CN106409525B - Graphene, conducting fibre composite material and its with the preparation method of multi-stage porous carbon composite material, its product and application - Google Patents
Graphene, conducting fibre composite material and its with the preparation method of multi-stage porous carbon composite material, its product and application Download PDFInfo
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- CN106409525B CN106409525B CN201610886809.8A CN201610886809A CN106409525B CN 106409525 B CN106409525 B CN 106409525B CN 201610886809 A CN201610886809 A CN 201610886809A CN 106409525 B CN106409525 B CN 106409525B
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Abstract
The invention discloses a kind of graphene, conducting fibre composite material and its with the preparation method of multi-stage porous carbon composite material, its product and application, belong to new material and new energy application field.Each architectural characteristic, has the characteristics that high mechanical strength, multi-stage porous, good conductivity, lightweight, flexibility are good, stability is high and specific capacitance is high for the carbon material set carbon fiber, graphene and activated carbon.It is compound that the preparation method includes carbon fiber exhibition silk and graphene composite setting, graphene/conducting fibre/activated carbon in-situ activation.The carbon material has the comparable tensile strength of carbon fiber；The material can be directly used in ultracapacitor, and metal collector is not required；It is expected to be used for traffic（Lightweight electric car）, the fields such as energy conservation and environmental protection and medical treatment.
Description
Technical field
The present invention relates to a kind of graphene, conducting fibre composite material and its preparation sides with multi-stage porous carbon composite material
The application of product and products obtained therefrom in ultracapacitor, ultralight amount automobile made from method and use this method, belongs to new material
With new energy application field.
Background technology
The lightweight of automobile and motorized are the developing direction of automobile, are the supporting points of the economic innovation and development of pillar.Energy storage
Material is the key technology of motorcar electric, and the lightweight of automobile is the key that one of motorized.
Carbon fiber is a kind of material of filamental, has excellent toughness and tensile strength, and weight only has the 1/ of steel
4.Carbon fiber has been successfully used in the vehicle body of automobile as a kind of light-weight high-strength material, to mitigate the weight of automobile, but
It is never to have been reported that carbon fiber as vehicle body and the report of energy storage dual function.
The news report that graphene is also used for vehicle body coating is had recently emerged, but also without the function of energy storage.
There are no the reports that carbon fiber/graphite alkene composite material is used for automobile.
In order to meet motorcar electric, light-weighted demand, hence it is imperative that close with energy fast charging and discharging, high-energy
Degree and high power density, environmental-friendly, lightening, flexibility, the energy storage material of high intensity.Ultracapacitor is as a kind of new
High-performance electric chemistry energy storage device, possess high-energy density, be widely studied and applied in recent years.Ultracapacitor
Electrode material be the key factor for limiting ultracapacitor development, directly affect the amount of capacity of ultracapacitor, power is close
Degree, energy density, cycle life, temperature characterisitic, security feature etc..Carbon-based material is most widely used electrode material, mainly
Including：Activated carbon, carbon fiber, carbon nanotubes and graphite, also by the graphene of everybody extensive concern.Graphene is by monolayer carbon
The bi-dimensional cellular shape crystal structure that atom close-packed arrays form, each carbon atom pass through sp2The carbon atom of hydridization and surrounding is formed
Regular hexagon, this hexagonal cells are similar to phenyl ring, and each carbon atom there remains the p tracks of a non-bonding, these p tracks
Overlapped, the pi bond electronics for forming delocalization freely moves in lattice.Carbon simple substance of the graphene as newest form, as
A kind of emerging ultralight two-dimentional carbon material has many excellent performances, for example, the specific surface area of super large, good flexibility and
Superpower mechanical strength, quick electron mobility, outstanding thermal conductivity and translucency and excellent electric conductivity.These are excellent
Performance so that graphene is equal in the fields such as chemical sensor and flexible energy storage device, electronic device, composite material, photoelectric device
Have wide practical use.But the macroscopic body of graphene usually not mechanical strength, without metal support and collector, nothing
Method effectively uses.
Electrode of super capacitor usually requires to go conduction with metal collector, but metal collector can also reduce simultaneously it is whole
The specific discharge capacity of a capacitor.Thus, there is an urgent need to good conductivity, high mechanical strength, chemical stability is good, at low cost, matter
It measures light collector and removes substituted metal collector.
Carbon fiber is a kind of microcrystalline graphite material as obtained from organic fiber carbonization and graphitization processing, and carbon content is more than
A kind of 90% high-performance fiber, because its have unique high intensity, good conductive and heat conductivility, good mechanical flexibility,
It is at low cost, diameter is smaller, light weight, low-density, high-modulus, nontoxic, chemical inertness, it is easily prepared into three-dimensional material and multiple
The advantages that condensation material, therefore carbon based fibers can provide good flexible branch as new flexible carrier material for active material
Support.It can be good at substituted metal collector in ultracapacitor.
But carbon fibre tow and fabric are too thick, with millimeter rank is often arrived, are not used to energy storage electrode material.Thus
It needs to carry out fiber thin layer.
The thin layer of carbon based fibers refers to, to carbon based fibers big tow progress horizontal spreading, reach uniformly lossless ultralight ultra-thin
The technology of expansion, the exhibition fibre technology of the carbon based fibers of big tow is always a kind of challenge.Fiber sprawls thinner, mass area ratio
Smaller, physical property deviation is smaller, and the operability being coated with is also better, and mechanical property is more excellent, therefore to carbon based fibers tow
Broadening be directly related to the quality of subsequent fiber joint product.The fine good and bad degree of exhibition is directly related to the firm of composite material
A series of performances such as degree, intensity.At present fiber broadening arrangement process in mostly using air-flow method, hot milling process, supercritical ultrasonics technology,
Jet-impingement method, sonic method.Hot milling process melts sizing agent i.e. by heat effect, while squeezing by pressure roller and cord roller
Pressure acts on, and fibre bundle broadens thinning, due to the effect of heating, fibre structure is caused to change, the fiber power of this method expansion
It learns performance to be greatly reduced, has seriously affected the use of fiber, and this method speed is slower, it is less efficient；Supercritical ultrasonics technology utilizes
The acoustic cavitation effect that ultrasonic wave generates generates the percussive pressure of moment, causes the high-speed motion of molecule, so as to reach the fine mesh of exhibition
, this fiber broadening arrangement method fibre damage is big, and fibre damage is more than 20%.By the fibre strength and mould so handled
Amount reduces, and largely effects on the mechanical property and quality stability of composite products；Sonic method is to utilize low-frequency generator by electricity
Signal is changed into sound wave, using air vibration tow, tow is unfolded；Jet-impingement exhibition nanofarads utilize vertical fibers direction
Air-flow laterally moves fibre bundle, so that it is unfolded, the fibre bundle obtained by this exhibition method for fiber, extension width
Greatly, stability is good, and interfibrous intersection is less, and fluffing is few, becomes the research hotspot of the fine technical field of exhibition.It can carbon fiber is use up
During energy expansion exhibition is thin, also to ensure the integrality and mechanical property of carbon mono-filaments as far as possible, avoid fiber buckling, fluffing
The defects of generation.In order to reduce fibre damage, improvement fibre bundle sprawls effect, and a kind of mode of single use is not answered to open up fibre, and
It is the combination that should use the fine mode of a variety of exhibitions.The fine mode of existing exhibition is made a general survey of, none is carried out using electrochemistry combination flow perturbation
Exhibition fibre.Carbon fiber, the preparation process of activated carbon and graphene these three carbon materials are entirely different, are usually all using dividing completely
Prepared by vertical technique, they are all inert solid materials, are combined highly difficult.There is presently no a kind of carbon materials to wrap simultaneously
Three kinds of carbon fiber-containing, activated carbon and graphene forms, more organically can not in situ combine carbon fiber, activated carbon and graphene
Get up, be provided simultaneously with the excellent properties of three.
