CN106847534A - A kind of preparation method of Graphene/absorbent charcoal composite material, Graphene/active carbon combined electrode piece and ultracapacitor - Google Patents
A kind of preparation method of Graphene/absorbent charcoal composite material, Graphene/active carbon combined electrode piece and ultracapacitor Download PDFInfo
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- CN106847534A CN106847534A CN201611164241.5A CN201611164241A CN106847534A CN 106847534 A CN106847534 A CN 106847534A CN 201611164241 A CN201611164241 A CN 201611164241A CN 106847534 A CN106847534 A CN 106847534A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Present invention relates particularly to a kind of preparation method of Graphene/absorbent charcoal composite material, Graphene/active carbon combined electrode piece and ultracapacitor, belong to ultracapacitor energy storage device arts.Comprise the following steps：Activated carbon is carried out into acid treatment；Graphene oxide is dissolved in solvent, then condensation reaction occurs with polymer and obtain the positively charged graphene oxide colloid in surface；By the activated carbon (2 20%) in mass ratio after graphene oxide colloid and acid treatment：(80 98%) mix, and ultrasonic disperse, graphene oxide is formed by electrostatic self-assembled technology and coats absorbent charcoal composite material slurry, slurry drying is obtained into reduced graphene/absorbent charcoal composite material powder；By powder in reducing atmosphere, heat treatment obtains Graphene/absorbent charcoal composite material in 28 hours under conditions of 800 1600 DEG C.Graphene of the invention/absorbent charcoal composite material density is high, high pressure resistant, and electrode density is high, electrode volume energy density.
Description
Technical field
Present invention relates particularly to a kind of preparation method of Graphene/absorbent charcoal composite material, Graphene/activated carbon compound electric
Pole piece and ultracapacitor, belong to the new energy energy storage device technical field such as ultracapacitor.
Background technology
Ultracapacitor have power density high, can fast charging and discharging, million rank long circulation lifes, remarkable low
Warm nature can and the characteristic such as safe and reliable, be widely used in the fields such as the traffic of city common-rail, hybrid vehicle.But mesh
Preceding super capacitor energy density is relatively low, commercial activated carbon super capacitor energy density only 5-7Wh/kg.In order to meet constantly
The demand of growth, develops high-energy-density and power density, and macrocyclic ultracapacitor is the skill for being badly in need of solving at present
Art problem.
Activated carbon because its density it is high, it is cheap be the currently the only electrode material for obtaining commercial applications.But activated carbon
Poorly conductive, influences utilization rate of its power density, high rate performance and electrode material etc..The specific surface area of Graphene Yin Qigao
(2630m2/ g), excellent electric conductivity (106S/m) and the characteristic such as two-dimension flexible structure, ultracapacitor is applied to, it takes into account and leads
Electricity and energy storage double grading, it is considered to be a kind of excellent electrode material.In actual applications, it is typically special using Graphene
Two-dimension flexible structure and ion high and electronic conduction ability it is compound with activated carbon improving its capacity, cycle characteristics and big electricity
Banish electrical characteristics etc..
But, graphite alkenes carbon nanomaterial porosity is high and density is very low, and the introducing of Graphene can be reduced in activated carbon
Electrode density, also resulting in inside combination electrode has substantial amounts of space to be filled by electrolyte, increase only device weight and simultaneously
Capacity is not contributed, the performance of integral device has been dragged down, it is difficult to the excellent properties of Graphene are embodied onto final device.This
Outward, the usual chemical constitution of graphenic surface is complicated, and under high potential, its surface impurity is mutually easy to induce side reaction, and then influences
The chemical property of device.
The content of the invention
The purpose of the present invention is directed to the above-mentioned problems in the prior art, there is provided a kind of high density, high voltage bearing stone
The preparation method of black alkene/absorbent charcoal composite material.
