CN104240964A - 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
- Publication number
- CN104240964A CN104240964A CN201410479313.XA CN201410479313A CN104240964A CN 104240964 A CN104240964 A CN 104240964A CN 201410479313 A CN201410479313 A CN 201410479313A CN 104240964 A CN104240964 A CN 104240964A
- Authority
- CN
- China
- Prior art keywords
- graphene
- active carbon
- supercritical fluid
- temperature
- intercalation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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 a kind of method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon.
Background technology
Active carbon has high volumetric surface area, and cost is low, with the feature such as electrolyte compatibility is good, is the most widely used electrode material for super capacitor.But at present, there is the problems such as conductivity is poor, thermal diffusivity is low, specific area is less in conventional carbon-based material, cannot meet the energy storage requirement of ultracapacitor, define industry bottleneck.
Graphene is carbon atom with the tightly packed cellular Colloidal particles carbon nanomaterial of sp2 hybrid systems.Because Graphene has unique two-dimensional structure, excellent conductivity, outstanding mechanics and thermal property, the specific area of super large and the surface of opening, be conducive to the formation at electrode material/electrolyte electric double layer interface, make the application of graphene-based material in ultracapacitor have great potentiality.Utilize Graphene to build tridimensional network between activated carbon granule, the specific area of active carbon can not only be improved, also help and reduce the migration resistance of ion in hole, improve the heat dispersion of ultracapacitor.
Although Graphene has excellent performance, still there is bottleneck in use, the twice dispersing of graphene powder and Cost Problems are the topmost limiting factors that restriction Graphene uses on a large scale.The preparation method of existing Graphene mainly contains oxidation-reduction method and chemical vapour deposition technique etc. in the market, but the graphene powder that above method obtains in use all is difficult to again disperse, cause with active material phase compound after performance boost not obvious.And above method is batch production, not only product quality consistency is difficult to ensure, and preparation cost is high, expensive.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of conduction, the heat conductivility that improve active carbon are provided, the supercritical fluid that utilizes effectively enhancing the specific area of active carbon realizes the method for Graphene In-situ reaction active carbon, novel graphite alkene/the absorbent charcoal composite material prepared especially is suitable as the electrode material of ultracapacitor, will effectively improve the comprehensive of ultracapacitor.
Object of the present invention can be achieved through the following technical solutions:
Supercritical fluid is utilized to realize the method for Graphene In-situ reaction active carbon, supercritical fluid is utilized to carry out intercalation to graphite, then active carbon is added, supercritical fluid is utilized to carry out re-activation to active carbon and after fully mixing with the expanded graphite after intercalation, with single-point or multiple spot, the form to spray is ejected in high-temperature pressure pyrolysis oven mixed material, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off fast for Graphene, Graphene in the course of injection of multiphase flow with re-activation after the real-time compound of active carbon, prepare Graphene finely dispersed composite material in re-activation active carbon, concrete employing following steps:
(1) graphite powder and solvent are uniformly mixed in a reservoir;
(2) material is delivered in autoclave, to control in autoclave more than temperature of charge and pressure to the super critical point of solvent, to make material stop 30 ~ 120 minutes in autoclave, make graphite layers by the abundant intercalation of supercritical fluid molecule;
(3) active carbon is joined in supercritical fluid fully mix with the expanded graphite after intercalation, and stop 30 ~ 120 minutes, make supercritical fluid play re-activation effect to active carbon;
(4) filter solvents, obtains expanded graphite slurry;
(5) high pressure-temperature nitrogen is utilized to carry expanded graphite slurry, slurry is injected in high-temperature pressure pyrolysis oven with single-point or multiple-spot detection to spray mode simultaneously, controlling pyrolysis oven temperature is 800 ~ 1200 DEG C, slurry stops 0.1-10 minute in pyrolysis oven, recycling high-voltage high-speed pressure release and high-temperature hot environment realize the quick stripping of expanded graphite, and multiphase flow to spray process in realize the real-time high-efficiency compound of Graphene and super-activated carbon;
(6) utilize the high pressure nitrogen of conveying slurry in the high-temperature residual heat partition heating steps (5) of high-temperature pressure pyrolysis oven afterbody, and the material that pyrolysis oven is produced is cooled;
(7) namely material obtains the super-active carbon composite of graphene in-situ modified after carrying out gas solid separation.