The content of the invention
The present invention is intended to provide a kind of graphene, conducting fibre composite material and its system with multi-stage porous carbon composite material
The application of product and products obtained therefrom in ultracapacitor, ultralight amount automobile made from Preparation Method and use this method.
The present invention provides a kind of graphenes and the compound method of conducting fibre silk, it is characterised in that：Conducting fibre
Tow is lain on perforated membrane, and conducting fibre is as cathode（Cathode）, conductive lead wire is as anode（Anode）, graphene dispersion
In the electrolytic solution, electrolyte adheres to and soaks conducting fibre and membrane interface, and the electrolysis that is powered generates bubble, while perpendicular to electricity
The ullage for solving liquid applies flow perturbation, and the spacing of dynamic control anodic-cathodic, driving liquid is solid and fiber movement scatters, and controls
Amount and the liquid-solid boundary effect of liquid so that fiber exhibition silk is simultaneously compound with graphene simultaneously, then removes electrolyte, graphene with
Perforated membrane is dissociated after composite fiber membrane drying, obtains graphene, conducting fibre composite material.
The graphene can with but be not limited to prepare by the method for electrochemical stripping graphite, this prepares the side of graphene
Method refers to CN 103693638A.
Further, the conducting fibre is：Carbon fiber or graphene fiber；The conductive lead wire is：Graphite paper, height
At least one of the processed graphene film of temperature, Ti nets or nickel foam；The electrolyte is：H2SO4、NaOH、Na2SO4Or
(NH4)2SO4At least one of；The mass concentration of electrolyte is：5%~25%；The concentration of the graphene in the electrolytic solution is：
0.1~10 mg/mL。
In above-mentioned electrolytic process, the spacing of anodic-cathodic be it is dynamic, number, spreading width with conducting fibre amount,
Electrolyte is how many and conductive lead wire is related, and specific scope is related with experimental size.
The voltage of the electrolysis is 3 ~ 40 V, and electric current is：The A of 0.02 A ~ 0.9, time is：5~10 min；Gas is released in electrolysis
The speed of body is 1.0 ~ 10 ml/cm2·s。
Use electrochemistry and mode that flow perturbation is combined by the concrete operations of big boundling conducting fibre drawout for：
First the conducting fibre of silk to be opened up is lain on a clean PP film, is subsequently poured into electrolyte to fiber complete wetting, it will
Conducting fibre boundling is as cathode, and just extremely strips of conductive substance carries out it using the charge mode of single cathode, double anodes
It charges, meanwhile, it is being sent into flow perturbation perpendicular to the top of electrolysis liquid surface；The current rate is：250 ~ 1200 W, air-flow go out
Mouth and liquid level distance：10 ~ 20 cm, flow perturbation area：400~600 cm2。
The present invention is released gas, is generated bubble using electrochemistry driving conducting fibre exhibition silk, mainly electrolysis, and driving is fine
Dimension expansion, therefore the gas generated is more, the repulsive force between fibre single thread is bigger；It can also identical charges repel each other by ionic charge
With the principle that there is a natural attraction between the sexes, the same same charge of electrode adsorption and repel, and moved to the opposite charge direction of another pole band
It is dynamic.Preferably to open up silk, on the basis of electrolysis, it can also dry from surrounding and liquid surface, be added with air-flow and liquid flow movement
Speed strengthens exhibition silk.
Therefore, present invention firstly provides a kind of combination electrochemistry and the flow perturbation sides fine to carbon based fibers Shu Jinhang exhibitions
Method increases substantially the fine speed of exhibition, can greatly enhance the exhibition fibre effect of carbon based fibers beam so that carbon based fibers beam spreading width
Uniform and frivolous, because during electrochemistry exhibition is fine, carbon fiber surface is graphene-supported so that conducting fibre mechanical property
Can be more preferable, while carbon based fibers reliable in quality, carbon based fibers thickness can be effectively controlled, fiber expansion mode device simply closes
Reason, by selecting different parameters, be adapted to the expansion of different amounts of carbon based fibers, equipment investment expense is low, it is easy to operate,
Improve production efficiency；In addition, after electrolyte volatilization is dry, graphene plays the role of conducting fibre of shaping, and can finally obtain
One graphene/carbon base fiber composite film.
The carbon based fibers that traditional carbon based fibers cloth laterally longitudinally interweaves need the braiding by machine, and the present invention can make
Standby a large amount of graphene/carbon base composite fiber membranes, then by these films successively horizontal longitudinal arrangement, with a small amount of water infiltration graphene it
It treats its moisture drying again afterwards, due to the filming function of graphene, each composite membrane can be bonded together, you can obtain carbon-based fibre
The full carbon cloth of the graphene/carbon base fiber composite of the horizontal longitudinally staggered arrangement of dimension, according to actual needs, can adjust different thickness
Degree.Graphene/carbon base fiber composite film has excellent electric conductivity, capability of electromagnetic shielding, anti-seismic performance, mechanical strength, soft
Property, foldable, density is low.
The mode of flow perturbation is：When air-flow flows vertically through fibre bundle, the air-flow at fiber beam center and both sides position
Speed, pressure have differences, fiber is subject to airflow acting force to be moved in the width direction and to carry out exhibition fine.Air-flow runs into fibre bundle
Backward both sides shunting simultaneously generates the fiber at edge certain active force, and air-flow continues at the surface center of boundling to both sides point
Stream, and the monofilament of the disengaging collection of filaments is pushed to both sides under the cross stream velocity component of air-flow, air-flow enters the hole between fiber,
Form a plurality of streamline that fiber is promoted to both sides.When the flat-pushing power of gas transverse flowing water is more than resistance, fiber is transported to both sides
Dynamic, the fibre bundle of aggregation scatter.Therefore the air-flow lateral velocity acted on fiber is bigger, and air-flow gets over the motive force of fiber
Greatly, fiber is more readily expanded.Under the interaction of air-flow and liquid stream, carbon based fibers is made to be more prone to scattered development in a liquid
It is wide.
Due to electrolyte and the liquid-solid boundary active force of fiber（Such as soak the surface tension of generation）And fiber, electrolyte
With the solid-liquids such as film are solid, solid interface interaction power and promote the motion and standstill of fiber.So electrolysis, air-flow, gas-liquid and liquid are consolidated
4 kinds of interface interaction etc. and its more than collective effect can drive conducting fibre exhibition silk film forming.
There is solid-liquid active force between graphene and electrolyte, there is solid solid interface active force, fiber between graphene and fiber
There is stronger solid solid interface active force between perforated membrane, can dynamically adjust content and the position of electrolyte to cause fiber
Silk is unfolded and shapes.Pass through the control to direct current power source voltage, electric current, electrolyte type and concentration, graphene concentration, positive and negative electrode
System makes carbon based fibers beam become more frivolous, the fine effect of exhibition more preferable.It the advantage is that and greatly reduce fiber during expansion
Damage ratio reduces the generation of the burr of fracture of wire, improves the uniformity of fiber architecture, improves exhibition silk efficiency.
It is of the invention to open up fibre the difference is that the fiber after opening up fibre is collected without complicated device, in the present invention with traditional
In, it only needs in the electrolytic solution according to actual needs, to add in certain density graphene, after liquid to be electrolysed is done, graphene is used for fixed
Type expansion carbon based fibers monofilament, then directly tear from perforated membrane, you can obtain the equally distributed graphene of carbon based fibers/
Carbon based fibers composite membrane.
The present invention provides the products that above-mentioned graphene and the compound method of conducting fibre are prepared.
Since the film forming ability of graphene is strong, there is leakproofness, electrical and thermal conductivity is good, has excellent electromagnet shield effect, leads
While conductive fiber or graphite fibre exhibition silk are shaped with graphene In-situ reaction, conducting fibre film forming ability can be significantly improved
And capability of electromagnetic shielding.
Under normal conditions, conducting fibre tow is all to be compiled into cloth close to grade is other.And use the present invention's
Method, carbon fiber（Graphite fibre）It within 45 micron thickness or even is controlled with the thickness control of graphene composite film to monofilament
Thickness, and the tensile strength of composite membrane is kept approximately constant with carbon fiber, up to 3.0 more than GPa.
For the specific surface area of graphene usually more than 500 m2 gs, flexibility is fabulous, good conductivity, so stone can be improved
The specific surface area of black alkene/conducting fibre composite material so that composite material is provided simultaneously with the high intensity of three, high-specific surface area
Highly conductive and high-flexibility high-performance.
The present invention provides the preparation methods of a kind of graphene, conducting fibre and multi-stage porous carbon composite material, first will
Graphene is compound with conducting fibre, after the drying of the composite membrane of graphene and conducting fibre, will contain graphene, activated carbon
The mixed slurry of charcoal source and chemical activating agent is coated uniformly on two surfaces of the composite membrane, is finally dried, activates, acid
It washes, wash.Specifically include following steps：
（1）The preparation of graphene：By the method graphene of electrochemical stripping graphite, preparation method can refer to CN
103693638 A；
（2）Electrolyte quota：By graphene ultrasonic disperse in water, conductive materials are added in thereto to be uniformly mixed,
Obtain electrolyte 1；
（3）Fiber opens up silk：Multifibres bundle fiber is immersed in electrolyte 1, the mode being combined with the gentle flow disturbance of electrochemistry,
In electrolysis both perpendicular to electrolysis liquid surface blowing gas stream, carbon based fibers boundling is unfolded, after solvent volatilization is dry in liquid to be electrolysed, is left
Graphene be used for the carbon based fibers monofilament of fixed expansion, obtain the composite membrane 2 of graphene/carbon base fiber；
（4）It is prepared by mixed slurry：By certain mass than graphene and activated carbon charcoal source ultrasonic disperse in water, stirring is mixed
Centrifugation removal supernatant after closing uniformly, then leaching are put in chemical activation agent solution, are uniformly mixed to obtain mixed slurry 3；
（5）Mixed slurry 3 is coated in step（3）Described 2 liang of surfaces of composite membrane, are placed in argon gas in tube furnace after drying
High-temperature activation obtains film 4 under atmosphere；
（6）By step（5）The film 4 with hydrochloric acid and deionized water clean repeatedly repeatedly until pH value for 7 to get to one kind
The high intensity, porous full carbon material of ultracapacitor is can apply to, i.e. graphene, conducting fibre and the multi-stage porous carbon is answered
Condensation material.
Further, the conducting fibre includes but is not limited to：Carbon fiber or graphene fiber.
The electrolyte is：H2SO4、NaOH、Na2SO4Or (NH4)2SO4At least one of；The mass concentration of electrolyte
For：5%~25%；The concentration of the graphene in the electrolytic solution is：0.1~10 mg/mL.Conductive lead wire is anode, conductive lead wire
For：At least one of graphene film, Ti nets or nickel foam that graphite paper, high-temperature process are crossed；
The voltage of the electrolysis is 3 ~ 40 V, and electric current is：The A of 0.02 A ~ 0.9, time is：5~10 min；Gas is released in electrolysis
The speed of body is 1.0 ~ 10 ml/cm2·s。
The concrete operations of big boundling carbon based fibers drawout are by the mode that electrochemistry and flow perturbation are combined：It will first treat
The conducting fibre of exhibition silk is lain on a clean PP film, electrolyte 1 is subsequently poured into fiber complete wetting, by electric conductivity
The collection of filaments fills it using the charge mode of single cathode, double anodes as anode as cathode, strips of conductive substance
Electricity, meanwhile, it is being sent into flow perturbation perpendicular to the top of electrolysis liquid surface.The current rate is：250 ~ 1200 W, air stream outlet
With liquid level distance：10 ~ 20 cm, flow perturbation area：400~600 cm2.It is in this method, carbon based fibers electrochemistry is gentle
The mode that flow disturbance is combined carries out exhibition fibre, and the carbon based fibers monofilament of expansion is finally fixed with graphene, while uses graphene
Conductive fiber is protected, during preventing follow-up in-situ activation, corrosion of the alkali activator to carbon based fibers keeps carbon based fibers
Mechanical property.
The activated carbon charcoal source includes but is not limited to using biomass carbon source：Microcrystalline cellulose, carboxymethyl cellulose
At least one of plain sodium, pitch, catkin；The chemical activating agent is：NaOH、KOH、ZnCl2、CaCl2At least one of；
The preparation process of the mixed slurry includes, but are not limited to：
（1）Graphene and activated carbon charcoal source are uniformly mixed into 10 ~ 14 h, are then centrifuged for washing repeatedly, 60 ~ 80 DEG C
Then vacuum drying removes extra chemical activating agent with centrifugation after 20 ~ 28 h of chemical activating agent immersion of 5 ~ 9 mol/L；
（2）Hydro-thermal process will be carried out up to graphite containing the mixed slurry of graphene-activated carbon charcoal source-chemical activating agent
The mixed slurry of alkene-activated carbon charcoal source-chemical activating agent three.