In order to reach foregoing invention purpose, the present invention uses following technical scheme：A kind of high-density graphite alkene/activated carbon is multiple
The preparation method of condensation material, described preparation method is comprised the following steps：
S1, activated carbon is carried out into acid treatment；
S2, graphene oxide is first dissolved in solvent, then condensation reaction occurs with polymer obtaining the positively charged oxidation in surface
Graphene colloid；
S3, by the activated carbon after graphene oxide colloid and acid treatment (2-20%) in mass ratio：(80-98%) is uniformly mixed
Close, then first ultrasonic disperse, then graphene oxide is formed by electrostatic self-assembled technology and coat absorbent charcoal composite material slurry, will
Slurry drying obtains reduced graphene/absorbent charcoal composite material powder；
S4, by graphene oxide coat absorbent charcoal composite material powder in reducing atmosphere, in 800-1600 DEG C of bar
Heat treatment obtains Graphene/absorbent charcoal composite material in 2-8 hours under part.
The present invention prepares graphene oxide and coats absorbent charcoal composite material by electrostatic self-assembled technology first, then uses
Solvent contraction technology prepares high-density graphite alkene/active carbon combined electrode piece.Graphene oxide has special flexible characteristic,
Monolayer Dispersion can be realized in solution, the oxygen-containing functional group such as the abundant epoxy radicals in its surface, hydroxyl, carbonyl and carboxyl has very strong
Chemism, it is prone to which the covalent bond such as condensation reaction is modified, so as to realize the regulation and control of its surface electrochemistry.Graphene oxide
Make its surface positively charged by covalent bond modification, graphite oxide is obtained by electrostatic self-assembled effect with the activated carbon after acidifying
Alkene uniformly coats absorbent charcoal composite material, and three-dimensional conductive network is constructed with " surface-to-surface " way of contact.Then mixed slurry is through overdrying
Dry treatment obtains reduced graphene/absorbent charcoal composite material, with the volatilization of solvent in drying process, in the effect of surface tension
Under, the flexible graphene oxide outside activated carbon granule is wrapped in contract, so as to cause the same of three-dimensional grapheme conductive network
Step is shunk.After its internal substantial amounts of solvent volatilization, hole is drastically shunk, Graphene high crimp dense arrangement, and its volume is acute
Subtract, density is substantially improved, form the Graphene/absorbent charcoal composite material of densification.Again because of the presence of activated carbon granule, and
The fold crimp properties of Graphene, cause graphene sheet layer infinitely to shrink, so as to ensure that the preservation of original porous channel,
The specific surface area of integral material is not reduced, and what is obtained is the porous complex carbon material of high density with micropore and mesopore.
Secondly, high-temperature heat treatment is carried out to densification Graphene/absorbent charcoal composite material in reducing atmosphere, is effectively gone
Except surface functional group, and then lift the voltage endurance capability and its stability of ultracapacitor.
Activated carbon described in step S1 selects commercial commercially available high power capacity activated carbon, and specific surface area is 1800-2000m2/ g,
7-10 μm of grain diameter.
Acid treatment described in step S1 is that in the acid solution of 10-30%, reflow treatment 0.5-4 is small at 60-120 DEG C
When, then through filtering, cleaning, dry.If activated carbon acid treatment degree is too high, the excessive impurity oxygen-containing functional group of its surface graft,
These functional groups are unfavorable for the performance of activated carbon based super capacitor.Concentration, counterflow condition of the present invention by acid solution
Control realization activated carbon surface acid treatment degree regulation and control.
Described acid solution is one or more in nitric acid, sulfuric acid, acetic acid, phosphoric acid.Preferably, described acid solution
It is nitric acid, the concentration of nitric acid is 10-30%.Further preferably, the reflux temperature in acid treatment is 60-80 DEG C, return time 1-2
Hour, concentration of nitric acid is 12-18%.
The individual layer rate of the graphene oxide described in step S2>90%, 5-15 μm of lamella size, oxygen content 40-60%.Oxygen
The selection of graphite alkene is particularly critical, individual layer rate, lamella magnitude relationship graphene oxide high-specific surface area, it is special it is flexible,
It is easy to the features such as covalent bond modification.The graphene oxide number of plies is too many, can influence the specific surface of Graphene/absorbent charcoal composite material
Product；Lamella is too big or too small, it is difficult to form the composite construction of uniform cladding；The oxygen content destruction to graphene-structured too high is tight
Weight, electric conductivity is deteriorated, and oxygen content is too low, and lamella is typically thicker.Preferably, the individual layer rate of graphene oxide>95%, lamella is big
It is small 7-10 μm, oxygen content 50%.
