CN110342488A - A kind of preparation method of high-performance foam carbon - Google Patents
A kind of preparation method of high-performance foam carbon Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The invention belongs to C-base composte material preparation technical fields, and in particular to a kind of preparation method of high-performance foam carbon.Functionalization graphene is added into catalytic cracking (FCC) slurry oil of polishing purification, the modified FCC slurry of high dispersive graphene is made；By heating modifying process, presoma is made；Under high temperature, high pressure, presoma obtains graphene/foamy carbon raw material from foaming pyrolysis；Raw material are carbonized, are graphitized to obtain graphene enhancing high-performance foam carbon.Graphene enhancing foamed carbon material prepared by the present invention and pure foam carbon phase ratio, thermal conductivity can be improved 5% ~ 20%, and compressive strength can be improved 10 ~ 30%.
Description
Technical field
The invention belongs to C-base composte material preparation technical fields, and in particular to a kind of preparation side of high-performance foam carbon
Method.
Background technique
Foamy carbon is a kind of functional form carbon material with three-dimensional netted cellular structure, and pore structure is mainly by micron order
Hole bubble and ligament structure interconnected composition.After graphitization processing, solid carbon skeleton is by being in netted along hole wall direction
The graphite ligament of arrangement is constituted, and porosity is up to 70 ~ 80%.The characteristic of this unique structure and matrix carbon, so that foam
Carbon have low-density, high conductivity, low thermal coefficient of expansion, high intensity, high thermal conductivity coefficient, low water absorption, high temperature resistant, acid and alkali-resistance,
Anti-oxidant, paint having no volatile substances do not generate toxic gas, and have the advantages that good processable and formability energy.Therefore,
As a kind of lightweight functional structure material, foamy carbon has good in fields such as aerospace, chemical industry, the energy, environment, electronics
Development prospect.However, the high heat conducting foam carbon prepared by mesophase pitch as raw material in graphitizing process due to being also easy to produce
More crackle is substantially reduced foamy carbon intensity, and thermal conductivity is lower than theoretical thermal conductivity, constrains its large-scale application, because
It is necessary to carry out enhancing processing to it for this.
Currently, the research for being doped enhancing to foamy carbon is directly to mix reinforcement with mesophase pitch mostly
Obtained foam carbon matrix precursor, the mechanical property and heating conduction improvement to foamy carbon are unobvious, improve limited extent.
Summary of the invention
In order to solve dispersion problem of the graphene in foamy carbon, existing foamy carbon mechanical property and heating conduction are overcome
Insufficient defect, the invention proposes a kind of preparation methods of high-performance foam carbon.
A kind of preparation method of high-performance foam carbon, comprising the following steps:
(1) functionalization graphene is added into the catalytic cracking of polishing purification (FCC) slurry oil, the modified FCC oil of graphene is made
Slurry；
(2) FCC slurry modified to the graphene of step (1), heating modification, is made presoma；
(3) under high temperature, high pressure, the presoma of step (2), which passes through from foaming pyrolysis, obtains graphene/foamy carbon raw material；
(4) raw material of step (3) are carbonized, are graphitized to obtain graphene enhancing high-performance foam carbon.
The preparation method of functionalization graphene in the step (1): it adds graphene oxide into ultrasonic in organic solution 1
Processing 0.5 ~ 3h obtain dispersion liquid, be subsequently added into small molecule monomer, under atmospheric condition at 30 ~ 80 DEG C 4 ~ 8h of back flow reaction,
Functionalization graphene material is obtained after filtering and washing.
Preferably, the organic solvent 1 is ethyl alcohol, isopropanol, acetone, benzene,toluene,xylene, chloroform, tetrahydro furan
It mutters, one or more of hexamethylene, N,N-dimethylformamide, dimethyl sulfoxide.
Preferably, the small molecule monomer is ether epoxy, isocyanates, stearic acid, oleic acid, octadecylamine, oleyl amine, ethyl alcohol
One or more of amine, ethylenediamine, hexamethylene diamine.
