CN107938323A - A kind of graphene carbon fiber, its preparation method and its application - Google Patents

A kind of graphene carbon fiber, its preparation method and its application Download PDF

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Publication number
CN107938323A
CN107938323A CN201810004622.XA CN201810004622A CN107938323A CN 107938323 A CN107938323 A CN 107938323A CN 201810004622 A CN201810004622 A CN 201810004622A CN 107938323 A CN107938323 A CN 107938323A
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carbon fiber
preparation
graphene
carbon
passed
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CN107938323B (en
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董前程
孙久铭
曾云
张朋
李正宏
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Beijing North Power Technology Co Ltd
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Beijing North Power Technology Co Ltd
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08Materials not undergoing a change of physical state when used
    • C09K5/14Solid materials, e.g. powdery or granular
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40Fibres of carbon

Abstract

The present invention provides a kind of graphene carbon fiber, its preparation method and its application, belongs to graphene and carbon fibre composite technical field.The preparation method of graphene carbon fiber, includes the following steps:Carbon fiber is added in alloy complex liquid, 15~30min of dipping obtains carbon fiber wet feed.Dry carbon fiber wet feed obtains the carbon fiber siccative containing coagent.After carbon fiber siccative is heated to 600~900 DEG C under atmosphere of inert gases again, more carbon cracking gases are passed through, carrying out CVD by the catalytic cracking effect of coagent reacts 0.5~2h.Graphene in-situ deposition between carbon fiber layer is grown by this preparation method, improves interlayer structure, obtained graphene carbon fiber has good electric conductivity and thermal conductivity, can be applied as a kind of new conduction, heat-conductive composite material.

Description

A kind of graphene carbon fiber, its preparation method and its application
Technical field
The present invention relates to carbon fibre composite technical field, in particular to a kind of graphene carbon fiber, its preparation Method and its application.
Background technology
Carbon fiber (carbon fiber, abbreviation CF), is a kind of high intensity of phosphorus content more than 95%, high modulus fibre New fiber materials.It is to be piled up to form along fiber axial direction by organic fibers such as flake graphites, through carbonization and stone Microcrystalline graphite material obtained from blackization processing.Carbon fiber " soft outside but hard inside ", quality is lighter than metallic aluminium, but intensity is higher than steel Iron, and there is corrosion-resistant, high-modulus characteristic, all it is important materials in defence and military and civilian aspect.It not only has carbon The intrinsic intrinsic property of material, and have both the soft machinability of textile fabric, it is reinforcing fiber of new generation.
The structure of carbon fiber is made of the orderly crystallization of bidimensional and hole, and content, size and the distribution of its Hole are to carbon The performance of fiber has a great influence.Hole is mainly distributed between fibre bundle and at interface layer.Voids content is higher, the ruler of hole It is very little bigger, the area of interface layer in laminate is reduced, when material stress, easily along interlaminar failure, this is also interlayer shear The reason for intensity is to hole rdativery sensitive.In addition it is area of stress concentration at hole, bearing capacity is weak, when stressed, expansion of pores Long crack is formed, so as to be destroyed.
Since the interlayer of carbon fiber leaves many big hole defects, cause Cloud Distribution uneven, electric transmission is obstructed, material The electric conductivity and poor heat conduction of material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of graphene carbon fiber, pass through the catalysis of alloy coagent More carbon cracking gases are cracked deposition, finally realize that graphene growth in situ between carbon fiber layer is compound by effect at a lower temperature, Improve the interlayer structure of fiber.
The graphene carbon fiber being prepared another object of the present invention is to provide a kind of above-mentioned preparation method, has very Good electric conductivity and thermal conductivity.
The third object of the present invention is to provide a kind of graphene carbon fiber as conductive, Heat Conduction Material application, can be with For preparing the products such as the carbon paper in the fields such as infrared electric heating, electric precipitation environmental protection and electromagnetic shielding, carbon felt.
