains mixed system, during reaction, magnetic agitation, magnetic
Rotor speed is 600r/min.
Step 2：Above-mentioned mixed system is transferred in 100mL reaction kettles, is warming up to 120 DEG C with the rate of 4 DEG C/min, dimension
8h is held, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is filtered using Buchner funnel, suction filtration finishes, and adds again into filter residue
Enter washes of absolute alcohol and filter, be repeated several times.Finally plus water cleaning filters until filtrate pH value is in neutrality.Filter residue is sprayed
Mist is dried, and temperature is 80 DEG C.Obtained sample is grey powder solid.
After tested, sample fluorine content is as a result shown as 13.80wt%, and the piece number of plies is about 3 layers.
Embodiment 10
Step 1：Into graphene oxide (oxygen content 30%) aqueous solution of a concentration of 2mg/mL of 15mL add in 45mL go from
Sub- water is diluted to the graphene oxide water solution of a concentration of 0.5mg/mL, then into the graphene oxide water solution that dilution obtains
The HF acid of a concentration of 30wt% of 2mL is added dropwise, adds in magneton after mixing, loads onto reflux condensate device, react 6h at 80 DEG C,
Obtain mixed system, during reaction, magnetic agitation, magneton rotating speed is 300r/min.
Step 2：Reaction gained mixed system is transferred in 100mL reaction kettles, 160 are warming up to the rate of 5 DEG C/min
DEG C, it maintains for 24 hours, reaction finishes cooled to room temperature, obtains suspension.
Step 3：The suspension obtained by step 2 is filtered using Buchner funnel, suction filtration finishes, and is added in into filter residue different
Propyl alcohol cleans and continues to filter, repeatedly after plus water test pH value, until cleaning solution pH value is in neutrality.Filter residue is carried out to add water
Disperse and be transferred in surface plate to be freeze-dried 40h.Obtained sample is black spongy solid.
After tested, sample fluorine content is as a result shown as 10.52wt%, and the piece number of plies is about 3 layers.
Comparative example
Step 1：30mL is added in into graphene oxide (oxygen content 30%) aqueous solution of a concentration of 2mg/mL of 30mL to go
Ionized water is diluted to the graphene oxide water solution of 1mg/mL, and it is a concentration of that 4mL is then added dropwise into the solution that dilution obtains
The HF acid of 40wt%, adds in 50mL reaction kettles after mixing, is warming up to 120 DEG C with the rate of 4 DEG C/min, maintains 8h, instead
Cooled to room temperature should be finished, obtains suspension.
Step 2：After being centrifuged using centrifuge to the suspension obtained by step 1, add absolute ethyl alcohol again into precipitation
Clean and centrifuge, repeatedly after plus water survey its pH value, until cleaning solution pH value is in neutrality.Turn to precipitation plus a small amount of water and together
It moves in surface plate, is put into freeze dryer and carries out freeze-drying 60h, obtained sample is black spongy solid.
After tested, sample fluorine content is as a result shown as 2.57wt%, and the piece number of plies is about 2 layers.
The fluorinated graphene material of embodiment 1-10 and comparative example offer is respectively adopted to AlH3It is coated, is wrapped with Al powder
Coating method is：
By AlH3(or Al powder) is configured to suspension A, wherein dispersion solvent used is tetrahydrofuran, AlH3(or Al powder) exists
Mass fraction in suspension A is 1%；Fluorinated graphene material is configured to dispersion liquid B, solvent for use is N- crassitudes
Ketone, a concentration of 2mg/ml of the fluorinated graphene material in dispersion liquid B；It is 1 according to volume ratio：1 ratio, by suspension A and
Dispersion liquid B is mixed, and dodecyl sodium sulfate is added dropwise, the quality of added dodecyl sodium sulfate is the AlH3(or Al powder) quality
1%, toluene is then added in into mixed system, the volume for adding in toluene is identical with the total volume of suspension A and dispersion liquid B,
Complete fluorinated graphene and AlH3The self assembly of (or Al powder), filtering, drying, obtains the AlH of fluorinated graphene cladding3(or Al
Powder).
