CN109836812A - A kind of sulphur replaces oxidation fluorinated graphene/composite polyimide material and its preparation method and application - Google Patents
A kind of sulphur replaces oxidation fluorinated graphene/composite polyimide material and its preparation method and application Download PDFInfo
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Abstract
A kind of sulphur replaces oxidation fluorinated graphene/polyamide compoiste material and its preparation method and application；The sulphur replaces the electric conductivity for aoxidizing the fabulous mechanical property of fluorinated graphene/polyamide compoiste material, excellent heating conduction, superelevation.The sulphur replaces oxidation fluorinated graphene surface to contain active group, compared to graphene, it is not susceptible to agglomeration, dispersibility is preferable in the polymer, stronger interaction can be directly formed between polymer interface, realize that sulphur replaces reinforcing effect of the oxidation fluorinated graphene in polymer matrix composite；The sulphur, which replaces oxidation fluorinated graphene to can be used for preparing sulphur substitution oxidation fluorinated graphene described in sulphur substitution oxidation fluorinated graphene/polyamide compoiste material, to be mixed by one kettle way with polyamide, ultrasound, stirring, heating, drying and other steps are prepared sulphur and replace oxidation fluorinated graphene/polyamide compoiste material.The preparation process simple possible, easy to operate, universality is strong.
Description
Technical field
The invention belongs to sulphur to replace oxidation fluorinated graphene and technical field of composite materials, and in particular to a kind of sulphur substitution
Aoxidize fluorinated graphene, sulphur replaces the preparation method and purposes for aoxidizing fluorinated graphene/composite polyimide material, the two.
Background technique
The researchers such as University of Manchester Geim in 2004 peel a small amount of graphene from graphite and study its performance, hair
Now it is with special characteristic electron and excellent mechanics, electricity, optics, calorifics and magnetic performance, to start graphite
The upsurge of alkene application study.Graphene has excellent conductive, thermally conductive and mechanical property, it can be used as, and to prepare high-strength conducting compound
The ideal nanofiller of material, while can also mix and then be polymerized to form compound with the polymer monomer of dispersion in the solution
Material system can assign composite material different functionality, show excellent mechanics and electric property, excellent processability
Can, broader practice space is provided for composite material.However, itself holds since graphene surface lacks active group again
It is easy to reunite, it is dispersed poor in the polymer, it is difficult directly to form stronger interaction between polymer interface, cannot achieve
The reinforcing effect of graphene in polymer composites.Therefore, it is necessary to carry out necessary modification to graphene, then again with it is poly-
It is compound to close object progress, reaches and proposes high performance purpose.
Summary of the invention
In order to improve the deficiencies in the prior art, an object of the present invention is to provide a kind of sulphur substitution oxidation fluorinated graphene
And its preparation method and application, the sulphur replaces oxidation fluorinated graphene surface to contain active group, compared to graphene, no
Agglomeration easily occurs, dispersibility preferably, can directly form stronger interaction between polymer interface in the polymer,
Realize that sulphur replaces reinforcing effect of the oxidation fluorinated graphene in polymer matrix composite.
The second object of the present invention is to provide a kind of sulphur to replace oxidation fluorinated graphene/polyamide compoiste material and its preparation
Method and purposes；The sulphur replaces oxidation fluorinated graphene/polyamide compoiste material to have good dispersion, heat-resist；Material
The advantages that hardness increases, impact resistance enhances.
The invention provides the following technical scheme:
A kind of sulphur substitution oxidation fluorinated graphene, wherein the sulphur replaces the quality percentage of sulphur in oxidation fluorinated graphene
Content is 0.5-5%, such as 1-2%, such as 1.26%.
Preferred embodiment according to the present invention, the sulphur replace the mass percentage of oxygen in oxidation fluorinated graphene to be 5-
15%, such as 6-10%, such as 6.7%.
Preferred embodiment according to the present invention, the sulphur replace the mass percentage of fluorine in oxidation fluorinated graphene to be 1-
6%, such as 2-4%, such as 2.14%.
Preferred embodiment according to the present invention, the sulphur replace oxidation fluorinated graphene to have following at least one structure or property
Energy parameter:
(1) sulphur replaces the specific surface area of oxidation fluorinated graphene to be 50-100m2/ g, such as 83m2/g；
(2) sulphur replace oxidation fluorinated graphene with a thickness of 10nm-20 μm；
(3) sulphur replaces the number of plies of oxidation fluorinated graphene to be 10-60 layers.