The condition of the modified FCC slurry of graphene in the step (1) are as follows: step (1) is added in functionalization graphene
In the organic solution 2, then by the mixed solution 0.5 ~ 3h of ultrasound, the functionalization graphene suspension dispersed is connect
Functionalization graphene suspension carried out with the FCC slurry of polishing purification to magnetic agitation according to a certain percentage mix and ultrasound point
It dissipates, extra organic solvent is then removed by vacuum distillation and obtains the modified FCC slurry of graphene；
The organic solvent 1 be ethyl alcohol, isopropanol, acetone, benzene,toluene,xylene, chloroform, tetrahydrofuran, hexamethylene, N,
One or more of dinethylformamide, dimethyl sulfoxide.
Preferably, the FCC slurry of polishing purification as described in step (1) is the purification slurry oil that ash content is less than 100ppm,
Sulfur content≤2500ppm, asphalitine≤9%.
Preferably, above method functionalization graphene additive amount as described in step (1) accounts for FCC slurry mass percent and is
0.01%~0.50%。
The specific preparation process of presoma in the step (2) are as follows: it is anti-that the modified FCC slurry of graphene is placed in high pressure
It answers and carries out direct thermal polycondensation in kettle, under the stirring rate of inert atmosphere and 300 ~ 600r/min, by the mixture with 1 ~ 5 °
The rate of C/min rises to 350 ~ 450 DEG C from room temperature, then regulates and controls in kettle pressure to 0.5 ~ 5.0MPa, and protect under constant-pressure conditions
Temperature 4 ~ 10 hours obtains precursor after cooling.
The graphene of the step (the 3)/specific preparation process of foamy carbon raw material are as follows: before graphene/mesophase pitch
100 ~ 200 meshes are crossed after body grinding to foam in a high pressure reaction kettle under inert gas protection, maintain in kettle constant pressure to 4 ~
8MPa is warming up to 320 ~ 360 DEG C with the heating rate of 1 ~ 3 DEG C/min, 1 ~ 4h is kept the temperature, again with 1 ~ 3 DEG C/min's after heat preservation
Heating rate is warming up to 420 ~ 530 DEG C, keeps the temperature 1 ~ 3h, obtains graphene/foamy carbon raw material after cooling.
The preparation process of step (4) the graphene enhancing high-performance foam carbon are as follows: be put into graphene/foamy carbon raw material
In retort, 800 ~ 1000 DEG C are warming up to the heating rate of 1 ~ 5 DEG C/min, keeps the temperature 1 ~ 3h；High temperature graphitization is put it into again
In furnace, 2400 ~ 2800 DEG C are warming up to the heating rate of 5 ~ 10 DEG C/min, 0.5 ~ 2h is kept the temperature, is naturally cooled to after heat preservation
Room temperature obtains graphene enhancing high-performance foam carbon composite.
The present invention compared with prior art the utility model has the advantages that
(1) present invention carries out functional modification to graphene using small molecule monomer, improves graphene lipophilicity, promotes graphene
With the compatibility between FCC slurry raw material, and reunion of the graphene in FCC slurry is prevented, the dispersibility for solving graphene is asked
Topic, is conducive to graphene and forms nano-dispersion system in FCC slurry.
(2) functionalization graphene that the present invention is added in FCC slurry plays the role of nucleating agent, can substantially speed up
The thermal polycondensation process of FCC slurry promotes the formation of presoma, shortens the time of thermal polycondensation reaction, saves production cost；
(3) present invention can be by the addition of functionalization graphene, and graphene sheet layer structure and its surface functional group can be to warm
The property and structure of presoma after processing carry out Effective Regulation, and preparation has suitable softening point, carbon yield, toluene insoluble
The presoma of the properties such as object content, quinoline insolubles content and institutional framework and interphase content >=98% is the system of foamy carbon
It is standby that quality raw materials are provided.
