CN104240964B - Method for achieving in situ composition of graphene and activated carbon through supercutical fluid - Google Patents
Method for achieving in situ composition of graphene and activated carbon through supercutical fluid Download PDFInfo
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Abstract
The invention relates to a method for achieving in situ composition of graphene and activated carbon through supercutical fluid. According to the method, intercalation is conducted on graphite through the supercutical fluid, and then the activated carbon is added; secondary activation is conducted on the activated carbon through the supercutical fluid and the activated carbon is completely mixed with the expanded graphite generated after the intercalation is conducted, then the mixed material is ejected to a high-temperature normal-pressure thermal decomposition furnace in a single-point or multi-point oppositely-ejecting mode, and the expanded graphite generated after the intercalation is conducted can be stripped to be graphene through rapid decompression under the high-temperature thermal environment; the graphene is composited with the activated carbon generated after the secondary activation is conducted in real time in the multiphase flow ejection process, and the composite material of the graphene evenly dispersed in the secondary activation activated carbon is prepared. Compared with the prior art, the problem that the graphene is extremely easy to cluster, the graphene is made to be evenly mixed with the super activated carbon, so that the super activated carbon composite material is obtained through graphene in situ modification.
Description
Technical field
The invention belongs to functional material preparing technical field, especially relate to one kind and realize Graphene using supercritical fluid
The method of In-situ reaction activated carbon.
Background technology
Activated carbon has high volumetric surface area, low cost, the features such as good with electrolyte compatibility, is most widely used
Electrode material for super capacitor.But at present, conventional carbon-based material has that electric conductivity is poor, thermal diffusivity is low, specific surface area is less
The problems such as it is impossible to the energy storage meeting ultracapacitor requires, define industry bottleneck.
Graphene is carbon atom with the tightly packed cellular Colloidal particles carbon nanometer material of sp2 hybrid systems
Material.Because Graphene has the two-dimensional structure of uniqueness, the ratio table of excellent electric conductivity, outstanding mechanics and thermal property, super large
Area and open surface, are conducive to the formation at electrode material/electrolyte electric double layer interface so that graphene-based material is super
Application in level capacitor has great potentiality.Build tridimensional network using Graphene between activated carbon granule, no
It is only capable of improving the specific surface area of activated carbon, also help reduction migration resistance in hole for the ion, improve ultracapacitor
Heat dispersion.
Although Graphene has excellent performance, still suffer from bottleneck, the twice dispersing of graphene powder in use
It is the topmost limiting factor of restriction Graphene large-scale use with Cost Problems.The system of existing Graphene in the market
Preparation Method mainly has oxidation-reduction method and chemical vapour deposition technique etc., but the graphene powder that above method obtains is using process
In be all difficult to again disperse, lead to active material phase be combined after performance boost inconspicuous.And, above method is batch (-type)
Produce, not only product quality concordance is difficult to ensure, and preparation cost is high, expensive.
Content of the invention
The purpose of the present invention is exactly to overcome the defect of above-mentioned prior art presence to provide one kind to improve activated carbon
Conduction, heat conductivility, the utilization supercritical fluid effectively enhancing the specific surface area of activated carbon realizes Graphene In-situ reaction
The method of activated carbon, the novel graphite alkene/absorbent charcoal composite material preparing is particularly suitable as the electrode of ultracapacitor
Material, will effectively improve the comprehensive of ultracapacitor.