The present invention also provides the preparation methods that above-mentioned sulphur replaces oxidation fluorinated graphene, and the method is with fluorine oxide fossil
Ink is the cathode and anode of electrolytic cell, the electrolyte of electrolytic cell is made into the electrolyte containing element sulphur, in external direct current power supply
Under effect, cell reaction is carried out, sulphur is prepared and replaces oxidation fluorinated graphene.
Preferred embodiment according to the present invention, described method includes following steps:
(1) to aoxidize fluorographite as the cathode and anode of electrolytic cell, electrolyte and electrolyte containing element sulphur is added
Solvent, and it is optionally electrolysed auxiliary agent, it is assembled into electrolytic cell system；
(2) under external direct current power supply effect, electrolysis stripping reaction is carried out to the electrolytic cell system of step (1), is prepared into
Replace oxidation fluorinated graphene to the sulphur of dispersion in the electrolytic solution.
Preferred embodiment according to the present invention, the method also includes following steps:
(3) sulphur in collection step (2) replaces oxidation fluorinated graphene, and re-ultrasonic dispersion in organic solvent, is shelled
From；Dispersion liquid is centrifuged, top section is collected and is rinsed with organic solvent, filtering, drying.Since electrolytically generated sulphur takes
Generation oxidation fluorinated graphene is lighter, after centrifugation, can float on solution surface, so to collect top section, then carry out
Filter, washing, drying.
Preferred embodiment according to the present invention, in step (1), the electrolyte containing element sulphur is selected from those skilled in the art
Any electrolyte containing element sulphur that can be adapted for electrolytic cell system of the invention known；Preferably, the sulfur-bearing member
The electrolyte of element is selected from thiocarbamide, mercaptan etc..
Preferred embodiment according to the present invention, in step (1), the electrolyte solvent is as known to those skilled in the art suitable
Any electrolyte solvent for electrolytic cell system of the invention；Preferably, the electrolyte solvent be selected from propene carbonate,
Ethylene carbonate, diethyl carbonate etc..
Preferred embodiment according to the present invention, in step (1), the electrolysis auxiliary agent is being applicable in as known to those skilled in the art
In any electrolysis auxiliary agent of electrolytic cell system of the invention；Preferably, the electrolysis auxiliary agent is selected from cetyl trimethyl bromine
Change ammonium, tetraethyl ammonium tetrafluoroborate etc..
Preferred embodiment according to the present invention, in step (1), the matter of the oxidation fluorographite and the electrolyte containing element sulphur
Amount is than being (1-10): (2-25), for example, 2:(4-5).The mass ratio of the electrolysis auxiliary agent and the electrolyte containing element sulphur is (0-
10): (2-25), for example, 2:(4-5).The volume mass ratio of the electrolyte solvent and the electrolyte containing element sulphur is (20-
200mL): (2-25g), for example, 40mL:(4-5g).
Preferred embodiment according to the present invention, in step (2), the external direct current power supply is as known to those skilled in the art
It is suitable for the invention any external direct current power supply of electrolytic cell system；Preferably, the external direct current power supply is selected from constant pressure
External direct current power supply；The voltage range of the DC power supply is between 10-30V, for example, 15V.The time of the cell reaction
It is 1 hour or more, for example, 3 hours.
Preferred embodiment according to the present invention, in step (3), the time of the ultrasonic disperse is 0.5-5h；The ultrasound point
Scattered purpose be realize to sulphur replace in oxidation fluorinated graphene the remaining sulphur that is not completely exfoliated replace oxidation fluorographite into
Row removing is prepared the thinner sulphur of the number of plies and replaces oxidation fluorinated graphene.
Preferred embodiment according to the present invention, in step (3), the organic solvent is selected from ethyl alcohol, tetrahydrofuran, DMF, acetone
At least one of.
The present invention also provides the purposes that above-mentioned sulphur replaces oxidation fluorinated graphene, are used for supercapacitor, solar energy etc.
In the fields such as new energy battery, or it is used to prepare in field of compound material.
The present invention also provides a kind of sulphur to replace oxidation fluorinated graphene/polyamide compoiste material, and the composite material includes
Above-mentioned sulphur replaces oxidation fluorinated graphene and polyamide.