Preferably, adopt graphite powder to be natural graphite powder or expanded graphite powder in step (1), solvent comprises inorganic solvent or organic solvent, can select one or more.
As the execution mode be more preferably, described organic solvent includes but not limited to Ergol, 1-METHYLPYRROLIDONE, dimethylacetylamide, DMI, NVP, 1-dodecyl-2-Pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), N-octyl group-2-Pyrrolidone, oxolane, acetonitrile.
Described inorganic solvent comprises CO
2, H
2o, methyl alcohol, methane, ethanol, ethane, ethene, propane, acetone, propylene, isopropyl alcohol, ammonia, cyclohexane.
Above-mentioned solvent preferred alcohol, acetone, CO
2, dimethyl formamide, oxolane, dimethyl sulfoxide (DMSO), acetonitrile or pyrrolidones.
In step (1), the ratio of graphite powder weight and solvent volume is 1 ~ 100kg/m
3.
In step (2) mesohigh still, the temperature of material is 30 ~ 400 DEG C, and pressure is 3 ~ 60Mpa.
In step (3), active carbon comprises wood activated charcoal, active fruit shell carbon, raw mineral materials active carbon, synthetic resin active carbon, rubber/plastic living charcoal or regenerated carbon, and the addition of active carbon is 5 ~ 100 times of graphite quality.
In step (5), the solid and gas mass ratio of nitrogen amount used and expanded graphite slurry is 100 ~ 500kg/kg.In step (5), the pressure of nitrogen used is 1 ~ 40MPa, and temperature is 100 ~ 800 DEG C.
In step (5), nozzle quantity is more than or equal to one, when nozzle quantity is more than or equal to two, to spray angle degree between 0 ° ~ 180 °.
As preferred embodiment, carry out spray in 180 ° of angles between nozzle.
When material is ejected in high temperature pyrolysis stove time, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off fast for Graphene, active carbon real-time in-situ compound in the course of injection of multiphase flow after the instant Graphene that produces and re-activation, and multiinjector impinging stream will improve efficiency and the uniformity of compound, thus prepare Graphene and the uniform composite material of re-activation active carbon high degree of dispersion.Due to the Graphene that produces in the quick stripping process of expanded graphite and active carbon real-time in-situ compound, thus avoid in conventional complex method the scattering problem again using graphene powder; And the technology of the present invention can make the finely disseminated Graphene with active carbon give full play to that it conducts electricity, heat conduction and the character such as surface area is huge, improve the quality of active carbon comprehensively.
Compared with prior art, supercritical fluid is utilized to carry out quick intercalation to graphite; Be in due course and active carbon is sent in supercritical fluid, re-activation is carried out to active carbon; Multiply supercritical fluid is injected in high-temperature pressure pyrolysis oven to intersect to spray mode simultaneously, expanded graphite make intercalation under high-voltage high-speed pressure release and high-temperature hot environment double action after is peeled off fast, and multiphase flow to spray process in realize the real-time high-efficiency compound of Graphene and super-activated carbon, thus avoid in conventional complex method the scattering problem again using graphene powder.The technology of the present invention can make Graphene form uniform network structure in the composite, give full play of the characteristics such as the conduction of Graphene excellence, heat conduction, high surface, and then significantly improve conduction, the heat conductivility of active carbon, effectively enhance the specific area of active carbon.Novel graphite alkene/the absorbent charcoal composite material utilizing the method to prepare especially is suitable as the electrode material of ultracapacitor, will effectively improve the comprehensive of ultracapacitor.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Supercritical fluid is utilized to realize the method for Graphene In-situ reaction active carbon, supercritical fluid is utilized to carry out intercalation to graphite, then active carbon is added, supercritical fluid is utilized to carry out re-activation to active carbon and after fully mixing with the expanded graphite after intercalation, with single-point or multiple spot, the form to spray is ejected in high-temperature pressure pyrolysis oven mixed material, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off fast for Graphene, Graphene in the course of injection of multiphase flow with re-activation after the real-time compound of active carbon, prepare Graphene finely dispersed composite material in re-activation active carbon, above-mentioned is to the method brief description, the method specifically adopts following steps:
(1) graphite powder and solvent are uniformly mixed in a reservoir, the ratio of graphite powder weight and solvent volume is 1 ~ 100kg/m
3in this step, graphite powder is adopted to be natural graphite powder or expanded graphite powder, solvent comprises inorganic solvent or organic solvent, one or more can be selected, organic solvent includes but not limited to Ergol, 1-METHYLPYRROLIDONE, dimethylacetylamide, DMI, NVP, 1-dodecyl-2-Pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), N-octyl group-2-Pyrrolidone, oxolane, acetonitrile.Described inorganic solvent comprises CO
2, H
2o, methyl alcohol, methane, ethanol, ethane, ethene, propane, acetone, propylene, isopropyl alcohol, ammonia, cyclohexane.