The purpose of the present invention can be achieved through the following technical solutions：
The method realizing Graphene In-situ reaction activated carbon using supercritical fluid, is carried out to graphite using supercritical fluid
Intercalation, is subsequently adding activated carbon, using supercritical fluid, activated carbon is carried out with re-activation and fills with the expanded graphite after intercalation
After point mixing, mixed material is ejected in high-temperature pressure pyrolysis oven in the form of single-point or multiple spot are to spray, quick pressure releasing and high temperature
Expanded graphite after thermal environment makes intercalation is quickly peeled off as Graphene, and Graphene is in the course of injection of multiphase flow with two
Activated carbon after secondary activation is combined in real time, prepares Graphene finely dispersed composite in re-activation activated carbon,
Specifically adopt following steps：
(1) graphite powder is uniformly mixed in a reservoir with solvent；
(2) material is delivered in autoclave, controls in autoclave temperature of charge and pressure to more than the super critical point of solvent,
Material is made to stop in autoclave 30～120 minutes so that graphite layers are by the abundant intercalation of supercritical fluid molecule；
(3) activated carbon is added in supercritical fluid and is sufficiently mixed with the expanded graphite after intercalation, and stop 30
～120 minutes so that supercritical fluid plays re-activation effect to activated carbon；
(4) filter solvents, obtain expanded graphite slurry；
(5) high pressure-temperature nitrogen is utilized to convey expanded graphite slurry, slurry is same to spray mode with single-point or multiple-spot detection
When be injected in high-temperature pressure pyrolysis oven, control pyrolysis furnace temperature be 800～1200 DEG C, slurry stops 0.1-10 in pyrolysis oven
Minute, recycle high-voltage high-speed pressure release and high thermal environment to realize the quick stripping of expanded graphite, and in multiphase flow to being jetted through
The real-time high-efficiency realizing Graphene in journey with super-activated carbon is combined；
(6) utilize the elevated pressure nitrogen of conveying slurry in high-temperature residual heat partition heating stepses (5) of high-temperature pressure pyrolysis oven afterbody
Gas, and the material that pyrolysis oven produces is cooled down；
(7) obtain the super-active carbon composite of graphene in-situ modified after material carries out gas solid separation.
Preferably, in step (1) adopt graphite powder be natural graphite powder or expanded graphite powder, solvent include inorganic solvent or
Organic solvent, can select one or more.
As more preferred embodiment, described organic solvent includes but is not limited to benzyl benzoate, N- methyl pyrrole
Pyrrolidone, dimethyl acetylamide, DMI, NVP, 1- dodecyl -2- pyrrole
Pyrrolidone, dimethylformamide, dimethyl sulfoxide, N- octyl group -2-Pyrrolidone, oxolane, acetonitrile.
Described inorganic solvent includes CO2、H2O, methanol, methane, ethanol, ethane, ethylene, propane, acetone, propylene, isopropyl
Alcohol, ammonia, hexamethylene.
Above-mentioned solvent preferred alcohol, acetone, CO2, dimethylformamide, oxolane, dimethyl sulfoxide, acetonitrile or pyrroles
Alkanone.
In step (1), the ratio of graphite powder weight and solvent volume is 1～100kg/m3.
In step (2) mesohigh kettle, the temperature of material is 30～400 DEG C, and pressure is 3～60Mpa.
In step (3), activated carbon includes wood activated charcoal, active fruit shell carbon, raw mineral materials activated carbon, synthetic resin activity
Charcoal, rubber/plastic activated carbon or regenerated carbon, the addition of activated carbon is 5～100 times of graphite quality.
In step (5), nitrogen amount used and the solid and gas mass ratio of expanded graphite slurry are 100～500kg/kg.Step (5)
In nitrogen used pressure be 1～40MPa, temperature be 100～800 DEG C.
In step (5) nozzle quantity be more than or equal to one, when nozzle quantity be more than or equal to two when, to spray angle degree 0 °～
Between 180 °.
As preferred embodiment, carry out to spray in 180 ° of angles between nozzle.
When material is ejected in high temperature pyrolysis stove, quick pressure releasing and high thermal environment make intercalation after expansion stone
Ink is quickly peeled off as Graphene, the activity after the Graphene immediately producing in the course of injection of multiphase flow and re-activation
Charcoal real-time in-situ is combined, and multiinjector impinging stream will improve compound efficiency and the uniformity, thus preparing Graphene and two
The uniform composite of secondary activated carbon high degree of dispersion.Due in the quick stripping process of expanded graphite produce Graphene with
Activated carbon real-time in-situ is combined, thus avoiding the redispersion problem using graphene powder in conventional complex method；And this
The property such as bright technology can make to give full play to its conductive, heat conduction with the finely disseminated Graphene of activated carbon and surface area is huge, entirely
The quality of activated carbon is improved in face.