Preferred embodiment according to the present invention, the sulphur replace the mass percentage of oxidation fluorinated graphene and polyamide not have
There is special restriction, can contain for any quality percentage that composite material can be prepared as known to those skilled in the art
Amount；Preferably, the sulphur replaces the mass percentage of oxidation fluorinated graphene to be 0.05-8wt%；The quality of the polyamide
Percentage composition is 92-99.95wt%.It is further preferred that the sulphur replaces the mass percentage of oxidation fluorinated graphene to be 0.1-
5wt%；The mass percentage of the polyamide is 95-99.9wt%.
Preferred embodiment according to the present invention, there is no particular limitation for the selection of the polyamide, can be this field skill
The polyamide of any molecular weight and polymer that art personnel know is suitable for compound system of the present invention, described poly-
Amide is prepared using any method as known to those skilled in the art；Preferably, the polyamide is polycaprolactam.
Preferred embodiment according to the present invention, the sulphur replace oxidation fluorinated graphene/polyamide compoiste material to have at least
A kind of performance:
(1) sulphur replaces oxidation fluorinated graphene/polyamide compoiste material tensile strength to be 70-80MPa；
(2) sulphur replaces oxidation fluorinated graphene/polyamide compoiste material notch impact strength to be 4-10kJ/m2。
The present invention also provides above-mentioned sulphur to replace oxidation fluorinated graphene/polyamide compoiste material preparation method, the side
Method comprises the following steps that
A) replace oxidation fluorinated graphene, water and amide monomer to mix sulphur, obtain mixed system；
B) initiator, stabilizer and optionally other auxiliary agents, reaction are added into the mixed system of step a) to solidify,
Sulphur is prepared and replaces oxidation fluorinated graphene/polyamide compoiste material.
Preferred embodiment according to the present invention, step a) specifically comprise the following steps:
A ') by sulphur replace oxidation fluorinated graphene ultrasonic disperse in water, formed slurry；Then amide monomer is added to continue
Ultrasonic disperse obtains mixed system；Mixed system is carried out to remove the moisture of 80-90wt% in mixed system except water process.
Preferably, step a ') in, the time of the ultrasonic disperse is 0.5-10 hours.
Preferably, step a ') in, when water content is larger in the mixed system that is obtained using ultrasonic dispersion, after being unfavorable for
The preparation of continuous composite material；Therefore preferably above-mentioned mixed system remove water except water process for example, by using rotary evaporation.
Preferred embodiment according to the present invention, step a) specifically comprise the following steps:
A ") replace oxidation fluorinated graphene and amide monomer to mix sulphur after be packed into ball grinder, water is added, carries out high temperature ball
Grind dispersion mixing.
Preferably, step a ") in, the revolving speed of the ball milling is 300-500 revs/min, and the time of ball milling is 4-8 hours.
Preferred embodiment according to the present invention, in step a), sulphur replaces oxidation fluorinated graphene and acyl in the mixed system
There is no particular limitation for the proportionate relationship of amine monomers；It is able to achieve sulphur described in the composite material being prepared and replaces fluorine oxide fossil
The mass percentage of black alkene and polyamide is full of defined above.Preferably, the sulphur replaces oxidation fluorinated graphene
Mass ratio with amide monomer is 0.05-10:100.
Preferred embodiment according to the present invention, in step a), the amide monomer is selected from caprolactam.
Preferred embodiment according to the present invention, step a ') in, the mass ratio of the sulphur substitution oxidation fluorinated graphene and water is
1:400-800, such as 1:600.
Preferred embodiment according to the present invention, step a ") in, the mass ratio of the sulphur substitution oxidation fluorinated graphene and water is
1:10-20, such as 1:15.
Preferred embodiment according to the present invention, in step b), the initiator is selected from water or alcohol；When the initiator selects water
When, the water in step a) can be derived from, the water rejoined is also possible to.The dosage of the initiator is amide monomer
1-15wt%；Preferably 5-10wt%, for example, 6wt%.
Preferred embodiment according to the present invention, in step b), the stabilizer is selected from adipic acid or acetic acid；The stabilizer
Dosage is amide monomer 0.1-10wt%；It is preferred that 0.2-5wt%, for example, 0.5wt%.