(4) foamy carbon prepared by the present invention, evenly dispersed graphene can effectively contain the generation of crackle or defect, simultaneously
Using the lamellar structure of its own, foamy carbon is enhanced；Meanwhile graphene surface functional group can effectively promote graphene increasing
The interface bond strength of Qiang Tiyu pitch carbon matrix prevents the interfacial mechanical stripping problem in graphitizing process, improves foam
The structural strength of carbon.Graphene prepared by the present invention enhancing foamed carbon material and pure foam carbon phase ratio, thermal conductivity can be improved 5% ~
20%, compressive strength can be improved 10 ~ 30%.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the SEM figure that graphene prepared by embodiment 1 enhances high-performance foam carbon.
Specific implementation method
The present invention is further elaborated in the following with reference to the drawings and specific embodiments.
Embodiment one:
Step 1: adding graphene oxide into ultrasonic treatment 1h in ethanol solution and obtain dispersion liquid, be then added dropwise into dispersion liquid
Octadecylamine monomer, the back flow reaction 8h at 60 DEG C obtain the graft-functionalized grapheme material of octadecylamine after filtering and washing.
Step 2: octadecylamine graft grapheme material being added in ethyl alcohol, then by mixed solution ultrasound 1h, is divided
Scattered functionalization graphene suspension will then account for the functionalization graphene suspension of gross mass 0.2% and the FCC of polishing purification
Slurry oil carries out magnetic agitation mixing and ultrasonic disperse, and extra alcohol solvent is then removed by way of vacuum distillation and is mixed
Close object.
Step 3: the mixture material that step 2 is obtained, which is placed in autoclave, carries out direct thermal polycondensation, in N2Atmosphere
Under the stirring rate of 500r/min, the mixture is risen to 420 DEG C from room temperature with the rate of 2 °C/min, then regulates and controls kettle
Interior pressure keeps the temperature 8 hours to 3.5MPa, and under constant-pressure conditions, and the precursor that softening point is 260 °C is obtained after cooling.
Step 4: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 350 DEG C to 6MPa with the heating rate of 1 DEG C/min, keep the temperature 4h,
500 DEG C are warming up to the heating rate of 1 DEG C/min again after heat preservation, keeps the temperature 2h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 5: graphene/foamy carbon raw material being put into retort, are warming up to 1000 with the heating rate of 5 DEG C/min
DEG C, keep the temperature 3h；It is put it into high temperature graphitization furnace again, is warming up to 2800 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 1h, protect
Cooled to room temperature after temperature obtains graphene enhancing high-performance foam carbon composite.
The density of obtained graphene enhancing high-performance foam carbon composite is 0.51 g/cm3, compressive strength is
8.1 MPa, thermal conductivity are 125 W/mK.
Embodiment two:
Step 1: adding graphene oxide into ultrasonic treatment 3h in n,N-Dimethylformamide solution and obtain dispersion liquid, in nitrogen
Isocyanate-monomer is added dropwise into dispersion liquid under gas atmosphere protection, is stirred to react 8h under 30 °C, is obtained after filtering and washing
The graft-functionalized grapheme material of isocyanates.
Step 2: isocyanates graft grapheme being added in toluene, then by mixed solution ultrasound 2h, is dispersed
Isocyanates graft grapheme suspension, will then account for the functionalization graphene suspension and polishing purification of gross mass 0.5%
FCC slurry carries out magnetic agitation mixing and ultrasonic disperse, and extra toluene solvant is then removed by way of vacuum distillation and is obtained
To mixture.
Step 3: the mixture material that step 2 is obtained, which is placed in autoclave, carries out direct thermal polycondensation, in N2Atmosphere
Under the stirring rate of 400r/min, the mixture is risen to 400 DEG C from room temperature with the rate of 3 °C/min, then regulates and controls kettle
Interior pressure keeps the temperature 10 hours to 5.0MPa, and under constant-pressure conditions, and the precursor that softening point is 254 °C is obtained after cooling.