Solvent described in step S2 is water, ethanol, methyl alcohol, ethylene glycol, toluene, tetrahydrofuran, dimethylformamide, N-
One or more in N-methyl pyrrolidines, carbon tetrachloride.In drying process, by solvent contraction technology lifted Graphene/
The density of absorbent charcoal composite material, the capillarity of solvent has played key effect, and capillarity size is opened with the surface of solvent
Power size direct correlation, solvent surface tension influences final densification effect.The surface tension of above-mentioned solvent reclaimed water is maximum, causes
Densification most pronounced effects, other solvents take second place.Densified materials will take into account the equilibrium relation between density, aperture, specific surface area, institute
It is water and/or ethanol as preferred, described solvent.
Polymer described in step S2 accounts for the 3-10% of graphene oxide mass fraction, and described polymer is DOPA
Amine, ethylenediamine, polydimethylacrylamiin (PDMA), PolyEtherImide (PEI), diallyl dimethyl amine hydrochlorate
(PDDA), one or more in 2,5- dimercaptos -134- thiadiazoles (DMCT).Graphene oxide in the present invention by with tool
There is condensation reaction and realize that covalent bond is modified in the polymer for having the positively charged class of Amino End Group or hydroxyl, make surface of graphene oxide band
Positive charge.Graphene oxide covalent bond modification be carboxyl, hydroxyl by the use of graphene oxide as reaction site, by additional tool
There is the polymeric reagent of the positively charged of Amino End Group or hydroxyl, realize that covalent bond is modified by condensation reaction, make graphene oxide table
Face is positively charged.Preferably, the positively charged polymeric reagent is polydimethylacrylamiin (PEI).
Because the amount of oxidation of graphene oxide is 50%, weightless about 50% after thermal reduction, so present invention oxidation stone
The mass ratio of activated carbon is (2-20%) after black alkene colloid and acidifying：(80-98%), during its final Graphene/activated carbon is compound
The mass ratio of the two is about (1-10%)：(90-99%).
Dry temperature described in step S3 is 40-300 DEG C.Drying temperature influences dry efficiency and densification effect,
Temperature it is higher, it is necessary to time it is shorter, densification effect it is better, otherwise conversely.Preferably, the dry temperature is 60-
150℃。
Reducibility gas described in step S4 are H2、CO、SO2、NO2、NO、NH3、H2One kind or many in S, HBr, HI
Kind.In above-mentioned reducibility gas atmosphere, after high-temperature heat treatment, Graphene/absorbent charcoal composite material surface functional group is had
The removal of effect.Preferably, described reducibility gas are H2。
The temperature being heat-treated described in step S4 is 900-1300 DEG C, and heat treatment time is 2-5 hours.In certain limit,
Heat treatment temperature is higher, surface functional group removal effect it is more obvious, it is necessary to heat treatment time relative can reduce, and then improve table
Face functional group removal efficiency.Preferably, the temperature of the heat treatment is 1000-1200 DEG C, heat treatment time is 2-4 hours.
Second object of the present invention is to provide a kind of Graphene/active carbon combined electrode piece, by above-mentioned Graphene/work
Property carbon composite and bonding agent (85-95%) in mass ratio：(5-15%) mixes, and rolls to be formed by two steps after high speed shear
Carbon film；Carbon film is pasted together with collector by conducting resinl again, is heating and curing prepared.
Electrode slice of the invention using highdensity Graphene/absorbent charcoal composite material and with dry method electrode machining technology,
Mode is rolled by vertically and horizontally two steps and further improve electrode density, further improve the continuity of electrode slice, uniform
Property and high density characteristic.