Preferred embodiment according to the present invention, in step b), other described auxiliary agents are selected from fire retardant (such as antimony oxide), anti-
At least one of oxidant.The dosage of other auxiliary agents is the 0.1-10wt% of amide monomer；Preferably 0.5-5wt%, example
For example 1wt%.
Preferred embodiment according to the present invention, in step b), the temperature of the reaction is 250-300 DEG C, such as 270 DEG C；It is described
The time of reaction is 0.5-12 hours.
Preferred embodiment according to the present invention, in step b), the cured temperature is 200-250 DEG C, such as 230 DEG C；It is described
The cured time is 0.5-12 hours.
The present invention also provides a kind of sulphur to replace oxidation fluorinated graphene/polyamide compoiste material purposes, is used for battery
In the fields such as material, electronic device, coating material.
Beneficial effects of the present invention:
1. the present invention provides a kind of sulphur to replace oxidation fluorinated graphene and its preparation method and application.The sulphur replaces oxygen
Change fluorinated graphene surface and contain active group, compared to graphene, is not susceptible to agglomeration, it is dispersed in the polymer
Preferably, stronger interaction can be directly formed between polymer interface, realize that sulphur replaces oxidation fluorinated graphene polymerizeing
Reinforcing effect in object based composites；The sulphur replaces oxidation fluorinated graphene to can be used for preparing sulphur and replaces fluorine oxide fossil
Black alkene/polyamide compoiste material.
2. replacing oxidation fluorinated graphene/polyamide compoiste material and preparation method thereof the present invention provides a kind of sulphur and using
On the way；The sulphur, which replaces, aoxidizes the fabulous mechanical property of fluorinated graphene/polyamide compoiste material, excellent heating conduction, superelevation
Electric conductivity.The sulphur replaces oxidation fluorinated graphene that can mix by one kettle way with polyamide, ultrasound, and stirring adds
Temperature, drying and other steps are prepared sulphur and replace oxidation fluorinated graphene/polyamide compoiste material.The preparation process simply may be used
Row, easy to operate, universality is strong.
Detailed description of the invention
Fig. 1 is the SEM figure that sulphur described in embodiment 1 replaces oxidation fluorinated graphene.
Fig. 2 is that sulphur as described in example 2 replaces oxidation fluorinated graphene/polyamide compoiste material SEM figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read content disclosed in this invention, ability
Field technique personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within protection defined by the present invention
Within the scope of.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., are commercially available unless otherwise specified.
Embodiment 1
Sulphur replaces the preparation of oxidation fluorinated graphene
2g oxidation fluorographite is weighed, is fitted into porous plastics pipe and sticks on aluminium or nickel electrode, the cathode as electrolysis
And anode.Addition 4.5g mercaptan is electrolyte, and 40ml ethyl alcohol is helped as electrolyte, 2.0g tetraethyl ammonium tetrafluoroborate as electrolysis
Agent cell reaction 3 hours, obtains finely dispersed sulphur and replaces oxidation fluorinated graphene molten under the effect of 15V external direct current power supply
Liquid；This dispersion liquid is subjected to ultrasonic removing, centrifugal treating, with organic solvent washing, is filtered, freeze-drying.Collect sample.
The sulphur being prepared replaces the mass percentage of sulphur in oxidation fluorinated graphene to be 1.26%, the quality percentage of oxygen
Content is 6.7%, and the mass percentage of fluorine is 2.14%.
Embodiment 2
Sulphur replaces the preparation of oxidation fluorinated graphene
6g oxidation fluorographite is weighed, is fitted into porous plastics pipe and sticks on aluminium or nickel electrode, the yin as electrolytic cell
Pole and anode.Addition 15g sulphur urine is electrolyte, and 120ml acetylacetone,2,4-pentanedione is as electrolyte, 5.0g tetraethyl ammonium tetrafluoroborate conduct
It is electrolysed auxiliary agent.Positive and negative anodes are connected on direct current potentiostat, are quickly stirred, fluorination is aoxidized with the DC potential electrolysis stripping of 15V
Graphite 3h obtains finely dispersed sulphur and replaces oxidation fluorinated graphene solution.This dispersion liquid is subjected to centrifugal treating, uses deionization
Water washing filters, freeze-drying.Collect sample.