The present invention is realized using following technical scheme:
A kind of preparation method of graphene carbon fiber, includes the following steps:
(1), carbon fiber is added in alloy complex liquid, 15~30min of dipping obtains carbon fiber wet feed;
(2), dry carbon fiber wet feed obtains the carbon fiber siccative containing coagent;
(3), after carbon fiber siccative being heated to 600~900 DEG C under atmosphere of inert gases, more carbon cracking gases are passed through, Under coagent catalytic cracking effect, complete CVD and react 0.5~2h.
Further, in preferred embodiments of the present invention, the preparation method of above-mentioned alloy complex liquid is:Chromiumcopper is helped Agent is added to the water 10~15min of stirring, adds iron-nickel alloy auxiliary agent under conditions of 80~90 DEG C, continue stirring reaction 4~ 8h。
Further, in preferred embodiments of the present invention, the mass ratio of above-mentioned chromiumcopper auxiliary agent and iron-nickel alloy auxiliary agent For 1:1~2.
Further, in preferred embodiments of the present invention, in above-mentioned steps (1), the quality of carbon fiber and alloy complex liquid Than for 1:8~10.
Further, in preferred embodiments of the present invention, in above-mentioned steps (2), in the condition that temperature is 120~160 DEG C 4~6h of lower drying.
Further, in preferred embodiments of the present invention, in above-mentioned steps (3), more carbon cracking gases be selected from methane, ethane, At least one of propane, normal butane, iso-butane, pentane, isopentane, neopentane, ethene, propylene, n-butene and isobutene.
Further, in preferred embodiments of the present invention, in above-mentioned steps (3), monitoring fluidized-bed reactor is further included In tail gas the step of hydrogen volume percentage.
Further, in preferred embodiments of the present invention, after above-mentioned steps (3), further include and stop the logical of more carbon cracking gases Enter, stop heating, after being cooled to 20-30 DEG C, stopping is passed through inert gas, the step of the graphene carbon fiber removed.
The graphene carbon fiber that a kind of preparation method of above-mentioned graphene carbon fiber is prepared.
If above-mentioned graphene carbon fiber is as conductive, Heat Conduction Material application.
The beneficial effect of preparation method for the graphene carbon fiber that presently preferred embodiments of the present invention provides is:It is complexed in alloy Add carbon fiber in liquid, 15~30min of dipping obtains carbon fiber wet feed, enables alloy complex liquid well into arriving carbon fiber In the hole of interlayer structure or carbon fiber.Dry carbon fiber wet feed obtains carbon fiber siccative, removes the moisture in carbon fiber wet feed, Remaining alloy coagent facilitates subsequent reactions.After carbon fiber siccative is heated to 600~900 DEG C under atmosphere of inert gases, More carbon cracking gases are passed through, through coagent catalytic pyrolysis, CVD is carried out and reacts 0.5~2h.Under atmosphere of inert gases, carbon is avoided Fiber siccative is contacted with the oxygen in air, and carbon fiber burns after preventing subsequent heat, after being heated to 600~900 DEG C, is led to Enter more carbon cracking gases and carry out CVD 0.5~2h of reaction, more carbon cracking gases are passed through at high temperature, due to the catalysis of alloy coagent Effect, makes more carbon cracking gases occur to crack deposition reaction at relatively low temperature, finally in carbon fiber interlayer structure and hole Growth in situ generation graphene is carried out in gap, improves interlayer structure, so as to get graphene carbon fiber there is good electric conductivity And thermal conductivity.
The beneficial effect of graphene carbon fiber provided by the invention is:Using the preparation method system of above-mentioned graphene carbon fiber It is standby to obtain, the interlayer structure of carbon fiber and the hole of carbon fiber are modified by mesoporous graphene, the Cloud Distribution made More uniformly, increase the electron transport efficiency of carbon fiber interlayer structure, improve the electric conductivity and thermal conductivity of graphene carbon fiber.