Compared with prior art, using supercritical fluid, quick intercalation is carried out to graphite；It is in due course activated carbon
It is sent in supercritical fluid, re-activation is carried out to activated carbon；Multiply supercritical fluid is sprayed in cross-pair spray mode simultaneously
Enter in high-temperature pressure pyrolysis oven, the expanded graphite after making intercalation under high-voltage high-speed pressure release and high thermal environment dual function is fast
Speed is peeled off, and it is compound with the real-time high-efficiency of super-activated carbon, thus avoiding to realize Graphene in multiphase flow is to spray process
Using the redispersion problem of graphene powder in conventional complex method.The technology of the present invention can make Graphene shape in the composite
Uniformly network structure, gives full play of the characteristics such as the excellent conduction of Graphene, heat conduction, high surface, and then significantly improves
The conduction of activated carbon, heat conductivility, effectively enhance the specific surface area of activated carbon.The new stone being prepared using the method
Black alkene/absorbent charcoal composite material is particularly suitable as the electrode material of ultracapacitor, will effectively improve the comprehensive of ultracapacitor
Conjunction property.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
The method realizing Graphene In-situ reaction activated carbon using supercritical fluid, is carried out to graphite using supercritical fluid
Intercalation, is subsequently adding activated carbon, using supercritical fluid, activated carbon is carried out with re-activation and fills with the expanded graphite after intercalation
After point mixing, mixed material is ejected in high-temperature pressure pyrolysis oven in the form of single-point or multiple spot are to spray, quick pressure releasing and high temperature
Expanded graphite after thermal environment makes intercalation is quickly peeled off as Graphene, and Graphene is in the course of injection of multiphase flow with two
Activated carbon after secondary activation is combined in real time, prepares Graphene finely dispersed composite in re-activation activated carbon,
Above-mentioned is to the method brief description, and the method specifically adopts following steps：
(1) graphite powder being uniformly mixed in a reservoir with solvent, the ratio of graphite powder weight and solvent volume is 1～
100kg/m3, in this step, it is natural graphite powder or expanded graphite powder using graphite powder, solvent includes inorganic solvent or organic
Solvent, can select one or more, organic solvent includes but is not limited to benzyl benzoate, N-Methyl pyrrolidone, dimethyl
Acetamide, DMI, NVP, 1- dodecyl -2-Pyrrolidone, dimethyl
Methanamide, dimethyl sulfoxide, N- octyl group -2-Pyrrolidone, oxolane, acetonitrile.Described inorganic solvent includes CO2、H2O, first
Alcohol, methane, ethanol, ethane, ethylene, propane, acetone, propylene, isopropanol, ammonia, hexamethylene.
From technique effect, when solvent selects ethanol, acetone, CO2, dimethylformamide, oxolane, dimethyl sub-
When sulfone, acetonitrile or ketopyrrolidine, the properties of product finally giving are optimal；
(2) material is delivered in autoclave, controls in autoclave temperature of charge and pressure to more than the super critical point of solvent,
In general, can be by the temperature control of material in autoclave at 30～400 DEG C, Stress control, in 3～60Mpa, makes material exist
30～120 minutes are stopped so that graphite layers are by the abundant intercalation of supercritical fluid molecule in autoclave；
(3) activated carbon is added in supercritical fluid and is sufficiently mixed with the expanded graphite after intercalation, the work of use
Property charcoal can be wood activated charcoal, active fruit shell carbon, raw mineral materials activated carbon, synthetic resin activated carbon, rubber/plastic activated carbon
Or regenerated carbon, addition is 5～100 times of graphite quality and stops 30～120 minutes so that supercritical fluid is to activity
Charcoal plays re-activation effect；
(4) filter solvents, obtain expanded graphite slurry；
(5) high pressure-temperature nitrogen is utilized to convey expanded graphite slurry, the solid and gas matter of nitrogen amount used and expanded graphite slurry
Amount ratio is 100～500kg/kg, and the pressure of nitrogen is 1～40MPa, and temperature is 100～800 DEG C, by slurry with single-point or multiple spot
Cross-pair spray mode is injected in high-temperature pressure pyrolysis oven simultaneously, when multiple-spot detection is to spraying, to spray angle degree between 0 °～180 °,
Optimum technical scheme is exactly that 180 ° of angles are carried out to spray, controls pyrolysis furnace temperature to be 800～1200 DEG C, slurry is in pyrolysis oven
Stop 0.1-10 minute, recycle high-voltage high-speed pressure release and high thermal environment to realize the quick stripping of expanded graphite, and in multiphase
That flows is compound with the real-time high-efficiency of super-activated carbon to realizing Graphene in spray process；
(6) utilize the elevated pressure nitrogen of conveying slurry in high-temperature residual heat partition heating stepses (5) of high-temperature pressure pyrolysis oven afterbody
Gas, and the material that pyrolysis oven produces is cooled down；
(7) obtain the super-active carbon composite of graphene in-situ modified after material carries out gas solid separation.
Embodiment 1
By expanded graphite grain weight amount and dimethylformamide (DMF) volume ratio 2kg/m3, graphite powder and organic solvent are added
Enter in container, deliver to after mix homogeneously under ultrasonication in autoclave, control temperature of charge in autoclave to be 370 DEG C, pressure
For 6MPa, material is made to stop in supercritical fluid 30 minutes so that graphite layers are by the abundant intercalation of supercritical fluid molecule.So
By 10 times of graphite quality, cocoanut active charcoal is sent in supercritical fluid afterwards and is fully mixed with the expanded graphite after intercalation
Close, and stop 60 minutes so that supercritical fluid plays further activation to activated carbon.Organic solvent is filtered out, obtains
Expanded graphite after intercalation and the mixed slurry of re-activation activated carbon.Using solid and gas mass ratio be 300kg/kg, temperature be 300
DEG C, pressure is that the nitrogen of 6MPa conveys mixed slurry.By mixed material, from a nozzle, single-point is injected to temperature is 800 DEG C
In normal pressure pyrolysis oven, the expanded graphite after quick pressure releasing and high thermal environment make intercalation is quickly peeled off as Graphene, and
Graphene is combined with the activated carbon real-time high-efficiency after activation in the course of injection of multiphase flow.Control material is in high temperature pyrolysis stove
The time of staying be 10 seconds, using high pressure nitrogen at room partition cool down pyrolysis oven afterbody discharge material, simultaneously nitrogen reach plus
Heat.Finally material is carried out gas solid separation, obtain the super-active carbon composite of graphene in-situ modified.
Embodiment 2
Press natural graphite powder weight and solvent volume than for 20kg/m3, graphite powder and solvent are added in container, solvent
For dimethylformamide (DMF) and liquid CO2Mixed solvent, dimethylformamide (DMF) and liquid CO2Mass ratio be 1:
1.Delivered to after material mix homogeneously in autoclave using mechanical agitation mode, control temperature of charge in autoclave to be 100 DEG C, pressure
Power is 8MPa, so that material is stopped in supercritical fluid 50 minutes so that graphite layers are by the abundant intercalation of supercritical fluid molecule.
Then by 20 times of graphite quality, coal mass active carbon is sent in supercritical fluid and carries out fully with the expanded graphite after intercalation
Mixing, and stop 30 minutes so that supercritical fluid plays further activation to activated carbon.Organic solvent is filtered out, obtains
Expanded graphite to after intercalation and the mixed slurry of re-activation activated carbon.It is that 500kg/kg, temperature are using solid and gas mass ratio
400 DEG C, pressure is that the nitrogen of 8MPa conveys mixed slurry.Mixed material is guided with two pipelines, respectively from nozzle with 90 °
Spray angle vertically to being sprayed onto in the normal pressure pyrolysis oven that temperature is 1200 DEG C, after quick pressure releasing and high thermal environment make intercalation
Expanded graphite is quickly peeled off as Graphene, and Graphene is real-time with the activated carbon after activation in the course of injection of multiphase flow
Compound, impinging stream increased the compound uniformity and efficiency simultaneously.The time of staying in high temperature pyrolysis stove for the control material is 20
Second, the material that pyrolysis oven afterbody is discharged is cooled down using high pressure nitrogen at room partition, nitrogen temperature gets a promotion simultaneously.Finally by thing
Material carries out gas solid separation, obtains the super-active carbon composite of graphene in-situ modified.
Embodiment 3
Compare 50kg/m by expanded graphite grain weight amount and solvent volume3, graphite powder and solvent are added in container, solvent is
N-Methyl pyrrolidone (NMP) and H2The mixed solvent of O, NMP and H2The mass ratio of O is 1: 1.Using ultrasonic agitation mode by thing
Deliver in autoclave after material mix homogeneously, control temperature of charge in autoclave to be 375 DEG C, pressure is 23MPa, so that material is faced super
60 minutes are stopped so that graphite layers are by the abundant intercalation of supercritical fluid molecule in boundary's fluid.Then press graphite quality 50 times
Synthetic resin activated carbon is sent in supercritical fluid and is sufficiently mixed with the expanded graphite after intercalation, and stop 60 minutes
Make supercritical fluid that activated carbon is played with further activation.Organic solvent is filtered out, obtains the expansion stone after intercalation
Ink and the mixed slurry of re-activation activated carbon.Using solid and gas mass ratio be 400kg/kg, temperature be 350 DEG C, pressure be 23MPa
Nitrogen conveying mixed slurry.Mixed material is guided with three pipelines, from three nozzles, 60 ° of sprays is become with same plane respectively
Firing angle degree to being sprayed onto in the normal pressure pyrolysis oven that temperature is 1000 DEG C, quick pressure releasing and high thermal environment make intercalation after expansion stone
Ink is quickly peeled off as Graphene, and Graphene is combined in real time with the activated carbon after activation in the course of injection of multiphase flow,
And impinging stream increased the compound uniformity and efficiency.The time of staying in high temperature pyrolysis stove for the control material is 60 seconds, adopts
High pressure nitrogen at room partition cools down the material that pyrolysis oven afterbody is discharged, and nitrogen temperature gets a promotion simultaneously.Finally material is carried out
Gas solid separation, obtains the super-active carbon composite of graphene in-situ modified.
The product that the application prepares significantly improves the electric conductivity of activated carbon, effectively enhances the ratio table of activated carbon
Area, the novel graphite alkene/absorbent charcoal composite material preparing is particularly suitable as the electrode material of ultracapacitor.Through
The modified activated carbon of present techniques contrasts and see table with the specific surface area of unmodified activated carbon and electric conductivity.
| Specific surface area (m2/g) | Electrical conductivity (S/m) | |
| Merchandise active carbon | 1584 | 3 |
| Example 1 Graphene modified activated carbon | 1936 | 205 |
| Example 2 Graphene modified activated carbon | 1802 | 131 |
| Example 3 Graphene modified activated carbon | 1845 | 107 |
Claims (12)
1. realize the method for Graphene In-situ reaction activated carbon it is characterised in that utilizing supercritical fluid using supercritical fluid
Intercalation is carried out to graphite, is subsequently adding activated carbon, using supercritical fluid activated carbon is carried out re-activation and with intercalation after
After expanded graphite is sufficiently mixed, mixed material is ejected in high-temperature pressure pyrolysis oven in the form of spraying with single-point or multiple spot, quickly
Expanded graphite after pressure release and high thermal environment make intercalation is quickly peeled off as Graphene, and Graphene is in the injection of multiphase flow
During be combined in real time with the activated carbon after re-activation, prepare Graphene finely dispersed in re-activation activated carbon
Composite.
2. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 1, its feature
It is, the method specifically adopts following steps：
(1) graphite powder is uniformly mixed in a reservoir with solvent；
(2) material is delivered in autoclave, control temperature of charge and pressure in autoclave to more than the super critical point of solvent, to make thing
Material stops 30～120 minutes so that graphite layers are by the abundant intercalation of supercritical fluid molecule in autoclave；
(3) activated carbon is added in supercritical fluid and is sufficiently mixed with the expanded graphite after intercalation, and stop 30～120
Minute is so that supercritical fluid plays re-activation effect to activated carbon；
(4) filter solvents, obtain expanded graphite slurry；
(5) utilize high pressure-temperature nitrogen to convey expanded graphite slurry, slurry is sprayed to spray mode with single-point or multiple-spot detection simultaneously
Enter in high-temperature pressure pyrolysis oven, control pyrolysis furnace temperature to be 800～1200 DEG C, slurry stops 0.1-10 in pyrolysis oven and divides
Clock, recycles high-voltage high-speed pressure release and high thermal environment to realize the quick stripping of expanded graphite, and in multiphase flow to spray process
Middle Graphene of realizing is combined with the real-time high-efficiency of super-activated carbon；
(6) utilize the high pressure nitrogen of conveying slurry in high-temperature residual heat partition heating stepses (5) of high-temperature pressure pyrolysis oven afterbody, and
The material that pyrolysis oven produces is cooled down；
(7) obtain the super-active carbon composite of graphene in-situ modified after material carries out gas solid separation.
3. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, the graphite powder described in step (1) is natural graphite powder or expanded graphite powder.
4. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, the solvent described in step (1) is one or more, including inorganic solvent or organic solvent,
Described organic solvent includes but is not limited to benzyl benzoate, N-Methyl pyrrolidone, dimethyl acetylamide, 1,3- diformazan
Base -2- imidazolone, NVP, 1- dodecyl -2-Pyrrolidone, dimethylformamide, dimethyl are sub-
Sulfone, N- octyl group -2-Pyrrolidone, oxolane, acetonitrile,
Described inorganic solvent includes CO2、H2O, methanol, methane, ethanol, ethane, ethylene, propane, acetone, propylene, isopropanol,
Ammonia, hexamethylene.
5. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 4, its feature
It is, described solvent is ethanol, acetone, CO2, dimethylformamide, oxolane, dimethyl sulfoxide, acetonitrile or pyrrolidine
Ketone.
6. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, in step (1), the ratio of graphite powder weight and solvent volume is 1～100kg/m3.
7. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, in step (2) mesohigh kettle, the temperature of material is 30～400 DEG C, pressure is 3～60Mpa.
8. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
Be, in step (3) activated carbon include wood activated charcoal, active fruit shell carbon, raw mineral materials activated carbon, synthetic resin activated carbon,
Rubber/plastic activated carbon or regenerated carbon, the addition of activated carbon is 5～100 times of graphite quality.
9. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, in step (5), nitrogen amount used and the solid and gas mass ratio of expanded graphite slurry are 100～500kg/kg.
10. the method realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, in step (5), the pressure of nitrogen used is 1～40MPa, temperature is 100～800 DEG C.
11. methods realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 2, its feature
It is, in step (5), nozzle quantity is more than or equal to one, when nozzle quantity is more than or equal to two, the angle between nozzle exists
Between 0 °～180 °.
12. methods realizing Graphene In-situ reaction activated carbon using supercritical fluid according to claim 11, it is special
Levy and be, when nozzle quantity is more than or equal to two in step (5), carry out to spray in 180 ° of angles between nozzle.
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| CN106941151B (en) * | 2016-01-05 | 2019-07-12 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| CN105645391B (en) * | 2016-01-06 | 2017-12-19 | 大连理工大学 | A kind of CO2Dislocation movement by slip effect is introduced in expanding liquid and peels off the method that natural graphite powder prepares graphene |
| CN107629255B (en) * | 2016-07-18 | 2019-11-12 | 郑州福流智能科技有限公司 | A kind of graphene-rubber and preparation method and application |
| CN108314012A (en) * | 2017-01-16 | 2018-07-24 | 山东恒华新材料有限公司 | Ammonia heat method batch prepares the production technology of graphene |
| CN107579232A (en) * | 2017-09-08 | 2018-01-12 | 绵阳梨坪科技有限公司 | A kind of preparation method of graphene in-situ modified graphite carbon electrode material |
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