Embodiment 3
Sulphur replaces oxidation fluorinated graphene/polyamide compoiste material preparation
The sulphur for weighing the preparation of 0.5g above-described embodiment 1 replaces oxidation fluorinated graphene, and ultrasonic disperse is formed in 300g water
Slurry；500g caprolactam is then added, continues ultrasonic disperse 30 minutes, stirs 1 hour, using rotary evaporation method, 90
At DEG C, the water of 90wt% is removed；It moves in reaction kettle, the adipic acid of 2.5g is added, be stirred to react at 270 DEG C 2 hours,
It places after reaction and carries out solidification 3 hours in 230 DEG C in an oven, sulphur can be obtained and replace oxidation fluorinated graphene/polyamide multiple
Condensation material.
Embodiment 4
Sulphur replaces oxidation fluorinated graphene/polyamide compoiste material preparation
The sulphur for weighing the preparation of 2.5g above-described embodiment 1 replaces oxidation fluorinated graphene, and ultrasonic disperse is formed in 300g water
Slurry；500g caprolactam is then added, continues ultrasonic disperse 1 hour, stirs 2 hours, using rotary evaporation method, at 90 DEG C
Under, remove 90% water；It moves in reaction kettle, the adipic acid of 2.5g is added, be stirred to react at 270 DEG C 4 hours, reacted
After place carried out in an oven in 230 DEG C solidification 3 hours, can obtain sulphur replace oxidation fluorinated graphene/polyamide composite wood
Material.
Embodiment 5
Sulphur replaces oxidation fluorinated graphene/polyamide compoiste material preparation
The sulphur for weighing the preparation of 5g above-described embodiment 1 replaces oxidation fluorinated graphene, and ultrasonic disperse forms slurry in 300g water
Material；500g caprolactam is then added, continues ultrasonic disperse 2 hours, stirs 4 hours, using rotary evaporation method, at 90 DEG C
Under, remove 90% water；It moves in reaction kettle, the adipic acid of 2.5g is added, be stirred to react at 270 DEG C 6 hours, reacted
After place carried out in an oven in 230 DEG C solidification 3 hours, can obtain sulphur replace oxidation fluorinated graphene/polyamide composite wood
Material.
Embodiment 6
Sulphur replaces oxidation fluorinated graphene/polyamide compoiste material preparation
The sulphur for weighing the preparation of 10g above-described embodiment 1 replaces oxidation fluorinated graphene, and ultrasonic disperse is formed in 300g water
Slurry；500g caprolactam is then added, continues ultrasonic disperse 3 hours, stirs 6 hours, using rotary evaporation method, at 90 DEG C
Under, remove 90% water；It moves in reaction kettle, the adipic acid of 2.5g is added, be stirred to react at 270 DEG C 8 hours, reacted
After place carried out in an oven in 230 DEG C solidification 3 hours, can obtain sulphur replace oxidation fluorinated graphene/polyamide composite wood
Material.
Embodiment 7
Sulphur replaces oxidation fluorinated graphene/polyamide compoiste material preparation
The sulphur for weighing the preparation of 20g above-described embodiment 1 replaces oxidation fluorinated graphene, mixes, is packed into 500g caprolactam
In ball grinder, 7.5g water is added, 400 revs/min of revolving speed, moves in reaction kettle within ball milling 6 hours, the adipic acid of 2.5g, 22.5g is added
Water, be stirred to react at 270 DEG C 8 hours, place after reaction carried out in an oven in 230 DEG C solidification 3 hours, can
It obtains sulphur and replaces oxidation fluorinated graphene/polyamide compoiste material.
The sulphur that testing example 3 is prepared respectively replaces oxidation fluorinated graphene/polyamide compoiste material and commodity
Tensile strength, the notch impact strength of the polyamide of change, concrete outcome is referring to table 1.
Table 1 is the performance data of the polyamide of the composite material being prepared of embodiment 3 and commercialization
| Tensile strength/MPa | Notch impact strength/kJ/m2 | |
| Embodiment 3 | 71.6 | 9.3 |
| Polyamide | 65.2 | 5.7 |
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of sulphur replaces oxidation fluorinated graphene, wherein the sulphur replaces the quality percentage of sulphur in oxidation fluorinated graphene to contain
Amount is 0.5-5%, such as 1-2%, such as 1.26%.
2. sulphur according to claim 1 replaces oxidation fluorinated graphene, wherein the sulphur replaces in oxidation fluorinated graphene
The mass percentage of oxygen is 5-15%, such as 6-10%, such as 6.7%.