Fluorinated graphene material provided in an embodiment of the present invention is to AlH3Or after Al powder is coated, AlH can be improved3Or
Al powder
The AlH that fluorinated graphene is coated3(or Al powder) and poly- nitrine glycerin ether/nitroglycerine (GAP/NG/BTTN) with
Mass ratio 1:1 be uniformly mixed obtain propellant, and the propellant is tested for the property, test result is shown in Table 1：
The AlH of the different fluorinated graphene material claddings of table 13The performance parameter of (or Al powder) corresponding propellant：
The non-detailed description of the present invention is known to the skilled person technology.
Claims (12)
1. a kind of preparation method of fluorinated graphene material, which is characterized in that include the following steps：
Step 1 mixes graphene oxide solution with HF acid, carries out being refluxed reaction at 20 DEG C -80 DEG C, obtains mixture
System；
Step 2, the mixed system for obtaining step 1 carry out hydro-thermal reaction, obtain suspension；
Excessive HF, drying, obtain fluorinated graphene in step 3, the removal suspension.
2. the preparation method of fluorinated graphene material according to claim 1, which is characterized in that the oxidation described in step 1
Graphene oxygen content is 30wt%-60wt%.
3. the preparation method of fluorinated graphene material according to claim 1 or 2, which is characterized in that oxidation described in step 1
A concentration of 0.5mg/mL-5mg/mL of graphene solution, the mass concentration of the HF acid are 20%-40%, the graphite oxide
The volume ratio of alkene solution and HF acid is 1:0.0125-0.25.
4. the preparation method of fluorinated graphene material according to claim 1, it is characterised in that：Progress described in step 1
It is refluxed reaction, reaction temperature is 20 DEG C -80 DEG C, reaction time 2h-60h, is by magnetic agitation, rotating speed during reaction
100r/min-600r/min。
5. the preparation method of fluorinated graphene material according to claim 1, it is characterised in that：Progress described in step 2
Hydro-thermal reaction, reaction temperature are 100 DEG C -180 DEG C, reaction time 4h-30h.
6. the preparation method of fluorinated graphene material according to claim 5, it is characterised in that：Heating rate in step 2
For 3 DEG C/min-6 DEG C/min.
7. the preparation method of fluorinated graphene material according to claim 1, it is characterised in that：Removal described in step 3
Excessive HF in the suspension, including：
The suspension is filtered, solvent is added in into filter residue and is cleaned and is filtered, until the filtered fluid pH value of cleaning
It is in neutrality；Or
The suspension is centrifuged, removes supernatant, continues solubilizer and cleans and centrifuge, until during supernatant pH value is
Property.
8. the preparation method of fluorinated graphene material according to claim 7, it is characterised in that：Solvent described in step 3
Including the one or more combination in deionized water, absolute ethyl alcohol, isopropanol.
9. the preparation method of fluorinated graphene material according to claim 1, it is characterised in that：Drying described in step 3,
Including freeze-drying, vacuum drying or spray drying.
10. the preparation method of fluorinated graphene material according to claim 9, it is characterised in that：The freeze-drying
Drying time is 30h-80h；The drying temperature of the vacuum drying is 40 DEG C -80 DEG C, and drying time is -48h for 24 hours；The spray
The drying temperature of mist drying is 40 DEG C -80 DEG C.
11. fluorinated graphene material prepared by claim 1-10 any one of them preparation method.