From technique effect, when solvent selects ethanol, acetone, CO
2, dimethyl formamide, oxolane, dimethyl sulfoxide (DMSO), acetonitrile or pyrrolidones time, the properties of product that finally obtain are best;
(2) material is delivered in autoclave, to control in autoclave more than temperature of charge and pressure to the super critical point of solvent, in general, can the temperature of material in autoclave be controlled at 30 ~ 400 DEG C, Stress control is at 3 ~ 60Mpa, make material stop 30 ~ 120 minutes in autoclave, make graphite layers by the abundant intercalation of supercritical fluid molecule;
(3) active carbon is joined in supercritical fluid fully mix with the expanded graphite after intercalation, the active carbon used can be wood activated charcoal, active fruit shell carbon, raw mineral materials active carbon, synthetic resin active carbon, rubber/plastic living charcoal or regenerated carbon, addition is 5 ~ 100 times of graphite quality and stops 30 ~ 120 minutes, makes supercritical fluid play re-activation effect to active carbon;
(4) filter solvents, obtains expanded graphite slurry;
(5) high pressure-temperature nitrogen is utilized to carry expanded graphite slurry, the solid and gas mass ratio of nitrogen amount used and expanded graphite slurry is 100 ~ 500kg/kg, the pressure of nitrogen is 1 ~ 40MPa, temperature is 100 ~ 800 DEG C, slurry is injected in high-temperature pressure pyrolysis oven with single-point or multiple-spot detection to spray mode simultaneously, when multiple-spot detection is to spray, to spray angle degree between 0 ° ~ 180 °, optimum technical scheme is exactly that 180 ° of angles carry out spray, controlling pyrolysis oven temperature is 800 ~ 1200 DEG C, slurry stops 0.1-10 minute in pyrolysis oven, recycling high-voltage high-speed pressure release and high-temperature hot environment realize the quick stripping of expanded graphite, and multiphase flow to spray process in realize the real-time high-efficiency compound of Graphene and super-activated carbon,
(6) utilize the high pressure nitrogen of conveying slurry in the high-temperature residual heat partition heating steps (5) of high-temperature pressure pyrolysis oven afterbody, and the material that pyrolysis oven is produced is cooled;
(7) namely material obtains the super-active carbon composite of graphene in-situ modified after carrying out gas solid separation.
Embodiment 1
By expanded graphite grain weight amount and dimethyl formamide (DMF) volume ratio 2kg/m
3, graphite powder and organic solvent are added in container, deliver to after mixing under ultrasonication in autoclave, controlling temperature of charge in autoclave is 370 DEG C, pressure is 6MPa, makes material stop 30 minutes in supercritical fluid, makes graphite layers by the abundant intercalation of supercritical fluid molecule.Then by 10 times of graphite quality cocoanut active charcoal is sent in supercritical fluid and fully mixes with the expanded graphite after intercalation, and stop and within 60 minutes, make supercritical fluid play further activation to active carbon.Organic solvent is filtered out, obtains the mixed slurry of the expanded graphite after intercalation and re-activation active carbon.Employing solid and gas mass ratio is 300kg/kg, temperature is 300 DEG C, and pressure is the nitrogen conveying mixed slurry of 6MPa.It is in the normal pressure pyrolysis oven of 800 DEG C that mixed material single-point from a nozzle is injected to temperature, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off as Graphene fast, and Graphene in the course of injection of multiphase flow with activation after active carbon real-time high-efficiency compound.Controlling the time of staying of material in high temperature pyrolysis stove is 10 seconds, and adopt the material that high pressure nitrogen at room partition cooling pyrolysis stove afterbody is discharged, nitrogen reaches heating simultaneously.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 with solvent volume than being 20kg/m
3, join in container by graphite powder and solvent, solvent is dimethyl formamide (DMF) and liquid CO
2mixed solvent, dimethyl formamide (DMF) and liquid CO