Step 4: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 360 DEG C to 4MPa with the heating rate of 3 DEG C/min, keep the temperature 3h,
530 DEG C are warming up to the heating rate of 3 DEG C/min again after heat preservation, keeps the temperature 1h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 5: graphene/foamy carbon raw material are put into retort, are warming up to 800 DEG C with the heating rate of 3 DEG C/min,
Keep the temperature 1h；It is put it into high temperature graphitization furnace again, is warming up to 2600 DEG C with the heating rate of 10 DEG C/min, keep the temperature 2h, heat preservation
After cooled to room temperature, obtain graphene enhancing high-performance foam carbon composite.
The density of obtained graphene enhancing high-performance foam carbon composite is 0.43 g/cm3, compressive strength is
7.3 MPa, thermal conductivity are 106 W/mK.
Embodiment three:
Step 1: adding graphene oxide into ultrasonic treatment 0.5h in cyclohexane solution and obtain dispersion liquid, then into dispersion liquid
Stearic acid monomers are added dropwise, the back flow reaction 4h at 80 DEG C obtains stearic acid grafted functionalization graphene material after filtering and washing
Material.
Step 2: stearic acid grafted graphene adding into acetone then by mixed solution ultrasound 1h, is dispersed
Stearic acid grafted graphene suspension will then account for the functionalization graphene suspension of gross mass 0.01% and the FCC of polishing purification
Slurry oil carries out magnetic agitation mixing and ultrasonic disperse, and extra acetone solvent is then removed by way of vacuum distillation and is mixed
Close object.
Step 3: the mixture material that step 2 is obtained, which is placed in autoclave, carries out direct thermal polycondensation, in N2Atmosphere
Under the stirring rate of 300r/min, the mixture is risen to 450 DEG C from room temperature with the rate of 5 °C/min, then regulates and controls kettle
Interior pressure keeps the temperature 4 hours to 3.0MPa, and under constant-pressure conditions, and the precursor that softening point is 255 °C is obtained after cooling.
Step 4: sieving with 100 mesh sieve, be put into detachable stainless steel mould, in N after precursor is ground2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 320 DEG C to 8MPa with the heating rate of 1 DEG C/min, keep the temperature 3h,
420 DEG C are warming up to the heating rate of 1 DEG C/min again after heat preservation, keeps the temperature 3h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 5: graphene/foamy carbon raw material being put into retort, are warming up to 1000 with the heating rate of 5 DEG C/min
DEG C, keep the temperature 1h；It is put it into high temperature graphitization furnace again, is warming up to 2400 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 1h, protect
Cooled to room temperature after temperature obtains graphene enhancing high-performance foam carbon composite.
The density of obtained graphene enhancing high-performance foam carbon composite is 0.61 g/cm3, compressive strength is
8.6 MPa, thermal conductivity are 95 W/mK.
Example IV:
Step 1: adding graphene oxide into ultrasonic treatment 3h in n,N-Dimethylformamide solution and obtain dispersion liquid, then
Ethylenediamine monomer is added dropwise into dispersion liquid, the back flow reaction 6h at 50 DEG C obtains ethylenediamine grafting functional after filtering and washing
Graphite alkene material.
Step 2: ethylenediamine graft grapheme being added in n,N-Dimethylformamide, then by mixed solution ultrasound
1h, the ethylenediamine graft grapheme suspension dispersed, will then account for the functionalization graphene suspension of gross mass 0.10% with
The FCC slurry of polishing purification carries out magnetic agitation mixing and ultrasonic disperse, and it is extra then to be removed by way of vacuum distillation
N,N-dimethylformamide solvent obtains mixture.
Step 3: the mixture material that step 2 is obtained, which is placed in autoclave, carries out direct thermal polycondensation, in N2Atmosphere
Under the stirring rate of 600r/min, the mixture is risen to 420 DEG C from room temperature with the rate of 1 °C/min, then regulates and controls kettle
Interior pressure keeps the temperature 8 hours to 0.5MPa, and under constant-pressure conditions, and the precursor that softening point is 268 °C is obtained after cooling.