Composite uses the one kind in hypervelocity shearing, air-flow crushing mixing, ball milling, mechanical agitation with the mixing of bonding agent
Or it is various.Preferably, using hypervelocity shear-mixed mode in the present invention.
The pressure for rolling is 100-300MPa, rolls and is rolled with level including vertical rolling.Pressure in the present invention
Size influence thickness, density and the density of final carbon film.If pressure is too small, carbon film void is larger, and density is relatively low, pole piece
It is thicker；Reverse pressure is too big, and carbon film fold even ftractures.Preferably, the pressure for rolling is 120-250MPa.Enter one again
Step is preferred, and the pressure for rolling is 150MPa.
Described bonding agent is Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE), butadiene-styrene rubber (SBR), carboxymethyl
Sodium cellulosate (CMC), polyvinylpyrrolidone (PVP), Kynoar-hexafluoropropene (PVDF-HFP), PVP- polyvinyl alcohol
One or more in butyral (PVP-PVB), native cellulose, PVDF-HFP/PVP.Preferably, described bonding agent is
PTFE.Because PTFE has good linear deformation mode, preferred PTFE makees good in dry process electrode process of the present invention
Good bonding agent.
Described conducting resinl is conducting resinl common in the prior art.
The temperature being heating and curing is 100-200 DEG C, and the time being heating and curing is 10-30min.
The surface density of obtained Graphene/active carbon combined electrode piece is 0.75-0.95g/cm3, thickness is 100-300 μ
m.If the density of compound electric pole piece is too small, the quality of the powder of the Graphene/activated carbon of filling is fewer in unit volume, unit
The energy of storage is fewer in volume, therefore obtained ultracapacitor device is just very big, is unfavorable for vehicle-mounted use.Present invention system
Graphene/active carbon combined electrode piece the density for obtaining is high, and using in the capacitor, the volume energy density of capacitor monomer is high.
And if the blocked up utilization rate that can influence material of compound electric pole piece, if compound electric pole piece is excessively thin, need more aluminum foil current collectors,
Reduce the energy density of integral device.Preferably, the thickness of the Activated Graphite alkene/active carbon combined electrode piece is 200-
230μm.Further preferably, the thickness of the Graphene/active carbon combined electrode piece is 200 μm.
Present invention also offers a kind of ultracapacitor, including Graphene/activated carbon obtained in above-mentioned preparation method is compound
The Graphene that material is made/active carbon combined electrode piece.
Compared with prior art, the preparation method of Graphene/absorbent charcoal composite material of the present invention is first by electrostatic from group
Dress technology prepares graphene coated absorbent charcoal composite material；Then composite is densified by solvent contraction technology,
The structure control of composite is densified by the control realization of shrinking solvent, drying condition；Pass through high-temperature heat treatment technology again
Effectively removal composite material surface functional group, improves density, high-voltage resistance capability and its stability of material.Pass through dry method electrode again
Process technology is processed into electrode slice, further lifts electrode density, improves the volume energy density of electrode, and the electrode slice has pole
Strong actual application value.
Brief description of the drawings
Fig. 1 is the electron-microscope scanning figure of Graphene/absorbent charcoal composite material in the embodiment of the present invention 1.
Fig. 2 is the electronic photo that carbon film is formed after 8 liang of steps of the embodiment of the present invention are rolled.
Specific embodiment
It is described with reference to the drawings the following is specific embodiment of the invention, technical scheme is made further to retouch
State, but the present invention is not limited to these embodiments.
Embodiment 1
It is 1800-2000m by specific surface area2/ g, the activated carbon of 7-10 μm of grain diameter is dispersed in 15% nitric acid
In solution, reflow treatment 1.5 hours at 80 DEG C, then through filtering, cleaning, being dried to obtain the activated carbon of acid treatment.
Configuration 1mg/mL graphene oxides, the mixed solution of second alcohol and water, the individual layer rate of graphene oxide>95%, lamella
7-10 μm of size, oxygen content 50%, the volume ratio of second alcohol and water is 5:5.Graphene oxide quality is accounted for addition in above-mentioned solution
The polydimethylacrylamiin (PEI) of the 7% of fraction, is stirred at room temperature reaction and obtains within 2 hours graphene oxide PEI and covalently repair
The colloidal solution of decorations.