Preferably, the sulphur substitution aoxidizes the mass percentage of fluorine in fluorinated graphene as 1-6%, such as 2-4%, such as
2.14%.
Preferably, the sulphur replaces oxidation fluorinated graphene to have following at least one structure or performance parameter:
(1) sulphur replaces the specific surface area of oxidation fluorinated graphene to be 50-100m2/ g, such as 83m2/g；
(2) sulphur replace oxidation fluorinated graphene with a thickness of 10nm-20 μm；
(3) sulphur replaces the number of plies of oxidation fluorinated graphene to be 10-60 layers.
3. sulphur of any of claims 1 or 2 replaces the preparation method of oxidation fluorinated graphene, the method is with fluorine oxide fossil
Ink is the cathode and anode of electrolytic cell, the electrolyte of electrolytic cell is made into the electrolyte containing element sulphur, in external direct current power supply
Under effect, cell reaction is carried out, sulphur is prepared and replaces oxidation fluorinated graphene.
4. preparation method according to claim 3, wherein described method includes following steps:
(1) to aoxidize fluorographite as the cathode and anode of electrolytic cell, electrolyte and electrolyte solvent containing element sulphur is added,
And it is optionally electrolysed auxiliary agent, it is assembled into electrolytic cell system；
(2) under external direct current power supply effect, electrolysis stripping reaction is carried out to the electrolytic cell system of step (1), is prepared point
The sulphur dissipated in the electrolytic solution replaces oxidation fluorinated graphene.
Preferably, the method also includes following steps:
(3) sulphur in collection step (2) replaces oxidation fluorinated graphene, and re-ultrasonic dispersion in organic solvent, is removed；It will
Dispersion liquid is centrifuged, and is collected top section and is rinsed with organic solvent, filtering, drying.
Preferably, in step (1), the electrolyte containing element sulphur is selected from thiocarbamide or mercaptan；The electrolyte solvent is selected from carbon
Acid propylene ester, ethylene carbonate or diethyl carbonate；The electrolysis auxiliary agent is selected from cetyl trimethylammonium bromide or tetraethyl
Ammonium tetrafluoroborate.
Preferably, in step (1), the mass ratio of the oxidation fluorographite and the electrolyte containing element sulphur is (1-10): (2-
25), for example, 2:(4-5).The mass ratio of the electrolysis auxiliary agent and the electrolyte containing element sulphur is (0-10): (2-25), such as
For 2:(4-5).The volume mass ratio of the electrolyte solvent and the electrolyte containing element sulphur is (20-200mL): (2-25g), example
For example 40mL:(4-5g).
Preferably, in step (2), the external direct current power supply is selected from constant pressure external direct current power supply；The voltage of the DC power supply
Range is between 10-30V, for example, 15V.
5. sulphur of any of claims 1 or 2 replaces the purposes of oxidation fluorinated graphene, it to be used for supercapacitor, solar energy etc.
In the fields such as new energy battery, or it is used to prepare in field of compound material.
6. a kind of sulphur replaces oxidation fluorinated graphene/polyamide compoiste material, the composite material includes claims 1 or 2 institute
The sulphur stated replaces oxidation fluorinated graphene and polyamide.
7. composite material according to claim 6, wherein the sulphur replaces the mass percentage of oxidation fluorinated graphene
For 0.05-8wt%；The mass percentage of the polyamide is 92-99.95wt%.It is further preferred that the sulphur replaces fluorine oxide
The mass percentage of graphite alkene is 0.1-5wt%；The mass percentage of the polyamide is 95-99.9wt%.
Preferably, the polyamide is polycaprolactam.
8. sulphur described in claim 6 or 7 replaces oxidation fluorinated graphene/polyamide compoiste material preparation method, the side
Method comprises the following steps that
A) replace oxidation fluorinated graphene, water and amide monomer to mix sulphur, obtain mixed system；
B) initiator, stabilizer and optionally other auxiliary agents, reaction are added into the mixed system of step a) to solidify, preparation
It obtains sulphur and replaces oxidation fluorinated graphene/polyamide compoiste material.