The beneficial effect of the application of graphene carbon fiber provided by the invention is:Conductive, Heat Conduction Material can be used as, can be with For preparing the products such as the carbon paper in the fields such as infrared electric heating, electric precipitation environmental protection and electromagnetic shielding, carbon felt, meet the need of client Ask, there is good commercial value.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair The restriction of scope, for those of ordinary skill in the art, without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings and fall within protection scope of the present invention.
Fig. 1 is the process flow chart of the preparation method of graphene carbon fiber provided by the invention.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer The condition of view carries out.Reagents or instruments used without specified manufacturer, is the conventional production that can be obtained by commercially available purchase Product.
The graphene carbon fiber of the embodiment of the present invention, its preparation method and its application are specifically described below.
Fig. 1 is the process flow chart of the preparation method of graphene carbon fiber provided by the invention.A kind of referring to Fig. 1, stone The preparation method of black olefinic carbon fiber, includes the following steps:
(1), alloy complex liquid is prepared:Chromiumcopper auxiliary agent is added to the water 10~15min of stirring, adds iron-nickel alloy Auxiliary agent, continues 4~8h of stirring reaction under conditions of 80~90 DEG C.First chromiumcopper auxiliary agent is added to the water, makes water and copper chromium Alloy auxiliary agent is uniformly mixed, and reduces the concentration of chromiumcopper auxiliary agent, is occurred both when avoiding adding iron-nickel alloy auxiliary agent acute Strong reaction, adds iron-nickel alloy auxiliary agent, both is reacted generation alloy complex liquid at a certain temperature, makes it as follow-up Catalysts, have good catalytic effect.
Preferably, the mass ratio of chromiumcopper auxiliary agent and water is 1:30~50, the alloy complexing of suitable concentration can be obtained Liquid, alloy complex liquid can be good at entering in the interlayer structure of carbon fiber and the hole of carbon fiber.In the present invention, water is to go Ionized water, avoids the catalytic effect of the impurity effect alloy complex liquid in water.
In the present invention, chromiumcopper auxiliary agent, deionized water and iron-nickel alloy auxiliary agent are stirred in stirred autoclave Reaction, equipment requirement is not high, and production cost is relatively low.
Preferably, the mass ratio of chromiumcopper auxiliary agent and iron-nickel alloy auxiliary agent is 1:1~2.The alloy obtained under this ratio Complex liquid has good catalytic effect, makes deposition effect of the graphene on carbon fiber more preferable.
(2), carbon fiber is added in alloy complex liquid, 15~30min of dipping obtains carbon fiber wet feed.
During dipping, alloy complex liquid is entered in the interlayer structure of carbon fiber and the hole of carbon fiber, make follow-up In reaction, alloy coagent makes more carbon cracking gases in the interlayer structure of carbon fiber and the hole of carbon fiber as catalyst Cracking deposition is carried out, realizes in-situ preparation graphene, is conducive to obtain electric conductivity and the graphene carbon of thermal conductivity function admirable is fine Dimension.
Meanwhile the process of dipping carries out in stirred autoclave, it is also transferred in other positive displacement containers and carries out.It is i.e. straight Carbon fiber is added in the alloy complex liquid being connected in stirred autoclave, but during carbon fiber is added, to stop stirring, Nature dipping is carried out, improves dipping effect.
In the present invention, carbon fiber is chopped carbon fiber, and the length of chopped carbon fiber is 1~100mm.
Preferably, the mass ratio of carbon fiber and alloy complex liquid is 1:8~10.Make in the interlayer structure and hole of carbon fiber Alloy complex liquid can be sufficiently submerged in, improves the effect of subsequent reactions.
(3), dry carbon fiber wet feed obtains carbon fiber siccative, removes the moisture in carbon fiber wet feed, avoids moisture from influencing Cracking reaction, facilitates follow-up reaction.
In the present invention, dry 4~6h under conditions of being 120~160 DEG C in temperature.The temperature had both avoided the combustion of carbon fiber Burn and coagent inactivation, and avoid drying time it is long cause to waste, make the drying effect of carbon fiber wet feed more preferable.
Preferably, by the uniform sabot of carbon fiber wet feed, it is placed in electrical heating baking oven and is dried.Make carbon fiber wet feed Drying effect is more preferable, and shortens the time of drying.
(4), after carbon fiber siccative being heated to 600~900 DEG C under atmosphere of inert gases, more carbon cracking gases are passed through, are led to The catalytic cracking of coagent is crossed, CVD is carried out and reacts 0.5~2h.Under atmosphere of inert gases, carbon fiber siccative and air are avoided In oxygen contact, carbon fiber burns after avoiding subsequent heat, is passed through more carbon cracking gases at high temperature, since alloy is active The catalytic action of auxiliary agent, makes more carbon cracking gases that cracking reaction occur at relatively low temperature, and in carbon fiber interlayer structure With in hole in-situ deposition generate graphene, improve interlayer structure, so as to get graphene carbon fiber there is good electric conductivity And thermal conductivity.
In detail, carbon fiber siccative is placed in fluidized-bed reactor, and inert gas is passed through in fluidized-bed reactor; Inert gas is passed through, discharges the air in fluidized-bed reactor, carbon fiber burns after avoiding subsequent heat.
In the present invention, the uniform padding and compacting of carbon fiber siccative is placed in fluidized-bed reactor, enable it is follow-up its with it is more Carbon cracking gas uniformly contacts, and is deposited on so as to graphene uniform in the interlayer structure of carbon fiber and the hole of carbon fiber.
Preferably, before inert gas is passed through, further include detection fluidized-bed reactor air-tightness the step of, avoid sending out Angry body leakage.In the present invention, inert gas is nitrogen or argon gas, it will not react with carbon fiber, avoid carbon fiber Structure changes.
Continuation is passed through inert gas in fluidized-bed reactor and after fluid bedreactors is heated to 600~900 DEG C, leads to Enter 0.5~2h of more carbon cracking solid/liquid/gas reactions.More carbon cracking gases are passed through at high temperature, contain carbon fiber and alloy network in carbon fiber siccative The dried alloy coagent of liquid is closed, the effect of dipping is first passed through, alloy auxiliary agent is penetrated into carbon fiber interlayer structure and carbon In the hole of fiber, recycle alloy coagent to be catalyzed more carbon cracking gases, make more carbon cracking gases at relatively low temperature Generation cracking deposition reaction generation graphene, completes mesoporous graphene growth, and pass through mesoporous graphene on carbon fibre carrier Increase electric transmission efficiency, improve interlayer structure, improve the electric conductivity and thermal conductivity of graphene carbon fiber.
Wherein, mode of heating can be Electric heating or other mode of heatings, if can fluid bedreactors into Row heating.
In the present invention, more carbon cracking gases are selected from methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, new At least one of pentane, ethene, propylene, n-butene and isobutene..When more carbon cracking gases are methane, fluidized-bed reactor Interior temperature is 800~900 DEG C, and the reaction time is 1~2h, and temperature is higher, and the reaction time is longer, the graphene carbon fiber of generation It is more preferable for substance structure, the electric conductivity and thermal conductivity of graphene carbon fiber.
When more carbon cracking gases are ethene, temperature in fluidized-bed reactor is 700~800 DEG C, the reaction time for 1~ 1.2h;When more carbon cracking gases for propylene or propane, butane when liquefied petroleum gas (LPG) gas mixture when, the temperature in fluidized-bed reactor is 600~700 DEG C, the reaction time is 0.5~0.7h, and the graphene carbon fiber of both generation is mainly multiplet.
In the present invention, the volume ratio for being passed through more carbon cracking gases and inert gas is:0.1~10:1, just start reaction when It is more to wait the amount that more carbon cracking gases are passed through, after reacting a period of time, as coagent amount reduces the interlayer knot with carbon fiber It deposited a part of graphene in the hole of structure and carbon fiber, so the demand of more carbon cracking gases is reduced, then reduced more The amount that carbon cracking gas is passed through.
The amount that more carbon cracking gases are passed through number with tail gas hydrogen content number it is related, just start reaction when, due to The effect of alloy auxiliary agent, the cracking reaction of more carbon cracking gases is very fast, and more hydrogen is contained in tail gas, monitors fluidized-bed reactor Hydrogen volume percentage in tail gas, as a result percentage by volume is 40%~50%, when the tail gas of monitoring fluidized-bed reactor When middle hydrogen volume percentage is 15%~20%, the intake of more carbon cracking gases is reduced, makes more carbon cracking gases and inert gas Volume ratio be 5:1.
In the present invention, fluidized-bed reactor is vertical fluidised reactor, can also use horizontal reactor, fixed reaction The reaction units such as device.And cracking reaction gas can also use segmentation pre-heating technique, be added continuously in fluidized-bed reactor.
(5), stop being passed through, stopping fluidized-bed reactor heating for more carbon cracking gases, treat that fluidized-bed reactor is cooled to 20- After 30 DEG C, stopping is passed through inert gas, the graphene carbon fiber removed, and it is detected, is packed.Hydrogen in tail gas Relative content when being less than 5%, stop being passed through of more carbon cracking gases, stop fluidized-bed reactor and heat, treat fluidized-bed reaction Device is cooled to room temperature, and stopping is passed through inert gas, the graphene carbon fiber removed.First stop being passed through for more carbon cracking gases, Being passed through for inert gas is kept in temperature-fall period, prevents after stopping cracking reaction, air is mixed into fluidized-bed reactor, favorably In the protection to graphene carbon fiber, its burning is avoided.
The technology that preparation method provided by the invention uses all uses common chemical industry kind equipment, except high temperature, anti-corrosion, It is explosion-proof to wait outside custom requirements, it is not relatively low using other more special equipment, production cost.
The graphene carbon fiber being prepared by the preparation method of above-mentioned graphene carbon fibrous composite, by mesoporous Graphene modifies the interlayer structure of carbon fiber and the hole of carbon fiber, and the Cloud Distribution made is more uniform, increases carbon The electron transport efficiency of fiber interlayer structure, improves the electric conductivity and thermal conductivity of graphene carbon fiber.
Above-mentioned graphene carbon fiber can be used for preparing infrared electric heating, electric precipitation as conductive, Heat Conduction Material application The products such as the carbon paper in field such as environmental protection and electromagnetic shielding, carbon felt.
Embodiment 1
A kind of preparation method of graphene carbon fiber, includes the following steps:
(1), impregnated carbon fiber 30min is added in alloy complex liquid and obtains carbon fiber wet feed.
(2), dry carbon fiber wet feed obtains carbon fiber siccative.
(3), after carbon fiber siccative being heated to 600 DEG C under atmosphere of inert gases, more carbon cracking solid/liquid/gas reactions 0.5h are passed through.
Embodiment 2
A kind of preparation method of graphene carbon fiber, includes the following steps:
(1), alloy complex liquid is prepared:Chromiumcopper auxiliary agent is added in the stirred autoclave equipped with deionized water and is stirred 10min, add iron-nickel alloy auxiliary agent continue under conditions of 90 DEG C stirring reaction 4h obtain alloy complex liquid, wherein, copper chromium The mass ratio of alloy auxiliary agent and water is 1:30, the mass ratio of chromiumcopper auxiliary agent and iron-nickel alloy auxiliary agent is 1:1.
(2), stop the stirring of stirred autoclave, chopped carbon fiber dipping 15min is added in alloy complex liquid and obtains carbon Fiber wet feed, wherein, the mass ratio of chopped carbon fiber and alloy complex liquid is 1:8.