Step 4: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 330 DEG C to 5MPa with the heating rate of 2 DEG C/min, keep the temperature 2h,
480 DEG C are warming up to the heating rate of 2 DEG C/min again after heat preservation, keeps the temperature 2h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 5: graphene/foamy carbon raw material being put into retort, are warming up to 1000 with the heating rate of 5 DEG C/min
DEG C, keep the temperature 1h；It is put it into high temperature graphitization furnace again, is warming up to 2800 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 1h, protect
Cooled to room temperature after temperature obtains graphene enhancing high-performance foam carbon composite.
The density of obtained graphene enhancing high-performance foam carbon composite is 0.53 g/cm3, compressive strength is
7.4 MPa, thermal conductivity are 118 W/mK.
Embodiment five:
Step 1: adding graphene oxide into ultrasonic treatment 1h in chloroformic solution and obtain dispersion liquid, be then added dropwise into dispersion liquid
Oleic acid monomer, the back flow reaction 5h at 80 DEG C obtain oleic acid modified functionalization graphene material after filtering and washing.
Step 2: oleic acid modified graphene being added in tetrahydrofuran, then by mixed solution ultrasound 2h, is dispersed
Oleic acid modified graphene suspension, will then account for the functionalization graphene suspension of gross mass 0.30% and the FCC of polishing purification
Slurry oil carries out magnetic agitation mixing and ultrasonic disperse, and extra tetrahydrofuran solvent is then removed by way of vacuum distillation and is obtained
To mixture.
Step 3: the mixture material that step 2 is obtained, which is placed in autoclave, carries out direct thermal polycondensation, in N2Atmosphere
Under the stirring rate of 500r/min, the mixture is risen to 430 DEG C from room temperature with the rate of 2 °C/min, then regulates and controls kettle
Interior pressure keeps the temperature 10 hours to 3.0MPa, and under constant-pressure conditions, and the precursor that softening point is 272 °C is obtained after cooling.
Step 4: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 320 DEG C to 6MPa with the heating rate of 3 DEG C/min, keep the temperature 2h,
530 DEG C are warming up to the heating rate of 3 DEG C/min again after heat preservation, keeps the temperature 2h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 5: graphene/foamy carbon raw material being put into retort, are warming up to 1000 with the heating rate of 5 DEG C/min
DEG C, keep the temperature 1h；It is put it into high temperature graphitization furnace again, is warming up to 2600 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 1h, protect
Cooled to room temperature after temperature obtains graphene enhancing high-performance foam carbon composite.
The density of obtained graphene enhancing high-performance foam carbon composite is 0.49 g/cm3, compressive strength is
6.7 MPa, thermal conductivity are 127 W/mK.
Comparative example one:
Step 1: the FCC slurry of polishing purification being placed in autoclave and carries out direct thermal polycondensation, in N2Atmosphere and 500r/
Under the stirring rate of min, the mixture is risen to 420 DEG C from room temperature with the rate of 2 °C/min, then regulate and control kettle in pressure extremely
3.5MPa, and 10 hours are kept the temperature under constant-pressure conditions, the precursor that softening point is 251 °C is obtained after cooling.
Step 2: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 350 DEG C to 6MPa with the heating rate of 1 DEG C/min, keep the temperature 4h,
500 DEG C are warming up to the heating rate of 1 DEG C/min again after heat preservation, 2h is kept the temperature, obtains foamy carbon raw material after cooling.
Step 3: foamy carbon raw material being put into retort, are warming up to 1000 DEG C with the heating rate of 5 DEG C/min, heat preservation
3h；It is put it into high temperature graphitization furnace again, is warming up to 2800 DEG C with the heating rate of 5 DEG C/min, 1h is kept the temperature, after heat preservation
Cooled to room temperature obtains foamed carbon material.
The density of obtained foamed carbon material is 0.64 g/cm3, compressive strength is 6.2 MPa, and thermal conductivity is 74 W/
m·K。
Comparative example two
Step 1: graphene being added in ethyl alcohol, then by mixed solution ultrasound 1h, graphene suspension is obtained, will then account for
The graphene suspension of gross mass 0.2% carries out magnetic agitation with the FCC slurry of polishing purification and mixes simultaneously ultrasonic disperse, then logical
The mode for crossing vacuum distillation removes extra solvent and obtains mixture.
Step 2: the mixture material that step 1 is obtained, which is placed in autoclave, carries out direct thermal polycondensation, in N2Atmosphere
Under the stirring rate of 500r/min, the mixture is risen to 420 DEG C from room temperature with the rate of 2 °C/min, then regulates and controls kettle
Interior pressure keeps the temperature 8 hours to 3.5MPa, and under constant-pressure conditions, and the precursor that softening point is 257 °C is obtained after cooling.
Step 3: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 350 DEG C to 6MPa with the heating rate of 1 DEG C/min, keep the temperature 4h,
500 DEG C are warming up to the heating rate of 1 DEG C/min again after heat preservation, keeps the temperature 2h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 4: graphene/foamy carbon raw material being put into retort, are warming up to 1000 with the heating rate of 5 DEG C/min
DEG C, keep the temperature 3h；It is put it into high temperature graphitization furnace again, is warming up to 2800 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 1h, protect
Cooled to room temperature after temperature obtains graphene composite foam carbon material.
The density of obtained graphene composite foam carbon material is 0.45 g/cm3, compressive strength is 4.4 MPa, thermally conductive
Rate is 59 W/mK.Graphene bad dispersibility in foamy carbon, mechanical property and heating conduction to foamy carbon bring negative shadow
It rings.
Comparative example three
Step 1: using asphalt powder as presoma, by its with 0.2% graphene oxide by ball milling mixing it is uniform, oxidation
The modified presoma of graphene.
Step 2: crossing 200 meshes after precursor is ground, be put into detachable stainless steel mould, in N2Under gas shield,
It foams in a high pressure reaction kettle, constant pressure in kettle is maintained to be warming up to 350 DEG C to 6MPa with the heating rate of 1 DEG C/min, keep the temperature 4h,
500 DEG C are warming up to the heating rate of 1 DEG C/min again after heat preservation, keeps the temperature 2h, it is raw to obtain graphene/foamy carbon after cooling
Material.
Step 3: graphene/foamy carbon raw material being put into retort, are warming up to 1000 with the heating rate of 5 DEG C/min
DEG C, keep the temperature 3h；It is put it into high temperature graphitization furnace again, is warming up to 2800 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 1h, protect
Cooled to room temperature after temperature obtains graphene composite foam carbon material.
The density of obtained graphene composite foam carbon material is 0.59 g/cm3, compressive strength is 4.9 MPa, thermally conductive
Rate is 78 W/mK.
Embodiment and the foamy carbon performance of comparative example preparation relatively see the table below.
1 embodiment of table and the foamy carbon performance of comparative example preparation compare
Claims (10)
1. a kind of preparation method of high-performance foam carbon, which comprises the following steps:
(1) functionalization graphene is added into the catalytic cracking of polishing purification (FCC) slurry oil, the modified FCC oil of graphene is made
Slurry；
(2) FCC slurry modified to the graphene of step (1), heating modification, is made presoma；
(3) under high temperature, high pressure, the presoma of step (2), which passes through from foaming pyrolysis, obtains graphene/foamy carbon raw material；
(4) raw material of step (3) are carbonized, are graphitized to obtain graphene enhancing high-performance foam carbon.