2mass ratio be 1: 1.Deliver in autoclave after adopting mechanical agitation mode that mixing of materials is even, controlling temperature of charge in autoclave is 100 DEG C, and pressure is 8MPa, makes material stop 50 minutes in supercritical fluid, makes graphite layers 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 fully mixes with the expanded graphite after intercalation, and stop and within 30 minutes, make supercritical fluid play further activation to active carbon.Organic solvent is filtered out, obtains the mixed slurry of the expanded graphite after intercalation and re-activation active carbon.Employing solid and gas mass ratio is 500kg/kg, temperature is 400 DEG C, and pressure is the nitrogen conveying mixed slurry of 8MPa.Mixed material two pipelines are guided, be vertically in the normal pressure pyrolysis oven of 1200 DEG C to being sprayed onto temperature with 90 ° of spray angles in nozzle respectively, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off fast for Graphene, and Graphene in the course of injection of multiphase flow with activation after the real-time compound of active carbon, simultaneously impinging stream adds the uniformity and the efficiency of compound.Controlling the time of staying of material in high temperature pyrolysis stove is 20 seconds, and adopt the material that high pressure nitrogen at room partition cooling pyrolysis stove afterbody is discharged, nitrogen temperature gets a promotion simultaneously.Finally material is carried out gas solid separation, obtain the super-active carbon composite of graphene in-situ modified.
Embodiment 3
50kg/m is compared with solvent volume by expanded graphite grain weight amount
3, join in container by graphite powder and solvent, solvent is 1-METHYLPYRROLIDONE (NMP) and H
2the mixed solvent of O, NMP and H
2the mass ratio of O is 1: 1.Deliver in autoclave after adopting ultrasonic agitation mode that mixing of materials is even, controlling temperature of charge in autoclave is 375 DEG C, and pressure is 23MPa, makes material stop 60 minutes in supercritical fluid, makes graphite layers by the abundant intercalation of supercritical fluid molecule.Then by 50 times of graphite quality synthetic resin active carbon is sent in supercritical fluid and fully mixes with the expanded graphite after intercalation, and stop and within 60 minutes, make supercritical fluid play further activation to active carbon.Organic solvent is filtered out, obtains the mixed slurry of the expanded graphite after intercalation and re-activation active carbon.Employing solid and gas mass ratio is 400kg/kg, temperature is 350 DEG C, and pressure is the nitrogen conveying mixed slurry of 23MPa.Mixed material three pipelines are guided, in three nozzles, 60 ° of spray angles are become to be in the normal pressure pyrolysis oven of 1000 DEG C to being sprayed onto temperature with same plane respectively, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off fast for Graphene, and Graphene in the course of injection of multiphase flow with activation after the real-time compound of active carbon, and impinging stream adds the uniformity and the efficiency of compound.Controlling the time of staying of material in high temperature pyrolysis stove is 60 seconds, and adopt the material that high pressure nitrogen at room partition cooling pyrolysis stove afterbody is discharged, nitrogen temperature gets a promotion simultaneously.Finally material is carried out gas solid separation, obtain the super-active carbon composite of graphene in-situ modified.
The product that the application prepares significantly improves the electric conductivity of active carbon, effectively enhances the specific area of active carbon, and the novel graphite alkene/absorbent charcoal composite material prepared especially is suitable as the electrode material of ultracapacitor.Contrast through the active carbon of present techniques modification and the specific area of unmodified active carbon and electric conductivity and see the following form.
| ? | Specific area (m 2/g) | 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 (10)
1. utilize supercritical fluid to realize the method for Graphene In-situ reaction active carbon, it is characterized in that, supercritical fluid is utilized to carry out intercalation to graphite, then active carbon is added, supercritical fluid is utilized to carry out re-activation to active carbon and after fully mixing with the expanded graphite after intercalation, with single-point or multiple spot, the form to spray is ejected in high-temperature pressure pyrolysis oven mixed material, expanded graphite after quick pressure releasing and high-temperature hot environment make intercalation is able to peel off fast for Graphene, Graphene in the course of injection of multiphase flow with re-activation after the real-time compound of active carbon, prepare Graphene finely dispersed composite material in re-activation active carbon.
2. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 1, it is characterized in that, the method specifically adopts following steps:
(1) graphite powder and solvent are uniformly mixed in a reservoir;
(2) material is delivered in autoclave, to control in autoclave more than temperature of charge and pressure to the super critical point of solvent, to make material stop 30 ~ 120 minutes in autoclave, make graphite layers by the abundant intercalation of supercritical fluid molecule;
(3) active carbon is joined in supercritical fluid fully mix with the expanded graphite after intercalation, and stop 30 ~ 120 minutes, make supercritical fluid play re-activation effect to active carbon;
(4) filter solvents, obtains expanded graphite slurry;
(5) high pressure-temperature nitrogen is utilized to carry expanded graphite slurry, slurry is injected in high-temperature pressure pyrolysis oven with single-point or multiple-spot detection to spray mode simultaneously, controlling pyrolysis oven temperature is 800 ~ 1200 DEG C, slurry stops 0.1-10 minute in pyrolysis oven, recycling high-voltage high-speed pressure release and high-temperature hot environment realize the quick stripping of expanded graphite, and multiphase flow to spray process in realize the real-time high-efficiency compound of Graphene and super-activated carbon;
(6) utilize the high pressure nitrogen of conveying slurry in the high-temperature residual heat partition heating steps (5) of high-temperature pressure pyrolysis oven afterbody, and the material that pyrolysis oven is produced is cooled;
(7) namely material obtains the super-active carbon composite of graphene in-situ modified after carrying out gas solid separation.
3. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, is characterized in that, the graphite powder described in step (1) is natural graphite powder or expanded graphite powder.
4. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, is characterized in that, the solvent described in step (1) is one or more, comprises inorganic solvent or organic solvent,
Described organic solvent includes but not limited to Ergol, 1-METHYLPYRROLIDONE, dimethylacetylamide, DMI, NVP, 1-dodecyl-2-Pyrrolidone, dimethyl formamide, dimethyl sulfoxide (DMSO), N-octyl group-2-Pyrrolidone, oxolane, acetonitrile.
Described inorganic solvent comprises CO
2, H
2o, methyl alcohol, methane, ethanol, ethane, ethene, propane, acetone, propylene, isopropyl alcohol, ammonia, cyclohexane.
Above-mentioned solvent preferred alcohol, acetone, CO
2, dimethyl formamide, oxolane, dimethyl sulfoxide (DMSO), acetonitrile or pyrrolidones.
5. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, is characterized in that, in step (1), the ratio of graphite powder weight and solvent volume is 1 ~ 100kg/m
3.
6. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, is characterized in that, in step (2) mesohigh still, the temperature of material is 30 ~ 400 DEG C, and pressure is 3 ~ 60Mpa.
7. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, it is characterized in that, in step (3), active carbon comprises wood activated charcoal, active fruit shell carbon, raw mineral materials active carbon, synthetic resin active carbon, rubber/plastic living charcoal or regenerated carbon, and the addition of active carbon is 5 ~ 100 times of graphite quality.
8. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, is characterized in that, in step (5), the solid and gas mass ratio of nitrogen amount used and expanded graphite slurry is 100 ~ 500kg/kg.
9. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, is characterized in that, in step (5), the pressure of nitrogen used is 1 ~ 40MPa, and temperature is 100 ~ 800 DEG C.