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 10% by solid masses：90% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 120 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere H2In, at 1000 DEG C
Under conditions of heat treatment obtain Graphene/absorbent charcoal composite material within 4 hours.By obtained Graphene/activated carbon in the embodiment
Composite carries out electron-microscope scanning, and electron-microscope scanning figure is as shown in Figure 1.As seen from the figure, after solvent shrinks, random activity
Charcoal primary particle is agglomerated into 50 μm or so of spherical second particle, and the graphene platelet of fold is coated on the table of activated carbon granule
Face, forms fine and close composite.
Embodiment 2
It is 1800-2000m by specific surface area2/ g, the activated carbon of 7-10 μm of grain diameter is dispersed in 20% nitric acid
In solution, reflow treatment 1 hour at 70 DEG C, then through filtering, cleaning, being dried to obtain the activated carbon of acid treatment.
Configuration 1mg/mL graphene oxides, the mixed solution of second alcohol and water, the individual layer rate of described graphene oxide>
95%, 7-10 μm of lamella size, oxygen content 50%, the volume ratio of second alcohol and water is 4:6.Oxidation stone is accounted for addition in above-mentioned solution
The polydimethylacrylamiin (PEI) of the 5% of black alkene mass fraction, is stirred at room temperature reaction and obtains graphene oxide in 2 hours
The colloidal solution of PEI covalent modifications；
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 15% by solid masses：85% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 100 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere H2In, at 1200 DEG C
Under conditions of heat treatment obtain Graphene/absorbent charcoal composite material within 2 hours.
Embodiment 3
It is 1800-2000m by specific surface area2/ g, the activated carbon of 7-10 μm of grain diameter is dispersed in 25% sulfuric acid
In solution, in 60 times reflow treatments 2 hours, then through filtering, cleaning, being dried to obtain the activated carbon of acid treatment.
1mg/mL graphene oxides are molten and the mixed solution of water for configuration, the individual layer rate of described graphene oxide>95%, piece
7-10 μm of size of layer, oxygen content 50%.The 6% of graphene oxide mass fraction polydiene propyl group is accounted for addition in above-mentioned solution
Dimethylamine hydrochloride (PDDA), be stirred at room temperature reaction obtain within 2 hours graphene oxide PDDA covalent modifications colloid it is molten
Liquid.
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 5% by solid masses：95% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 150 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere CO, at 1100 DEG C
Under conditions of heat treatment obtain Graphene/absorbent charcoal composite material within 2 hours.
Embodiment 4
It is 1800-2000m by specific surface area2/ g, the activated carbon of 7-10 μm of grain diameter is dispersed in 12% acetic acid
In solution, reflow treatment 3 hours at 90 DEG C, then through filtering, cleaning, being dried to obtain the activated carbon of acid treatment.
Configure the mixed solution of 1mg/mL graphene oxide ethanol, the individual layer rate of described graphene oxide>90%, lamella
5-15 μm of size, oxygen content 50%,.The 9% of graphene oxide mass fraction dimethyl allene is accounted for addition in above-mentioned solution
Acid amides (PDMA), is stirred at room temperature the colloidal solution that reaction obtains graphene oxide PDMA covalent modifications for 2 hours.
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 8% by solid masses：92% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 60 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere NO2In, at 950 DEG C
Under conditions of heat treatment obtain Graphene/absorbent charcoal composite material within 5 hours.
Embodiment 5
It is 1800-2000m by specific surface area2/ g, the activated carbon of 7-10 μm of grain diameter is dispersed in 28% nitric acid
In solution, reflow treatment 2.5 hours at 100 DEG C, then through filtering, cleaning, being dried to obtain the activated carbon of acid treatment.
The mixed solution of configuration 1mg/mL graphene oxides and N- N-methyl pyrrolidines, the individual layer of described graphene oxide
Rate>95%, 7-10 μm of lamella size, oxygen content 50%.The 4% of graphene oxide mass fraction is accounted for addition in above-mentioned solution
Ethylenediamine, is stirred at room temperature the colloidal solution that reaction obtains graphene oxide ethylenediamine covalent modification for 2 hours.
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 18% by solid masses：82% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 80 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere NH3In, 1250
Heat treatment obtains Graphene/absorbent charcoal composite material in 3 hours under conditions of DEG C.
Embodiment 6
It is 1800-2000m by specific surface area2/ g, the activated carbon of 7-10 μm of grain diameter is dispersed in 10% phosphoric acid
In solution, reflow treatment 0.5 hour at 120 DEG C, then through filtering, cleaning, being dried to obtain the activated carbon of acid treatment.
The mixed solution of configuration 1mg/mL graphene oxides and tetrahydrofuran, the individual layer rate of described graphene oxide>
90%, 5-15 μm of lamella size, oxygen content 50%.The 2 of the 3% of graphene oxide mass fraction are accounted for addition in above-mentioned solution,
5- dimercapto -134- thiadiazoles (DMCT), is stirred at room temperature the glue that reaction obtains graphene oxide DMCT covalent modifications for 2 hours
Liquid solution.
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 20% by solid masses：80% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 300 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere HBr, at 800 DEG C
Under conditions of heat treatment obtain Graphene/absorbent charcoal composite material within 8 hours.
Embodiment 7
Activated carbon is dispersed in the acid solution of 10-30%, reflow treatment 0.5-4 hours at 60-120 DEG C, then
Through the activated carbon for filtering, cleaning, be dried to obtain acid treatment.The specific surface area of activated carbon is 1800-2000m2/ g, grain diameter 7-
10μm；Acid solution is one or more in nitric acid, sulfuric acid, acetic acid, phosphoric acid.Reflux temperature in acid treatment is 60-80 DEG C, is returned
1-2 hours stream time, concentration of nitric acid is 12-18%.
The mixed solution of configuration 1mg/mL graphene oxides and toluene, the individual layer rate of described graphene oxide>90%, piece
5-15 μm of size of layer, oxygen content 50%.The 10% of graphene oxide mass fraction dopamine is accounted for addition in above-mentioned solution,
Stirring reaction obtains the colloidal solution of graphene oxide dopamine covalent modification for 2 hours at room temperature.
Activated carbon after modified graphene oxide colloidal solution and acidifying is compared 2% by solid masses：98% is uniform mixed
Close, ultrasonic disperse 2 hours, act on forming the slurry that graphene oxide coats absorbent charcoal composite material in electrostatic self-assembled；Then
Above-mentioned slurry is dried to obtain reduced graphene/absorbent charcoal composite material powder under conditions of 40 DEG C.
Reduced graphene/absorbent charcoal composite material powder is placed in tube furnace, in reducing atmosphere H2In, at 1600 DEG C
Under conditions of heat treatment obtain Graphene/absorbent charcoal composite material within 2 hours.
Embodiment 8
Obtained Graphene/absorbent charcoal composite material in embodiment 1 and bonding agent polytetrafluoroethylene (PTFE) (PTFE) are pressed into quality
Than 90%：10% mixing, rolls to form carbon film after high speed shear by two steps, and the pressure for rolling is 200MPa, rolls including hanging down
Straight rolling is rolled with level；Carbon film is pasted together with collector by conducting resinl again, be heating and curing 20min at 150 DEG C
Graphene/active carbon combined electrode piece is obtained, the surface density of the Graphene/active carbon combined electrode piece is 0.93g/cm3, thickness
It is 200 μm.The electronic photo that carbon film is formed after two steps are rolled in the embodiment is as shown in Figure 2.
Embodiment 9
Obtained Graphene/absorbent charcoal composite material in embodiment 2 and bonding agent Kynoar (PVDF) are pressed into quality
Than 88%：12% mixing, rolls to form carbon film after high speed shear by two steps, and the pressure for rolling is 180MPa, rolls including hanging down
Straight rolling is rolled with level；Carbon film is pasted together with collector by conducting resinl again, be heating and curing 25min at 140 DEG C
Graphene/active carbon combined electrode piece is obtained, the surface density of the Graphene/active carbon combined electrode piece is 0.90g/cm3, thickness
It is 220 μm.