2. preparation method according to claim 1, which is characterized in that the preparation of functionalization graphene in the step (1)
Method: it adds graphene oxide into 0.5 ~ 3h of ultrasonic treatment in organic solution 1 and obtains dispersion liquid, be subsequently added into small molecule list
Body, under atmospheric condition at 30 ~ 80 DEG C 4 ~ 8h of back flow reaction, functionalization graphene material is obtained after filtering and washing.
3. preparation method according to claim 2, which is characterized in that the organic solvent 1 is ethyl alcohol, isopropanol, third
One of ketone, benzene,toluene,xylene, chloroform, tetrahydrofuran, hexamethylene, N,N-dimethylformamide, dimethyl sulfoxide or
It is several.
4. preparation method according to claim 2, which is characterized in that the small molecule monomer is ether epoxy, isocyanic acid
Ester, stearic acid, oleic acid, octadecylamine, one or more of oleyl amine, ethanol amine, ethylenediamine, hexamethylene diamine.
5. preparation method according to claim 1, which is characterized in that the modified FCC oil of graphene in the step (1)
The condition of slurry are as follows: functionalization graphene is added in organic solution 2 described in step (1), then by the mixed solution ultrasound 0.5
~ 3h, the functionalization graphene suspension dispersed, then by the FCC slurry of functionalization graphene suspension and polishing purification
Magnetic agitation mixing and ultrasonic disperse are carried out according to a certain percentage, and extra organic solvent is then removed by vacuum distillation and is obtained
The modified FCC slurry of graphene；
The organic solvent 2 be ethyl alcohol, isopropanol, acetone, benzene,toluene,xylene, chloroform, tetrahydrofuran, hexamethylene, N,
One or more of dinethylformamide, dimethyl sulfoxide.
6. preparation method according to claim 1, which is characterized in that the FCC slurry of the polishing purification in the step (1)
It is less than the purification slurry oil of 100ppm, sulfur content≤2500ppm, asphalitine≤9% for ash content.
7. preparation method according to claim 1, which is characterized in that the functionalization graphene addition in the step (1)
It is 0.01% ~ 0.50% that amount, which accounts for FCC slurry mass percent,.
8. preparation method according to claim 1, which is characterized in that the specific preparation of presoma in the step (2)
Technique are as follows: the modified FCC slurry of graphene is placed in autoclave and carries out direct thermal polycondensation, inert atmosphere and 300 ~
Under the stirring rate of 600r/min, the mixture is risen to 350 ~ 450 DEG C from room temperature with the rate of 1 ~ 5 °C/min, is then adjusted
It controls in kettle pressure and keeps the temperature 4 ~ 10 hours to 0.5 ~ 5.0MPa, and under constant-pressure conditions, obtain precursor after cooling.
9. preparation method according to claim 1, which is characterized in that the graphene of affiliated step (3)/foamy carbon is raw
Expect specific preparation process are as follows: 100 ~ 200 meshes will be crossed after graphene/mesophase pitch precursor grinding, in inert gas shielding
Under, it foams in a high pressure reaction kettle, maintains in kettle constant pressure to 4 ~ 8MPa, 320 are warming up to the heating rate of 1 ~ 3 DEG C/min ~
360 DEG C, 1 ~ 4h is kept the temperature, is warming up to 420 ~ 530 DEG C again after heat preservation with the heating rate of 1 ~ 3 DEG C/min, keeps the temperature 1 ~ 3h, it is cooling
Graphene/foamy carbon raw material are obtained afterwards.
10. preparation method according to claim 1, which is characterized in that step (4) graphene enhances high-performance foam
The preparation process of carbon are as follows: graphene/foamy carbon raw material are put into retort, are warming up to 800 with the heating rate of 1 ~ 5 DEG C/min
~ 1000 DEG C, keep the temperature 1 ~ 3h；It is put it into high temperature graphitization furnace again, 2400 are warming up to the heating rate of 5 ~ 10 DEG C/min ~
2800 DEG C, 0.5 ~ 2h is kept the temperature, cooled to room temperature after heat preservation obtains graphene enhancing high-performance foam carbon composite wood
Material.
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