12. fluorinated graphene material prepared by claim 1-10 any one of them preparation method is in cladding AlH3Or in Al powder
Application.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233177A (en) * | 2018-08-08 | 2019-01-18 | 燕山大学 | A kind of molybdenum disulfide/fluorinated graphene-ptfe composite and its preparation method and application |
| CN110526945A (en) * | 2019-08-28 | 2019-12-03 | 西安近代化学研究所 | A kind of modified graphite alkenyl iron complex and its synthetic method |
| CN111892467A (en) * | 2020-08-20 | 2020-11-06 | 西南科技大学 | Al/Fe2O3Preparation method of nano energetic material |
| CN112062980A (en) * | 2020-08-28 | 2020-12-11 | 西安近代化学研究所 | Preparation method of energy-containing thermoplastic elastomer compound |
| CN113307260A (en) * | 2021-05-31 | 2021-08-27 | 杭州高烯科技有限公司 | Preparation method of low-viscosity single-layer graphene oxide |
| CN115259978A (en) * | 2022-08-12 | 2022-11-01 | 南京理工大学 | Polydopamine-coated aluminum trihydride compound with core-shell structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6524706B1 (en) * | 2001-03-27 | 2003-02-25 | The United States Of America As Represented By The Secretary Of The Army | Reduction of energetic filler sensitivity in propellants through coating |
| CN106397983A (en) * | 2016-09-07 | 2017-02-15 | 芜湖桑乐金电子科技有限公司 | Graphene fluoride modified resin plate and preparation method thereof |
| CN106477565A (en) * | 2016-10-24 | 2017-03-08 | 国家纳米科学中心 | A kind of fluorinated graphene quantum dot, and its production and use |
| CN106748600A (en) * | 2016-12-09 | 2017-05-31 | 湖北航天化学技术研究所 | Containing AlH3Theoretical specific impulse high and high density propellant and preparation method thereof |
-
2017
- 2017-12-18 CN CN201711363689.4A patent/CN108178143B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6524706B1 (en) * | 2001-03-27 | 2003-02-25 | The United States Of America As Represented By The Secretary Of The Army | Reduction of energetic filler sensitivity in propellants through coating |
| CN106397983A (en) * | 2016-09-07 | 2017-02-15 | 芜湖桑乐金电子科技有限公司 | Graphene fluoride modified resin plate and preparation method thereof |
| CN106477565A (en) * | 2016-10-24 | 2017-03-08 | 国家纳米科学中心 | A kind of fluorinated graphene quantum dot, and its production and use |
| CN106748600A (en) * | 2016-12-09 | 2017-05-31 | 湖北航天化学技术研究所 | Containing AlH3Theoretical specific impulse high and high density propellant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| RUI LI ET AL: ""Preparation and Characterization of Insensitive HMX/Graphene Oxide Composites"", 《PROPELLANTS EXPLOS. PYROTECH》 * |
| ZHAOFENG WANG ET AL: ""Synthesis of fluorinated graphene with tunable degree of fluorination"", 《CARBON》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233177A (en) * | 2018-08-08 | 2019-01-18 | 燕山大学 | A kind of molybdenum disulfide/fluorinated graphene-ptfe composite and its preparation method and application |
| CN110526945A (en) * | 2019-08-28 | 2019-12-03 | 西安近代化学研究所 | A kind of modified graphite alkenyl iron complex and its synthetic method |
| CN110526945B (en) * | 2019-08-28 | 2021-12-21 | 西安近代化学研究所 | Modified graphene-based iron complex and synthesis method thereof |
| CN111892467A (en) * | 2020-08-20 | 2020-11-06 | 西南科技大学 | Al/Fe2O3Preparation method of nano energetic material |
| CN112062980A (en) * | 2020-08-28 | 2020-12-11 | 西安近代化学研究所 | Preparation method of energy-containing thermoplastic elastomer compound |
| CN112062980B (en) * | 2020-08-28 | 2022-07-15 | 西安近代化学研究所 | Preparation method of energy-containing thermoplastic elastomer compound |
| CN113307260A (en) * | 2021-05-31 | 2021-08-27 | 杭州高烯科技有限公司 | Preparation method of low-viscosity single-layer graphene oxide |
| CN115259978A (en) * | 2022-08-12 | 2022-11-01 | 南京理工大学 | Polydopamine-coated aluminum trihydride compound with core-shell structure and preparation method thereof |
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