9. preparation method according to claim 8, wherein step a) specifically comprises the following steps:
A ') by sulphur replace oxidation fluorinated graphene ultrasonic disperse in water, formed slurry；Then amide monomer is added and continues ultrasound
Dispersion, obtains mixed system；Mixed system is carried out to remove the moisture of 80-90wt% in mixed system except water process.
Preferably, step a ') in, the sulphur replaces the mass ratio of oxidation fluorinated graphene and water to be 1:400-800, such as 1:600.
Preferably, step a) specifically comprises the following steps:
A ") replace oxidation fluorinated graphene and amide monomer to mix sulphur after be packed into ball grinder, water is added, carries out high energy ball milling point
Dissipate mixing.
Preferably, step a ") in, the sulphur replaces the mass ratio of oxidation fluorinated graphene and water to be 1:10-20, such as 1:15.
Preferably, in step a), the sulphur replaces the mass ratio of oxidation fluorinated graphene and amide monomer to be 0.05-10:100.
The amide monomer is selected from caprolactam.
Preferably, in step b), the initiator is selected from water or alcohol；The dosage of the initiator is the 1- of amide monomer
15wt%；Preferably 5-10wt%, for example, 6wt%.The stabilizer is selected from adipic acid or acetic acid；The dosage of the stabilizer
For amide monomer 0.1-10wt%；It is preferred that 0.2-5wt%, for example, 0.5wt%.Other described auxiliary agents are selected from fire retardant, antioxygen
At least one of agent.The dosage of other auxiliary agents is the 0.1-10wt% of amide monomer；Preferably 0.5-5wt%, such as
For 1wt%.
Preferably, in step b), the temperature of the reaction is 250-300 DEG C；The time of the reaction is 0.5-12 hours.It is described
Cured temperature is 200-250 DEG C；The cured time is 0.5-12 hours.
10. sulphur described in claim 6 or 7 replaces oxidation fluorinated graphene/polyamide compoiste material purposes, it to be used for battery
In the fields such as material, electronic device, coating material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105911120A (en) * | 2016-04-13 | 2016-08-31 | 中国科学院过程工程研究所 | Sulfur-doped graphene oxide modified glassy carbon electrode, preparation method and detection method for heavy metals in water |
| CN107151321A (en) * | 2017-06-06 | 2017-09-12 | 湖南工业大学 | A kind of fluorinated graphene/MC nylon composite materials and its preparation method and application |
| CN108484909A (en) * | 2018-03-29 | 2018-09-04 | 中国科学院福建物质结构研究所 | A kind of fluorine graphene oxide/composite polyimide material and its preparation method and application |
| US20180261884A1 (en) * | 2012-06-21 | 2018-09-13 | Molecular Rebar Design, Llc | Binders, Electrolytes and Separator Films for Energy Storage and Collection Devices Using Discrete Carbon Nanotubes |
| CN108701823A (en) * | 2016-02-01 | 2018-10-23 | 纳米技术仪器公司 | Electrode of super capacitor and production method with height-oriented and closelypacked graphene film |
-
2018
- 2018-12-26 CN CN201811603596.9A patent/CN109836812B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180261884A1 (en) * | 2012-06-21 | 2018-09-13 | Molecular Rebar Design, Llc | Binders, Electrolytes and Separator Films for Energy Storage and Collection Devices Using Discrete Carbon Nanotubes |
| CN108701823A (en) * | 2016-02-01 | 2018-10-23 | 纳米技术仪器公司 | Electrode of super capacitor and production method with height-oriented and closelypacked graphene film |
| CN105911120A (en) * | 2016-04-13 | 2016-08-31 | 中国科学院过程工程研究所 | Sulfur-doped graphene oxide modified glassy carbon electrode, preparation method and detection method for heavy metals in water |
| CN107151321A (en) * | 2017-06-06 | 2017-09-12 | 湖南工业大学 | A kind of fluorinated graphene/MC nylon composite materials and its preparation method and application |
| CN108484909A (en) * | 2018-03-29 | 2018-09-04 | 中国科学院福建物质结构研究所 | A kind of fluorine graphene oxide/composite polyimide material and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115650218A (en) * | 2022-11-16 | 2023-01-31 | 西安交通大学 | Normal-temperature molten salt with wide potential window, and preparation method and application thereof |
| CN115650218B (en) * | 2022-11-16 | 2024-05-24 | 西安交通大学 | Normal-temperature molten salt with wide potential window, preparation method and application |
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