(3), by the uniform sabot of carbon fiber wet feed, it is placed in electrical heating baking oven, it is dry under conditions of being 160 DEG C in temperature 4h obtains carbon fiber siccative.
(4), by carbon fiber siccative material uniform compaction, it is placed in fluidized-bed reactor, and be passed through inert gas.Continuation is being flowed It is passed through inert gas in fluidized bed reactor and after fluid bedreactors are heated to 600 DEG C, is passed through methane, ethane, ethene, third Alkane, propylene, normal butane, iso-butane, n-butene and isobutene mixed gas (liquefied petroleum gas) reaction 0.5h.
(5), stop being passed through, stopping fluidized-bed reactor heating for more carbon cracking gases, treat that fluidized-bed reactor is cooled to 20 After DEG C, stopping is passed through inert gas, the graphene carbon fiber removed, and it is detected, is packed.
Embodiment 3
A kind of preparation method of graphene carbon fiber, includes the following steps:
(1), alloy complex liquid is prepared:Chromiumcopper auxiliary agent is added in the stirred autoclave equipped with deionized water and is stirred 15min, add iron-nickel alloy auxiliary agent continue under conditions of 80 DEG C stirring reaction 8h obtain alloy complex liquid, wherein, copper chromium The mass ratio of alloy auxiliary agent and water is 1:50, the mass ratio of chromiumcopper auxiliary agent and iron-nickel alloy auxiliary agent is 1:2.
(2), stop the stirring of stirred autoclave, chopped carbon fiber dipping 30min is added in alloy complex liquid and obtains carbon Fiber wet feed, wherein, the mass ratio of chopped carbon fiber and alloy complex liquid is 1:10.
(3), by the uniform sabot of carbon fiber wet feed, it is placed in electrical heating baking oven, it is dry under conditions of being 120 DEG C in temperature 6h obtains carbon fiber siccative.
(4), by carbon fiber siccative material uniform compaction, it is placed in fluidized-bed reactor, and is passed through inert gas, continues flowing It is passed through inert gas in fluidized bed reactor and after fluid bedreactors are heated to 900 DEG C, is passed through methane, ethane, propane, positive fourth Alkane and iso-butane mixed gas (natural gas) reaction 2h.
(5), stop being passed through, stopping fluidized-bed reactor heating for more carbon cracking gases, treat that fluidized-bed reactor is cooled to 30 After DEG C, stopping is passed through inert gas, the graphene carbon fiber removed, and it is detected, is packed.
Embodiment 4
A kind of preparation method of graphene carbon fiber, includes the following steps:
(1), alloy complex liquid is prepared:Chromiumcopper auxiliary agent is added in the stirred autoclave equipped with deionized water and is stirred 12min, add iron-nickel alloy auxiliary agent continue under conditions of 85 DEG C stirring reaction 5h obtain alloy complex liquid, wherein, copper chromium The mass ratio of alloy auxiliary agent and water is 1:40, the mass ratio of chromiumcopper auxiliary agent and iron-nickel alloy auxiliary agent is 1:1.2.
(2), stop the stirring of stirred autoclave, chopped carbon fiber dipping 20min is added in alloy complex liquid and obtains carbon Fiber wet feed, wherein, the mass ratio of chopped carbon fiber and alloy complex liquid is 1:9.
(3), by the uniform sabot of carbon fiber wet feed, it is placed in electrical heating baking oven, it is dry under conditions of being 150 DEG C in temperature 5h obtains carbon fiber siccative.
(4), by carbon fiber siccative material uniform compaction, it is placed in fluidized-bed reactor, and is passed through inert gas, continues flowing It is passed through inert gas in fluidized bed reactor and after fluid bedreactors are heated to 800 DEG C, is passed through ethylene reaction 1.2h.
(5), stop being passed through, stopping fluidized-bed reactor heating for more carbon cracking gases, treat that fluidized-bed reactor is cooled to 25 After DEG C, stopping is passed through inert gas, the graphene carbon fiber removed, and it is detected, is packed.
Experimental example 1
The electric conductivity performance and heat conductivility of the graphene carbon fiber that is obtained to embodiment 1-4 and carbon fiber on the market Detection obtains table 1,
1 electric conductivity performance of table and heat conductivility contrast table
Electric conductivity (Ω/) Heat conductivility (w/mk)
Embodiment 1 1 2.2
Embodiment 2 1.2 2
Embodiment 3 1.1 2.1
Embodiment 4 0.9 1.9
Carbon fiber on the market >10 0.5
As it can be seen from table 1 graphene carbon fiber prepared by the preparation method for the black olefinic carbon fiber for passing through the present invention has Good electric conductivity and thermal conductivity, have excellent performance.
Embodiments described above is part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts Every other embodiment, belongs to the scope of protection of the invention.

Claims (10)

1. a kind of preparation method of graphene carbon fiber, it is characterised in that include the following steps:
(1), carbon fiber is added in alloy complex liquid, 15~30min of dipping obtains carbon fiber wet feed;
(2), the dry carbon fiber wet feed obtains the carbon fiber siccative containing coagent;
(3), after the carbon fiber siccative being heated to 600~900 DEG C under atmosphere of inert gases, more carbon cracking gases are passed through, are led to The catalytic cracking of coagent is crossed, CVD is carried out and reacts 0.5~2h, obtain graphene carbon fiber.
2. preparation method according to claim 1, it is characterised in that the preparation method of the alloy complex liquid is:By copper Evanohm auxiliary agent is added to the water 10~15min of stirring, adds iron-nickel alloy auxiliary agent, continues to stir under conditions of 80~90 DEG C React 4~8h.
3. preparation method according to claim 2, it is characterised in that the chromiumcopper auxiliary agent is helped with the iron-nickel alloy The mass ratio of agent is 1:1~2.
4. preparation method according to claim 1, it is characterised in that in the step (1), the carbon fiber and the conjunction The mass ratio of golden complex liquid is 1:8~10.
5. preparation method according to claim 1, it is characterised in that be 120~160 DEG C in temperature in the step (2) Under conditions of dry 4~6h.
6. preparation method according to claim 1, it is characterised in that in the step (3), more carbon cracking gases are selected from In methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, ethene, propylene, n-butene and isobutene At least one.
7. preparation method according to claim 1, it is characterised in that in the step (3), further include the monitoring fluidisation In the tail gas of bed reactor the step of hydrogen volume percentage.
8. preparation method according to claim 1, it is characterised in that after the step (3), further include and stop more carbon Cracking gas is passed through, stops heating, and after being cooled to 20-30 DEG C, stopping is passed through the inert gas, the graphene carbon removed The step of fiber.
A kind of 9. graphene carbon that preparation method such as claim 1~8 any one of them graphene carbon fiber is prepared Fiber.
10. graphene carbon fiber as claimed in claim 9 is as conductive, Heat Conduction Material application.
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CN110022623A (en) * 2019-04-04 2019-07-16 碳翁(北京)科技有限公司 A kind of preparation and application of high temperature resistant fibre electroheating
CN110258106A (en) * 2019-07-19 2019-09-20 中南林业科技大学 A kind of preparation method of the sandwich-type flexible electromagnetic shielding material based on carbon fibre fabric, metallic nickel nano granule and graphene
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CN114014659A (en) * 2021-11-05 2022-02-08 新疆农六师碳素有限公司 Novel high-end carbon product material for aluminum and preparation method thereof
CN115491784A (en) * 2022-08-24 2022-12-20 凯盛石墨碳材料有限公司 Preparation method of graphene/carbon fiber/polypropylene fiber with excellent conductivity

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