Embodiment 10
By obtained Graphene/absorbent charcoal composite material in embodiment 3 and bonding agent butadiene-styrene rubber (SBR) in mass ratio
92%：8% mixing, rolls to form carbon film after high speed shear by two steps, and the pressure for rolling is 220MPa, rolls including vertical stone roller
Pressure and level are rolled；Carbon film is pasted together with collector by conducting resinl again, the 15min that is heating and curing at 160 DEG C is obtained
Graphene/active carbon combined electrode piece, the surface density of the Graphene/active carbon combined electrode piece is 0.90g/cm3, thickness is
230μm。
Embodiment 11
Obtained Graphene/absorbent charcoal composite material in embodiment 4 and bonding agent sodium carboxymethylcellulose (CMC) are pressed into matter
Amount compares 86%：14% mixing, roll to form carbon film by two steps after high speed shear, the pressure for rolling be 120MPa, roll including
Vertical rolling is rolled with level；Carbon film is pasted together with collector by conducting resinl again, is heating and curing at 120 DEG C
12min is obtained Graphene/active carbon combined electrode piece, and the surface density of the Graphene/active carbon combined electrode piece is 0.89g/
cm3, thickness is 250 μm.
Embodiment 12
By obtained Graphene/absorbent charcoal composite material in embodiment 5 and bonding agent Kynoar-hexafluoropropene
(PVDF-HFP) in mass ratio 94%：6% mixing, rolls to form carbon film after high speed shear by two steps, and the pressure for rolling is
250MPa, rolls and is rolled with level including vertical rolling；Carbon film is pasted together with collector by conducting resinl again, 180
The 22min that is heating and curing at DEG C is obtained Graphene/active carbon combined electrode piece, and the face of the Graphene/active carbon combined electrode piece is close
It is 0.92g/cm to spend3, thickness is 150 μm.
Embodiment 13
By obtained Graphene/absorbent charcoal composite material in embodiment 6 and bonding agent PVP- polyvinyl butyral resins (PVP-
PVB) in mass ratio 95%：5% mixing, rolls to form carbon film after high speed shear by two steps, and the pressure for rolling is 300MPa, is ground
Briquetting includes vertical rolling and is rolled with level；Carbon film is pasted together with collector by conducting resinl again, is heated at 200 DEG C solid
Change 10min and Graphene/active carbon combined electrode piece is obtained, the surface density of the Graphene/active carbon combined electrode piece is 0.85g/
cm3, thickness is 100 μm.
Embodiment 14
By obtained Graphene/absorbent charcoal composite material in embodiment 7 and bonding agent native cellulose in mass ratio 85：
15% mixing, rolls to form carbon film after high speed shear by two steps, and the pressure for rolling is 100MPa, roll including it is vertical roll with
Level is rolled；Carbon film is pasted together with collector by conducting resinl again, the 30min that is heating and curing at 100 DEG C is obtained graphite
Alkene/active carbon combined electrode piece, the surface density of the Graphene/active carbon combined electrode piece is 082g/cm3, thickness is 300 μm.
Embodiment 15-21
A kind of ultracapacitor, respectively including the Graphene in embodiment 8-14/active carbon combined electrode piece.
In the above-described embodiments, the mode of the mixing can be in ball milling, air-flow mixing, mechanical agitation, hypervelocity shearing
One or more；Described conducting resinl is conducting resinl common in the prior art.
In addition, claimed technical scope midrange non-limit part and in embodiment technical scheme it is right
The new technical scheme that the equal replacement of single or multiple technical characteristics is formed, equally all in claimed model
In enclosing；Simultaneously the present invention program it is all enumerate or unrequited embodiment in, parameters in the same embodiment are only
Represent an example (i.e. a kind of feasible scheme) of its technical scheme.
Specific embodiment described herein is only to the spiritual explanation for example of the present invention.Technology neck belonging to of the invention
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be substituted using similar mode, but simultaneously
Do not deviate by spirit of the invention or surmount scope defined in appended claims.
It is skilled to this area although having made a detailed description and being cited some specific embodiments to the present invention
For technical staff, as long as it is obvious that can be made various changes without departing from the spirit and scope of the present invention or corrected.
Claims (10)
1. a kind of preparation method of Graphene/absorbent charcoal composite material, it is characterised in that described preparation method includes following step
Suddenly：
S1, activated carbon is carried out into acid treatment；
S2, graphene oxide is first dissolved in solvent, then condensation reaction occurs with polymer obtaining the positively charged graphite oxide in surface
Alkene colloid；
S3, by the activated carbon after graphene oxide colloid and acid treatment (2-20%) in mass ratio：(80-98%) uniformly mixes,
Then first ultrasonic disperse, then graphene oxide is formed by electrostatic self-assembled technology coat absorbent charcoal composite material slurry, will starch
Dry the reduced graphene/absorbent charcoal composite material powder of material；
S4, by graphene oxide coat absorbent charcoal composite material powder in reducing atmosphere, under conditions of 800-1600 DEG C
Heat treatment obtains Graphene/absorbent charcoal composite material in 2-8 hours.
2. the preparation method of Graphene/absorbent charcoal composite material according to claim 1, it is characterised in that in step S1
The specific surface area of described activated carbon is 1800-2000m2/ g, 7-10 μm of grain diameter；Graphene oxide described in step S2
Individual layer rate>90%, 5-15 μm of lamella size, oxygen content 40-60%.
3. the preparation method of Graphene/absorbent charcoal composite material according to claim 1, it is characterised in that in step S1
Described acid treatment is in the acid solution of 10-30%, reflow treatment 0.5-4 hours at 60-120 DEG C, then through filtering, clear
Wash, dry, described acid solution is one or more in nitric acid, sulfuric acid, acetic acid, phosphoric acid.
4. the preparation method of Graphene/absorbent charcoal composite material according to claim 1, it is characterised in that in step S2
Described solvent is water, ethanol, methyl alcohol, ethylene glycol, toluene, tetrahydrofuran, dimethylformamide, N- N-methyls pyrrolidines, four
One or more in chlorination carbon, dry temperature described in step S3 is 40-300 DEG C.
5. the preparation method of Graphene/absorbent charcoal composite material according to claim 1, it is characterised in that in step S2
Described polymer accounts for the 3-10% of graphene oxide mass fraction, and described polymer is dopamine, ethylenediamine, poly dimethyl
Acrylamide (PDMA), PolyEtherImide (PEI), diallyl dimethyl amine hydrochlorate (PDDA), 2,5- dimercaptos -134-
One or more in thiadiazoles (DMCT).
6. the preparation method of Graphene/absorbent charcoal composite material according to claim 1, it is characterised in that in step S4
Described reducibility gas are H2、CO、SO2、NO2、NO、NH3、H2One or more in S, HBr, HI, heat described in step S4
The temperature for the treatment of is 900-1300 DEG C, and heat treatment time is 2-5 hours.
7. a kind of Graphene/active carbon combined electrode piece, it is characterised in that by Graphene/activated carbon as claimed in claim 1
Composite and bonding agent (85-95%) in mass ratio：(5-15%) mixes, and rolls to form carbon by two steps after high speed shear
Film；Carbon film is pasted together with collector by conducting resinl again, is heating and curing prepared.
8. Graphene according to claim 7/active carbon combined electrode piece, it is characterised in that the pressure that rolls is
100-300MPa, rolls and is rolled with level including vertical rolling；The temperature being heating and curing is 100-200 DEG C, is heating and curing
Time be 10-30min.
9. Graphene according to claim 7/active carbon combined electrode piece, it is characterised in that Graphene/activated carbon is combined
The surface density of electrode slice is 0.75-0.95g/cm3, thickness is 100-300 μm.
10. a kind of ultracapacitor, it is characterised in that including Graphene/active carbon combined electrode piece.
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