The graphene and the mass ratio in activated carbon charcoal source are：4~35:100；The hydrothermal conditions are：150~190
4 ~ 8 h of hydro-thermal process in DEG C baking oven.
The mixed slurry is applied directly to uniform graphene/conducting fibre composite membrane both side surface, mixed slurry
After dry on graphene/conducting fibre composite membrane, activated carbon is obtained by chemical activation mode.
The chemical activation mode is：Dried is attached with the compound of graphene-activated carbon charcoal source-chemical activating agent
Film is put into high temperature process furnances, and 500 ~ 650 DEG C of 0.5 ~ 1.5 h of activation are to get to graphene-activated carbon-conduction under Ar protections
Property composite fiber membrane；Graphene is just as binding agent, relevant portion hydridization together.
The pickling, water-washing process are by the HCl of graphene-activated carbon -0.1 ~ 0.5 mol/L of carbon based fibers composite membrane
HCl is repeatedly first carried out with deionized water washing to wash, and removes K2O, K2CO3Substances are waited, are then washed with water until pH is 7, after dry
Obtain graphene, conducting fibre and multi-stage porous carbon composite material.
Preparation method the present invention also provides above-mentioned graphene, conducting fibre and multi-stage porous carbon composite material is prepared
Product.The tensile strength of products obtained therefrom is 3.0 more than GPa, specific surface area is 800 m2The ratio electricity of/more than g, super capacitor
Hold for 76 ~ 144 F/g.
The complex carbon material set conducting fibre, graphene and each self-structure of activated carbon and characteristic, have
The features such as high mechanical strength, multi-stage porous, good conductivity, lightweight, flexibility are good, stability is high and specific capacitance is high.
Gained graphene, conducting fibre and multi-stage porous carbon composite material are a kind of high intensity, porous full carbon material, the height
The full carbon material of strength porous has the characteristics that high high intensity, high specific area, area specific capacity, light weight and flexibility；Can weave,
Coating, can be with other materials interface cohesion；According to the needs of different capabilities preferred Lay up design can be used to make full use of
The anisotropy of conducting fibre accurately controls the ply stacking angle of every layer of conducting fibre, fully realizes uniformly accurate laying, real
Quality is most light, the highest structure of intensity to build for current minimum conducting fibre.
The present invention provides above-mentioned graphene, conducting fibre and multi-stage porous carbon composite material answering in ultracapacitor
With.
The comparable tensile strength of the conductive fiber of the carbon material（Data are shown up to 4.5 GPa）.The material can be straight
It connects for ultracapacitor, metal collector is not required.
The preparation method of the ultracapacitor is：Graphene, conducting fibre and multi-stage porous carbon composite material are punched
Into the disk of a diameter of 9 mm, then using " sandwich " structure, by carbon composite-membrane-carbon composite layer assembly,
It is finally putting into homemade cylindrical die, electrolyte encapsulation is added dropwise.The membrane is the film of ultracapacitor assembling, such as
3501 films of Celgard.
Graphene, conducting fibre and multi-stage porous carbon composite material, active material and collector all use carbon-based material, with
Collector of the carbon based fibers as ultracapacitor, using graphene and activated carbon as active material, carbon based fibers are also made simultaneously
For graphene and the support frame of activated carbon, manufactured electrode of super capacitor structure is similar to the structure of " armored concrete ",
Carbon based fibers are covered by just as " reinforcing bar " among " concrete " of graphene and activated carbon composition.
The present invention also provides above-mentioned graphene, conducting fibre and multi-stage porous carbon composite material in ultralight amount automobile
Using.
Graphene and conductive fiber composite material provided by the invention can be used for the vehicle body of automobile, provide lightweight, high-strength
Security protection and the function of energy storage.
The composite material of graphene provided by the invention, conductive fiber and multi-stage porous carbon, can be used for the vehicle body of automobile, provide
High-strength light, security protection, the function of super capacitor standby energy storage.Collect vehicle body and energy storage integrated, reach automotive light weight technology
Purpose.
The concrete mode in ultralight amount automobile is applied to be in graphene, conducting fibre and multi-stage porous carbon composite material：It will
Made graphene, conducting fibre and multi-stage porous carbon composite material is laid with layer by layer, is assembled into flexible super capacitor, this is super
Capacitor has the function of antidetonation, places in molding die, carries out preforming processing；Then apply in ultralight amount automobile, use
The flexible capacitor of graphene, conducting fibre and multi-stage porous carbon composite material composition is as automobile body covering piece.Further
Ground, the body outer skin include：One or more of front hatch cover, head cover, rear hatchcover, left and right gusset.
The automobile has a very high mechanical strength, light weight, while also serve as automobile energy storage device, as stand-by power supply,
Collect vehicle body and energy storage integrated, reach the target of automotive light weight technology design.The high intensity that body outer skin is prepared for the present invention
Porous full carbon material, body frame are traditional high-strength aluminum alloy space structure or carbon fibre composite, the ultralight amount of vehicle
Compared with similar type steel automobile, weight is substantially reduced for design.The manufactured full carbon porous material of high intensity is both used as body of a motor car,
Energy storage device is also served as simultaneously, largely reaches the target of automotive light weight technology design, and integral body can be improved
Intensity improves the course continuation mileage of vehicle.
Beneficial effects of the present invention：
（1）Graphene provided by the invention/conducting fibre laminated film has excellent electric conductivity, electromagnetic wave shielding
Energy, anti-seismic performance, mechanical strength, flexibility, it is foldable, density is low.
（2）Graphene provided by the invention, conducting fibre and multi-stage porous carbon composite material, are provided simultaneously with chemical stabilization
Good, good conductivity, specific surface area height, intensity are very high（3.0 more than GPa）, super capacitance electrode material without metal collector
Function.
（3）The low cost preparation method of multi-stage porous high-strength carbon material provided by the invention, selfcapacity melt with collector
It is integrated, takes full advantage of the advantage of carbon based fibers high mechanical strength, light weight, softness, reduce electrode quality, alleviate gold
Belong to the weight shared by collector, the energy density of final ultracapacitor can be improved.Ultracapacitor has the function of antidetonation, has
It hopes for electric vehicle.
（4）Present invention eliminates active materials in traditional electrode preparation process and conductive agent, the mistake of adhesion agent mixed pulp
Journey and coating procedure by the way of activated carbon is prepared in situ, avoid ultracapacitor contact resistance；Preparation method letter
Single, proper temperature, the time is shorter, and operation is easy.
（5）The present invention first protects carbon based fibers with graphene, is then coated with active matter slurry, prevents and work is prepared in situ
In property charcoal activation process, corrosion of the alkali activator to carbon based fibers maintains mechanical property.
（6）High intensity, porous full carbon material set conductive fiber, graphene and active carbon functional prepared by this method is in one
Body has highly conductive, the thermal conductivity of graphene, the high mechanical properties of carbon based fibers, the high-specific surface area of activated carbon, adsorptivity
Energy, chemical property, the SP of existing graphene2Hydbridized carbon atoms also have the SP of carbon based fibers and activated carbon3Hydbridized carbon atoms；It is multiple
Condensation material has that density is low, coefficient of thermal expansion is small, mechanical behavior under high temperature is excellent, anti-thermal shock and high temperature resistant ablation, resistant to chemical etching
The features such as.So all there is very big potential using value in aerospace field or in civil field.
（7）The present invention also serves as graphene and work using collector of the conductive fiber as electrode of super capacitor
The support frame of property charcoal.It can not only substitute traditional by the use of nickel foam, copper foil, aluminium foil as collector, reduce the matter of electrode slice
Amount, while carbon based fibers have certain mechanical strength, foldable, flexible, can be prepared into flexible wearable electronic product.
（8）This method does collector with carbon based fibers substitution is traditional with nickel foam, copper foil and aluminium foil, not only alleviates electricity
Pole quality, the energy density for improving final ultracapacitor, while electrode made of high intensity, porous carbon material is with very high
Mechanical strength, corrosion resistant have flexibility, additionally it is possible to carry out large-scale industrial production；Therefore it can be applied to ultralight amount garage
In industry, body of a motor car can be both used as, there is certain mechanical strength, anti-seismic performance, crush resistance energy, and energy storage can be used as
Device not only reduces the low voice speaking amount of vehicle, it is integrated with vehicle body can also to collect energy storage；It is expected to be used for traffic（Lightweight electric car）、
The fields such as energy conservation and environmental protection and medical treatment.
（9）The present invention uses biomass material as charcoal source, of low cost, environmental-friendly；High intensity prepared by the present invention is more
The full carbon material good conductivity in hole, density are small；The full carbon porous material of high intensity prepared by the present invention is flexible, foldable, can prepare
Into wearable electronic product, flexible super capacitor, meets the needs of people are to lightening and flexibility portable electronic product.
（10）High intensity, porous full carbon material provided by the invention has higher specific capacity and good cycle performance, close
Small, light weight is spent, has that good electric conductivity, film resistance be small, excellent thermal conductivity；Preparation method is environmentally friendly, easy to operate；This hair
The porous full carbon material of the high intensity of bright preparation has good absorption property, can also be applied to water process, gas purification, no
Only energy conservation and environmental protection, and can be recycled, facilitate recycling.
（11）High intensity, porous full carbon material area specific capacity is high, light weight, can be used according to the needs of different capabilities
Preferred Lay up design accurately controls the ply stacking angle of every layer of carbon fiber to make full use of the anisotropy of carbon fiber, fully real
Now uniform accurate laying realizes that quality is most light, the highest structure of intensity to build with minimum carbon fiber.
Description of the drawings
Fig. 1 is that 1 electrochemistry of embodiment and flow perturbation are combined the schematic device fine to carbon based fibers Shu Jinhang exhibitions.Carbon
Base fiber is as cathode, and graphite paper is as anode.Air-flow is sent into perpendicular to carbon based fibers from top.
Fig. 2 is that 1 electrochemistry of embodiment and flow perturbation combine process to carbon fibre stretching, and what four width figures showed is from taking
The fine device of the exhibition of building is powered to infiltration electrolyte is unfolded dry complete change in process.
Fig. 3 is the optical photograph of 1 graphene/carbon composite fiber membrane of embodiment.
Fig. 4 is the capability of electromagnetic shielding of 1 graphene/carbon composite fiber membrane of embodiment.
Fig. 5 is the mechanical property of carbon fiber of the embodiment 1 by electrochemistry and flow perturbation exhibition before and after fine.
Fig. 6 is the optical photograph of 1 graphene of embodiment, carbon fiber and multi-stage porous carbon composite material.
Fig. 7 is the original carbon fiber SEM characterizations without any processing.
Fig. 8 is SEM characterization of the carbon fiber after overload graphene, activated carbon.Carbon fiber surface has loaded fine and close
One layer graphene-absorbent charcoal composite material.
Fig. 9 is that the SEM of graphene, carbon fiber and multi-stage porous carbon composite material is characterized.Carbon fiber is wrapped by as reinforcing bar
Among the concrete of graphene-activated carbon composition.
Figure 10 is that the TEM of graphene, carbon fiber and multi-stage porous carbon composite material is characterized.
Figure 11 is the mechanical property figure of graphene, carbon fiber and multi-stage porous carbon composite material.
Figure 12 is（a）Without cellulose-graphene-KOH mixtures of hydro-thermal process with passing through 170 DEG C of hydro-thermal process
The thermogravimetric analysis of cellulose-graphene-KOH mixtures compare,（b）Graphene-activated carbon and predecessor graphene-cellulose
FTIR spectrum comparison,（c）The comparison that the XRD of graphene-activated carbon and graphene predecessor is composed,（d）Graphene-work of preparation
The Raman spectrograms of property charcoal.
Figure 13 is（a）CV graph of the electrode prepared by embodiment 1 in different scanning speed,（b）Prepared by embodiment 1
Specific capacity situation of change of the ultracapacitor under the current density of 1 ~ 21 A/g,（c）The impedance of electrode is ground prepared by embodiment 1
Study carefully,（d）The Ragone curves of electrode prepared by embodiment 1.
Figure 14 is（a）CV graph of the electrode prepared by embodiment 3 in the sweep speed of 0.005 V/s,（b）Embodiment
Charging and discharging curve figure of the ultracapacitor prepared by 3 when current density is 1 A/g.
Figure 15 is（a）CV graph of the electrode prepared by embodiment 4 in the sweep speed of 0.005 V/s,（b）Embodiment
Charging and discharging curve figure of the ultracapacitor prepared by 3 when current density is 1 A/g.
Specific embodiment
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Embodiment 1：
Firstth, electrochemistry and flow perturbation are combined the exhibition of big boundling carbon fiber broadening is thin
It is 0.5 g/L first to prepare graphene concentration, and sulfuric acid concentration is 20% electrolyte, is dispersed with stirring uniformly.Then one is taken
Beam quality is the carbon fiber of 0.15 g, is lain on pp films, and using carbon fiber as cathode, graphite paper is anode, using single cathode, double
The charge mode of anode, temperature are 25 DEG C, then infiltrate electrode with electrolyte, are charged with DC current regulator power supply,
Schematic diagram is shown in Fig. 1, and charging voltage is 15 V, and electric current is about 0.02 A.
After liquid moisture to be electrolysed is done, remaining graphene, finally will be dried for the carbon mono-filaments for expansion of shaping
Graphene/carbon composite fiber membrane is torn from pp films.The fine process of exhibition is shown in Fig. 2.From figure 2 it can be seen that a branch of carbon fiber passes through
After electrochemistry and flow perturbation exhibition are fine, broadening exhibition is thin in the width direction, and the thickness of graphene/carbon composite fiber membrane passes through control
Graphene concentration processed, amount of carbon fiber, air-flow size, voltage swing adjust the expansion degree of carbon fiber.
Extensive graphene/carbon composite fiber membrane optical photograph is shown in Fig. 3；In Fig. 3 as can be seen that the extensive graphene/
Carbon fiber composite membrane is flexible with good flexible foldable；Two width figures in Fig. 3 can be seen that graphene/carbon fiber and answer
It is very thin and foldable to close film.
Graphene/carbon composite fiber membrane has excellent capability of electromagnetic shielding, sees Fig. 4.
After electrochemistry and the exhibition of flow perturbation collective effect are fine, the exhibition fibre effect of carbon fiber is good, and mechanical property does not almost have
Have loss, shown in Fig. 5 exhibition it is fine before and after the mechanical property of carbon fiber kept well.In Figure 11, there is the carbon that graphene wraps up
Fiber is increased slightly compared with original carbon fiber mechanical property.
Secondth, graphene-activated carbon charcoal source-KOH mixed slurries are prepared
The graphene dispersing solution that first compound concentration is the cellulose aqueous solution of 0.1 g/ml and concentration is 5.3 mg/ml, connects
It is 4 the two according to graphene and cellulose mass ratio:96 amount uniformly mixes, and a night is stirred at room temperature after 1 h of ultrasound；
The mixture of graphene and cellulose is obtained after filtered, 60 DEG C of 6 h of vacuum drying, next, the leaching of this mixture is placed in 7
The mass ratio of 24 h in the KOH solution of mol/L, KOH and cellulose is 4:1, it is then centrifuged for obtaining graphene-cellulose-KOH and mix
Slurry is closed, then by 170 DEG C of 4 h of hydro-thermal process of this slurry, centrifugation removal supernatant liquid stays gained slurry spare.
3rd, high intensity, porous full carbon material is prepared
Gained slurry in second step is coated uniformly on gained graphene/carbon composite fiber membrane upper surface in the first step to treat
After dry tack free, then gained slurry in second step is uniformly coated in graphene/carbon composite fiber membrane lower surface, be subsequently placed in 80
Dry 10 h are to get graphene-cellulose-KOH- carbon fiber composite membranes in DEG C vacuum drying oven, from Figure 12（a）As can be seen that 650
DEG C when, graphene-cellulose is weightless more, therefore this film finally is activated 1 h 650 DEG C under an argon atmosphere, from Figure 12（b）It can be with
Find out, cellulose carbonization, most afterwards after the HCl and deionized water of 0.1 mol/L is washed repeatedly, in 80 DEG C of vacuum drying ovens
Dry 10 h are shown in Fig. 6, which has flexibility well, can roll over to get high intensity, porous full carbon material
It is folded flexible.Wherein active matter content 42.8%.The carbon fiber surface of most original is smooth, sees Fig. 7, by a series of processing
Afterwards, carbon fiber surface has loaded one layer of fine and close graphene-activated carbon active matter, sees Fig. 8, the high intensity, porous full carbon materials of gained
Material forms the structure of similar " armored concrete ", " coagulation that carbon fiber is formed as " reinforcing bar " by graphene and activated carbon
Soil " package.This material has very high mechanical strength, sees Fig. 9.Meanwhile Tu11Zhong, area load have graphene-activated carbon
Carbon fiber mechanical strength highest.
4th, electrochemical property test
The disk that high intensity, porous full carbon material is punched into a diameter of 9 mm obtains a kind of super electricity of the full carbon of high intensity
Container electrode.Then two electrode super capacitor devices are assembled into, in electrochemical workstation, using cyclic voltammetry, constant current is filled
Electric discharge, the chemical property of test capacitors, and pass through formula and calculate its specific capacity.Test result shows ultracapacitor
Electrode specific capacity when charging and discharging currents density is 1 A/g is up to 134 F/g and sees Figure 13（b）, it is 0.005 in sweep speed
During V/s, specific capacity is up to 144 F/g and sees Figure 13（a）.
Embodiment 2
Firstth, electrochemistry and flow perturbation are combined the exhibition of big boundling carbon fiber broadening is thin.
It is 0.5 g/L first to prepare graphene concentration, and sulfuric acid concentration is 20% electrolyte, is dispersed with stirring uniformly.Then one is taken
Beam quality be 0.15 g carbon fiber, lie on pp films, using carbon fiber as cathode, graphene film is anode, using single cathode,
The charge mode of double anodes, temperature are 25 DEG C, then infiltrate electrode with electrolyte, are filled with DC current regulator power supply
Electricity, schematic diagram are shown in Fig. 1, and charging voltage is 15 V, and electric current is about 0.06 A.After liquid moisture to be electrolysed is done, remaining graphene is used
The carbon mono-filaments of expansion are fixed, finally dried graphene/carbon composite fiber membrane are torn from pp films.
Secondth, graphene-cellulose-KOH mixed slurries are prepared
The graphene dispersing solution that first compound concentration is the cellulose aqueous solution of 0.1 g/ml and concentration is 6.5 mg/ml, connects
It is 10 the two according to graphene and cellulose mass ratio:90 amount uniformly mixes, and one is stirred at room temperature after 1 h of ultrasound
Night；The mixture of graphene and cellulose is obtained after filtered, 60 DEG C of 6 h of vacuum drying, next, the leaching of this mixture is placed in
The mass ratio of 24 h in the KOH solution of 7 mol/L, KOH and cellulose is 4:1, it is then centrifuged for obtaining graphene-cellulose-KOH
Mixed slurry, then by 170 DEG C of 2 h of hydro-thermal process of this slurry, centrifugation removal supernatant liquid stays gained slurry spare.
3rd, graphene-activated carbon-carbon-fiber film is prepared
About 5% CMC aqueous solutions will be added in the slurry of gained in second step（Mass content 1.5%）, mixed grinding is uniform,
Gained slurry is coated uniformly in the first step after gained graphene/carbon composite fiber membrane upper surface dries after upper surface, then
Graphene/carbon composite fiber membrane lower surface uniformly coats gained slurry, is subsequently placed in 80 DEG C of vacuum drying ovens dry 10 h, i.e.,
Graphene-cellulose-KOH- carbon-fiber films are obtained, by graphene-cellulose-KOH- carbon-fiber films in 300 kg/cm2Pressure under
Press 30 min.This film is finally activated into 1 h for 650 DEG C under an argon atmosphere, HCl and deionized water through 0.1 mol/L are washed repeatedly
After washing, dry 10 h are shown in Fig. 6, the high intensity, porous full carbon materials to get high intensity, porous full carbon material in 80 DEG C of vacuum drying ovens
Material has flexibility well, foldable flexible.
4th, electrochemical property test
The disk that high intensity, porous full carbon material is punched into a diameter of 9 mm obtains a kind of super electricity of the full carbon of high intensity
Container electrode.Then two electrode super capacitor devices are assembled into, in electrochemical workstation, using cyclic voltammetry, constant current is filled
Electric discharge, the chemical property of test capacitors, and pass through formula and calculate its specific capacity.Test result shows ultracapacitor
Electrode specific capacity when charging and discharging currents density is 1 A/g is up to 76 F/g, when sweep speed is 0.005 V/s, specific volume
Amount is up to 94 F/g.
Embodiment 3
Firstth, electrochemistry and flow perturbation are combined the exhibition of big boundling carbon fiber broadening is thin.
It is 0.5 g/L first to prepare graphene concentration, and sulfuric acid concentration is 20% electrolyte, is dispersed with stirring uniformly.Then one is taken
Beam quality is the carbon fiber of 0.15 g, is lain on pp films, and using carbon fiber as cathode, nickel foam is anode, using single cathode, double
The charge mode of anode, temperature are 25 DEG C, then infiltrate electrode with electrolyte, are charged with DC current regulator power supply,
Schematic diagram is shown in Fig. 1, and charging voltage is 15 V, and electric current is about 0.02 A.After liquid moisture to be electrolysed is done, remaining graphene is used for solid
Surely the carbon mono-filaments being unfolded finally tear dried graphene/carbon composite fiber membrane from pp films.
Secondth, graphene-activated carbon-KOH mixed slurries are prepared
The graphene aqueous dispersions that first compound concentration is the cellulose aqueous solution of 0.1 g/ml and concentration is 5.3 mg/ml,
Then it is 4 according to graphene and cellulose mass ratio by the two:96 amount uniformly mixes, and one is stirred at room temperature after 1 h of ultrasound
Night；The mixture of graphene and cellulose is obtained after filtered, 60 DEG C of 6 h of vacuum drying, next, the leaching of this mixture is put
The mass ratio of 24 h in the KOH solution of 7 mol/L, KOH and cellulose is 2:1, be then centrifuged for obtaining graphene-activated carbon-
KOH mixed slurries, centrifugation removal supernatant liquid stay gained slurry spare.
3rd, high intensity, porous full carbon material
About 5% ptfe solution will be added in the slurry of gained in second step（Solid content 60%）, it is then that gained slurry is equal
Graphene/carbon composite fiber membrane upper surface obtained by even coating in the first step, after being dried after upper surface, then it is fine in graphene/carbon
Dimension composite membrane lower surface uniformly coats gained slurry, is subsequently placed in 80 DEG C of vacuum drying ovens dry 10 h to get graphene-fibre
Tie up element-KOH- carbon-fiber films, finally by this film under an argon atmosphere 650 DEG C of activation 1 h, HCl through 0.1 mol/L and go from
After sub- water washs repeatedly, dry 10 h are shown in Fig. 6, the high intensity to get high intensity, porous full carbon material in 80 DEG C of vacuum drying ovens
Porous full carbon material has flexibility well, foldable flexible.
4th, electrochemical property test
The disk that high intensity, porous full carbon material is punched into a diameter of 9 mm obtains a kind of super electricity of the full carbon of high intensity
Container electrode.Then two electrode super capacitor devices are assembled into, in electrochemical workstation, using cyclic voltammetry, constant current is filled
Electric discharge, the chemical property of test capacitors, and pass through formula and calculate its specific capacity.Test result shows ultracapacitor
Electrode specific capacity when charging and discharging currents density is 1 A/g is up to 88 F/g and sees Figure 14（b）, it is 0.005 V/ in sweep speed
During s, specific capacity is up to 100 F/g and sees Figure 14（a）.
Embodiment 4
Firstth, electrochemistry and flow perturbation are combined the exhibition of big boundling carbon fiber broadening is thin.
It is 0.5 g/L first to prepare graphene concentration, and sulfuric acid concentration is 20% electrolyte, is dispersed with stirring uniformly.Then one is taken
Beam quality be 0.15 g carbon fiber, lie on pp films, using carbon fiber as cathode, Ti nets be anode, using single cathode, it is double just
The charge mode of pole, temperature are 25 DEG C, then infiltrate electrode with electrolyte, are charged with DC current regulator power supply, are shown
Intention is shown in Fig. 1, and charging voltage is 15 V, and electric current is about 0.10 A.After liquid moisture to be electrolysed is done, remaining graphene is used for shaping
The carbon mono-filaments of expansion finally tear dried graphene/carbon composite fiber membrane from pp films.
Secondth, graphene-absorbent charcoal composite material is prepared
The graphene dispersing solution that first compound concentration is the cellulose aqueous solution of 0.1 g/ml and concentration is 5.3 mg/ml, connects
It is 4 the two according to graphene and cellulose mass ratio:96 amount uniformly mixes, and a night is stirred at room temperature after 1 h of ultrasound；
The mixture of graphene and cellulose is obtained after filtered, 60 DEG C of 6 h of vacuum drying, next, the leaching of this mixture is placed in 7
The mass ratio of 24 h in the KOH solution of mol/L, KOH and cellulose is 4:1, it is then centrifuged for obtaining graphene-cellulose-KOH
Mixed slurry, it is then that this is pulp centrifuged, supernatant liquor is removed, dry 12 h is subsequently placed in 100 DEG C of vacuum drying chambers, connects
It and this mixture is activated into 1 h, after the HCl and deionized water of 0.1 mol/L is washed repeatedly, 80 for 650 DEG C under an argon atmosphere
Dry 10 h are to get graphene-activated carbon multistage hole composite material in DEG C vacuum drying oven.
3rd, high intensity, porous full carbon material is prepared
According to mass ratio it is 96 by gained graphene-absorbent charcoal composite material and CMC and SBR in second step:2:2 amount is mixed
It closes, water grinding is added to be modulated into slurry, then this slurry is uniformly coated in graphene/carbon composite fiber membrane upper surface, treats
After dry tack free, then in graphene/carbon composite fiber membrane another side this slurry is uniformly coated, be subsequently placed in 80 DEG C of vacuum and dry
For dry 12 h to get high intensity, porous full carbon material, which has flexibility well, foldable in case
It is flexible.
4th, electrochemical property test
The disk that high intensity, porous full carbon material is punched into a diameter of 9 mm obtains a kind of super electricity of the full carbon of high intensity
Container electrode.Then two electrode super capacitor devices are assembled into, in electrochemical workstation, using cyclic voltammetry, constant current is filled
Electric discharge, the chemical property of test capacitors, and pass through formula and calculate its specific capacity.Test result shows ultracapacitor
Electrode specific capacity when charging and discharging currents density is 1 A/g is up to 102 F/g and sees Figure 15（b）, it is 0.005 in sweep speed
During V/s, specific capacity is up to 120 F/g and sees Figure 15（a）.
Claims (20)
1. a kind of graphene and the compound method of conducting fibre, it is characterised in that：It is combined using electrochemistry and flow perturbation
Mode by big boundling conducting fibre drawout, conducting fibre tow is lain on perforated membrane, and conducting fibre is as negative
Pole, conductive lead wire is as anode, and in the electrolytic solution, electrolyte adheres to and soaks conducting fibre and membrane interface graphene dispersion,
The electrolysis that is powered generates bubble, while applies flow perturbation in the ullage perpendicular to electrolyte, dynamic control anodic-cathodic
Spacing drives liquid is solid to scatter with fiber movement, controls the amount of liquid and liquid-solid boundary effect so that fiber exhibition silk and while and stone
Black alkene is compound, then removes electrolyte, and graphene obtains graphene and electric conductivity with dissociating perforated membrane after composite fiber membrane drying
Fibrous composite.
2. graphene according to claim 1 and the compound method of conducting fibre, it is characterised in that：The electric conductivity is fine
It ties up and is：Carbon fiber or graphene fiber；The conductive lead wire is：Graphene film, Ti nets or the foam that graphite paper, high-temperature process are crossed
At least one of nickel；The electrolyte is：H2SO4、NaOH、Na2SO4Or (NH4)2SO4At least one of；The matter of electrolyte
Measuring concentration is：5%~25%；The concentration of the graphene in the electrolytic solution is：0.1~10 mg/mL.
3. graphene according to claim 1 and the compound method of conducting fibre, it is characterised in that：The electricity of the electrolysis
It presses as 3 ~ 40 V, electric current is：The A of 0.02 A ~ 0.9, time is：5~10 min；The speed that gas is released in electrolysis is 1.0 ~ 10 ml/
cm2·s。
4. graphene according to claim 1 and the compound method of conducting fibre, it is characterised in that：Using electrochemistry and
The concrete operations of big boundling conducting fibre drawout are by the mode that flow perturbation is combined：It is first that the electric conductivity of silk to be opened up is fine
Dimension is lain on a clean PP film, electrolyte is subsequently poured into fiber complete wetting, using conducting fibre boundling as negative
Pole, just extremely strips of conductive substance, charge to it using the charge mode of single cathode, double anodes, meanwhile, perpendicular to electricity
Flow perturbation is sent into the top for solving liquid level.
5. a kind of product that claim 1 ~ 4 any one of them graphene is prepared with the compound method of conducting fibre.
6. product according to claim 5, it is characterised in that：The thickness control of composite membrane is within 45 microns, film stretching
Intensity is up to 3.0 more than GPa.
7. a kind of preparation method of graphene, conducting fibre and multi-stage porous carbon composite material, it is characterised in that：First by graphite
Alkene is compound with conducting fibre, and complex method is carried out according to claim 1 ~ 4 any one of them method, treats graphene and conduction
Property fiber composite membrane drying after, the mixed slurry containing graphene, activated carbon charcoal source and chemical activating agent is coated uniformly on
Two surfaces of the composite membrane, be finally dried, activate, pickling, washing.
8. the preparation method of graphene according to claim 7, conducting fibre and multi-stage porous carbon composite material, feature
It is：The activated carbon charcoal source includes at least one of microcrystalline cellulose, sodium carboxymethylcellulose, pitch, catkin；Describedization
Learning activator is：NaOH、KOH、ZnCl2、CaCl2At least one of.
9. the preparation method of graphene according to claim 7, conducting fibre and multi-stage porous carbon composite material, feature
It is：The preparation process of the mixed slurry includes：
（1）Graphene and activated carbon charcoal source are uniformly mixed into 10 ~ 14 h, are then centrifuged for washing repeatedly, 60 ~ 80 DEG C of vacuum
Then drying removes extra chemical activating agent with centrifugation after 20 ~ 28 h of chemical activating agent immersion of 5 ~ 9 mol/L；
（2）Hydro-thermal process will be carried out up to graphene-work containing the mixed slurry of graphene-activated carbon charcoal source-chemical activating agent
The mixed slurry of property charcoal charcoal source-chemical activating agent three.
10. the preparation method of graphene according to claim 9, conducting fibre and multi-stage porous carbon composite material, special
Sign is：The graphene and the mass ratio in activated carbon charcoal source are：4 ~35 :100；The hydrothermal conditions are：150~190
4 ~ 8 h of hydro-thermal process in DEG C baking oven.
11. the preparation method of graphene according to claim 7, conducting fibre and multi-stage porous carbon composite material, special
Sign is：The mixed slurry is applied directly to uniform graphene/conducting fibre composite membrane both side surface, and mixed slurry applies
It overlays on graphene/conducting fibre composite membrane after drying, activated carbon is obtained by chemical activation mode.
12. the preparation method of graphene according to claim 11, conducting fibre and multi-stage porous carbon composite material, special
Sign is：The chemical activation mode is：Dried is attached with the compound of graphene-activated carbon charcoal source-chemical activating agent
Film is put into high temperature process furnances, and 500 ~ 650 DEG C of 0.5 ~ 1.5 h of activation are to get to graphene-activated carbon-conduction under Ar protections
Property composite fiber membrane.
13. the preparation method of graphene according to claim 7, conducting fibre and multi-stage porous carbon composite material, special
Sign is：The pickling, water-washing process are by the HCl of graphene-activated carbon -0.1 ~ 0.5 mol/L of carbon based fibers composite membrane
Washed with deionized water, first carry out HCl and wash, be then washed with water until pH is 7, obtained after dry graphene, conducting fibre and
Multi-stage porous carbon composite material.
14. a kind of preparation of claim 7 ~ 13 any one of them graphene, conducting fibre and multi-stage porous carbon composite material
The product that method is prepared.
15. product according to claim 14, it is characterised in that：The tensile strength of product is 3.0 more than GPa, specific surface
Product is 800 m2/ more than g, the specific capacitance of ultracapacitor can be up to 144 F/g made of the product.
16. a kind of application of the product described in claim 14 in ultracapacitor.
17. application according to claim 16, it is characterised in that：The preparation method of the ultracapacitor is：By graphite
Alkene, conducting fibre and multi-stage porous carbon composite material are punched into the disk of a diameter of 9 mm, then use " sandwich " structure, will
Carbon composite-membrane-carbon composite layer assembly, is finally putting into homemade cylindrical die, and electrolyte encapsulation is added dropwise.
18. a kind of application of the product in ultralight amount automobile described in claim 14.
19. application according to claim 18, it is characterised in that：Graphene, conducting fibre and multi-stage porous carbon is compound
Material applies the concrete mode in ultralight amount automobile to be：By made graphene, conducting fibre and multi-stage porous carbon composite material
It is laid with layer by layer, is assembled into flexible super capacitor, which has the function of antidetonation, places in molding die, carries out
Preforming processing；Then apply in ultralight amount automobile, formed with graphene, conducting fibre and multi-stage porous carbon composite material
Flexible capacitor is as automobile body covering piece.
20. application according to claim 19, it is characterised in that：The body outer skin includes：Front hatch cover, head cover, after
One or more of hatchcover, left and right gusset.
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