10. the method utilizing supercritical fluid to realize Graphene In-situ reaction active carbon according to claim 2, it is characterized in that, in step (5), nozzle quantity is more than or equal to one, when nozzle quantity is more than or equal to two, angle between nozzle, between 0 ° ~ 180 °, carries out spray in 180 ° of angles between preferred nozzle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410479313.XA CN104240964B (en) | 2014-09-18 | 2014-09-18 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410479313.XA CN104240964B (en) | 2014-09-18 | 2014-09-18 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104240964A true CN104240964A (en) | 2014-12-24 |
| CN104240964B CN104240964B (en) | 2017-02-15 |
Family
ID=52228858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410479313.XA Active CN104240964B (en) | 2014-09-18 | 2014-09-18 | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104240964B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105645391A (en) * | 2016-01-06 | 2016-06-08 | 大连理工大学 | Method for preparing graphene by stripping natural graphite powder in CO2 expanded liquid by introducing dislocation glide actions |
| CN106941151A (en) * | 2016-01-05 | 2017-07-11 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| 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 |
| CN107629255A (en) * | 2016-07-18 | 2018-01-26 | 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115078B (en) * | 2011-01-19 | 2012-12-26 | 上海交通大学 | Method for preparing graphene by using supercritical fluid |
| CN102107869A (en) * | 2011-03-21 | 2011-06-29 | 无锡索垠飞科技有限公司 | Method for preparing graphene by using modifying supercritical peeling technology |
| CN102139875B (en) * | 2011-04-27 | 2013-09-18 | 南京科孚纳米技术有限公司 | Method for preparing super activated carbon by utilizing modification supercritical oxidation technology |
| CN103183331B (en) * | 2011-12-28 | 2016-01-20 | 清华大学 | The preparation method of Graphene |
| CN102867650B (en) * | 2012-09-03 | 2016-01-20 | 中国科学院大连化学物理研究所 | A kind of high-magnification supercapacitor composite electrode material and preparation method thereof |
| JPWO2014087992A1 (en) * | 2012-12-04 | 2017-01-05 | 昭和電工株式会社 | Graphene sheet composition |
-
2014
- 2014-09-18 CN CN201410479313.XA patent/CN104240964B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106941151A (en) * | 2016-01-05 | 2017-07-11 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| 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 |
| CN105645391A (en) * | 2016-01-06 | 2016-06-08 | 大连理工大学 | Method for preparing graphene by stripping natural graphite powder in CO2 expanded liquid by introducing dislocation glide actions |
| CN107629255A (en) * | 2016-07-18 | 2018-01-26 | 郑州福流智能科技有限公司 | A kind of graphene rubber and preparation method and application |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104240964B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104240964A (en) | Method for achieving in situ composition of graphene and activated carbon through supercutical fluid | |
| CN103950929B (en) | A kind of chemical method prepares the method for granulated active carbon | |
| CN106986647B (en) | A kind of preparation method of the porous carbon network based on graphene | |
| CN102603348B (en) | A kind of nano-pore heat insulating materials and preparation method thereof | |
| CN103466616B (en) | The preparation method of coal mass active carbon is reclaimed for organic solvent | |
| CN104130538B (en) | A kind of method preparing graphene solution based on supercritical carbon dioxide inducing solution phase in version technology | |
| CN101927996B (en) | Method for preparing pitch-based foam carbon | |
| CN103056382B (en) | A kind of preparation method of nanostructured tungsten carbide/cobalt composite powder | |
| CN104592620A (en) | Resin/graphene conductive plastic master batch as well as preparation method and use thereof | |
| CN102115078A (en) | Method for preparing graphene by using supercritical fluid | |
| CN105489389A (en) | Carbon/nickel-cobalt layered double hydroxide composite material and preparation method and application thereof | |
| CN109873152A (en) | A kind of lithium ion battery graphene-silicon substrate composite negative pole material and preparation method thereof | |
| CN102702562A (en) | Preparation method for thermoplastic polyimide foaming particle and formed body thereof | |
| CN103555282A (en) | Preparation method of high-heat-conductivity paraffin/graphite phase-change composite material | |
| CN101961644A (en) | Chloride-carbonaceous skeleton composite adsorbent and preparation method thereof | |
| CN108735528A (en) | A kind of preparation process of the super capacitor electrode slice containing PTFE fiber | |
| CN102702561A (en) | Preparation method of low-density thermoplastic polyimide micro-foamed material | |
| CN103641100A (en) | Preparation method of cassava-starch-based grading-pore carbon microsphere material | |
| CN105990569B (en) | The preparation method and powder body material of a kind of sulphur carbon composite powder material and application | |
| CN106927456A (en) | A kind of use mechanical stripping method prepares the process units and method of Graphene | |
| CN103754870B (en) | One step activation method prepares the method for coke-based pressed active carbon | |
| CN104117327B (en) | A kind of low temperature method of granulating of powder lactic acid | |
| CN101733001A (en) | Method for adjusting petroleum coke-based tubular carbon-film pore structure | |
| CN103408723B (en) | The high flame retardant polyisocyanurate foamed plastics that spray coating foaming is shaping and preparation method | |
| CN105289442B (en) | A kind of coal pyrolysis in plasma producing acetylene reaction unit |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |