CN105480971B - A kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material - Google Patents
A kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material Download PDFInfo
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- CN105480971B CN105480971B CN201610059718.7A CN201610059718A CN105480971B CN 105480971 B CN105480971 B CN 105480971B CN 201610059718 A CN201610059718 A CN 201610059718A CN 105480971 B CN105480971 B CN 105480971B
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- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C01P2004/00—Particle morphology
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
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- C01P2006/16—Pore diameter
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material, belong to carbon materials field.By pitch, additive, dispersant by ball milling mixing, the wherein mass ratio of pitch and additive is 100 to the present invention:1~100, the mass fraction of dispersant is 0.1% 10%, the volume fraction of ball milling solvent is 0.1% 100%, and additive, dispersant and ball milling solvent purity are more than 99%, then pass through the techniques such as drying, charing, pickling to prepare a kind of three-dimensional grapheme material with meso-hole structure.Product purity of the invention is high（Purity 98 ~ 100%）, specific surface area it is big（500~2500m2/g）, size uniform, while fault of construction is few, the number of plies is less（1~5 layer）, and preparation cost is low, and it is simple to operate, promote easy.
Description
Technical field
The invention belongs to carbon structure Material Field, and in particular to a kind of preparation of asphaltic base three-dimensional meso-hole grapheme material
Method.
Background technology
Graphene is used as a kind of new carbon material, Two-dimensional Carbon honeycomb and excellent physical chemistry with uniqueness
Energy.The Graphene of individual layer has specific surface, good thermal conductivity, excellent characteristic electron and the superpower mechanical performance of superelevation,
Therefore it is latent with very big utilization in fields such as electronic device, detector, energy storage/conversion, sensor, biological medicine transports
Power.Scientific research and commercial Application based on Graphene application, are that the progress of energy field opens new development situation
And market, especially for storage device requirement storing hydrogen high, fuel cell, solar cell and lithium ion battery, electricity
The aspects such as container, Graphene all has excellent performance.
Porous graphene as a kind of grapheme material with tridimensional network, with uniform pore structure, can
On the basis of the intrinsic superperformance of Graphene is retained, overcome grapheme material itself to reunite and stack, farthest utilize
The performances such as the specific surface area and electron mobility of its super large.Good mechanical performance, excellent electric conductivity and thermal conductivity so that many
Graphene relatively other porous materials in hole more are had an optimistic view of by numerous researchers and enterprise.Additionally, different sizes and shapes
The presence in hole is Graphene provides great possibility with the compound of other materials, particularly in gas absorption, separates, deposits
The aspect such as storage and catalyst carrier will have more prominent application.
The method for preparing three-dimensional porous Graphene at present mainly has two classes：Template and non-template method.Template is divided into firmly
Template and soft template method.Hard template method includes chemical vapour deposition technique and epitaxial growth method, such as with the inorganic grain such as mesoporous silicon
Son is template, prepares aperture, the mesoporous grapheme material of morphology controllable；Soft template aspect is mainly with generated in-situ polymerization
Thing, porous metallic particles or oxide prepare porous graphene as template.Non-template refers mainly to chemical etching method and includes
The methods such as activation of potassium hydroxide method, nitric acid oxidation method, catalyst oxidizing process, raw material mainly uses graphene nanometer sheet, by changing
Reactive ion etching graphene nano lamella is learned, significantly to avoid the reunion of Graphene.But, there is product and lack in above-mentioned preparation method
Fall into it is many, not environmentally, complex process, yield poorly, production cost is high, Difficulty the problems such as.Therefore, one kind is invented similar to soft mode
The method that is inexpensive and can largely preparing porous graphene material of plate method is necessary and significant.
The content of the invention
It is an object of the invention to provide a kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material, obtained drip
The specific surface area of blue or green base three-dimensional meso-hole Graphene is 500~2500m2/ g, 1~5 layer of the number of plies, aperture 2nm~50nm, purity 98 ~
100%；Raw material sources enrich, and price is low；Process equipment is simple, it is easy to mass produce.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material, comprises the following steps that：
（1）The ball milling mixing of pitch, additive and dispersant
To grind in pitch, additive and the dispersant addition ball mill of sieving, being subsequently adding ball milling solvent carries out ball milling
Treatment, taking-up is dried；The mass ratio of pitch and additive is 100:1~100；The mass fraction of dispersant is 0.1%-
10%；The volume fraction of ball milling solvent is 0.1%-100%；Additive, dispersant and ball milling solvent purity are more than 99%；It is ground
Pitch granularity is 50-300 mesh after sieve；Ball milling parameter is：Rotational speed of ball-mill is 60r/min-1200r/min, and Ball-milling Time is 0.1h-
12h；Drying temperature is 40~120 DEG C, and drying time is 1 ~ 12h；
The pitch for being used for selected from coal tar pitch and petroleum asphalt, bitumen, slag oil asphalt, plant asphalt, synthetic asphalts, in
Between one kind in asphalt phase, emulsified asphalt, Aqua-mesophase, wood pitch；
The additive for being used is the nano alumina particles of different-grain diameter（2nm-50nm）, nano aluminium oxide liquid（Grain
Footpath scope 2nm-20nm, mass fraction 5-50%）With nano aluminium oxide water dispersion pulp（Particle size range 5nm-15nm, mass fraction 5-
50%）In one kind；
The dispersant for being used is polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyvinyl acetal, poly- second
Enol butyral, Sodium Polyacrylate, triethyl group hexyl phosphoric acid, alkyl sulfate, alkylsulfonate, alkylbenzenesulfonate, methyl
Amylalcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyethylene glycol ester, Tissuemat E, OPE, water
Solution HPMA, sodium glycocholate, glycerin monostearate, paraffin, phosphotidats, polyoxyethylene, polyacrylate, fiber two
The many aldehyde of glycolipid, alkyl polyglycoside, ring-type, many ketone of ring-type, quaternary ammonium salt, B oxidation fat alcohol, diglycollic amide, Macrogol Ester, fat
One kind in fat alcohol, APEO and fat alcohol ethoxyl compound；
The ball milling solvent for being used for water, ethanol, dichloromethane, acetone, chloroform, methyl alcohol, tetrahydrofuran, carbon tetrachloride,
Hexamethylene, isopropanol, 1,2- trichloroethanes, triethylamine, toluene, pyridine, ethylenediamine, butanol, acetic acid, chlorobenzene, paraxylene, two
Toluene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, DMAC N,N' dimethyl acetamide, N-METHYLFORMAMIDE, phenol, diformazan are sub-
Sulfone, ethylene glycol, 1-METHYLPYRROLIDONE, the one kind in formamide, sulfolane, glycerine；
（2）Charing
By step（1）The raw material for mixing is put into atmosphere furnace, is incubated after then heating to predetermined temperature, is cooled to room temperature
Take out；Charring process parameter is：
Heating rate：1 DEG C/min~50 DEG C/min
Predetermined temperature：1100 DEG C~2000 DEG C
Soaking time：0.1 h~10 h
Protective atmosphere：N2Or Ar2
Gas flow：25 mL/min~300 mL/min；
（3）Pickling
By step（2）Gained carbonizing production is placed in acid solution and stirs, and deionized water is fully washed to neutrality, is then placed in 40
1 ~ 12h is dried in~100 DEG C of vacuum drying ovens, vacuum is 1.0 × 10-1~1.0×105Pa；Acid cleaning process parameter is：
Acid solution：One kind in hydrochloric acid, oxalic acid, sulfuric acid, hydrofluoric acid
Acid solution molar concentration：0.05mol/L~6 mol/L
Mixing time：1~5h
Mixing speed：25~200 r/min.
The beneficial effects of the present invention are：
1）The specific surface area of obtained asphaltic base three-dimensional meso-hole grapheme material of the invention is 500~2500m2/ g, the number of plies 1
~5 layers, aperture 2nm~50nm, high purity 98 ~ 100%；
2）The raw material sources that preparation method of the invention is used enrich, and price is low；Process equipment is simple, it is easy to extensive
Production.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of the asphaltic base three-dimensional meso-hole grapheme material prepared using the technique of embodiment 1；
Fig. 2 is the transmission electron microscope picture of the asphaltic base three-dimensional meso-hole grapheme material prepared using the technique of embodiment 2；
Fig. 3 is the transmission electron microscope picture of the asphaltic base three-dimensional meso-hole grapheme material prepared using the technique of embodiment 3；
Fig. 4 is the transmission electron microscope picture of the asphaltic base three-dimensional meso-hole grapheme material prepared using the technique of embodiment 4；
Fig. 5 is the transmission electron microscope picture of the asphaltic base three-dimensional meso-hole grapheme material prepared using the technique of embodiment 5.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
It is 2nm nano aluminium oxide liquid that coal tar pitch is ground to after 180 mesh with particle diameter（Mass fraction 30%）Add ball grinder
In, the mass ratio of coal tar pitch and nano aluminium oxide is 1:1；Used as dispersant, mass fraction is selection polyvinylpyrrolidone
10%；Ball milling solvent is DMF, and volume fraction is 20%；It is 600r/min in rotational speed of ball-mill, after ball milling 3h, puts
It is placed in 80 DEG C of drying boxes, dries 8h and remove ball milling solvent.Drying sample is positioned in atmosphere furnace, argon gas is passed through（Argon gas stream
It is 100mL/min to measure）, 1800 DEG C are warming up to 15 DEG C/min, 2h is incubated, it is cooled to room temperature taking-up.Carbonizing production is positioned over
Hydrochloric acid solution（Acid solution molar concentration is 1mol/L）In, 5h is stirred, mixing speed is 120 revs/min, filters and is washed with deionized water
To neutrality.It is positioned over vacuum drying chamber（1.0×10-1Pa）60 DEG C of middle drying drying 12 hours, that is, obtain asphaltic base three-dimensional meso-hole
Graphene.Prepared mesoporous grapheme material performance is as follows：The number of plies is 1-3 layers, and aperture size is 2nm-5nm, specific surface area
It is 2500m2/ g, purity 98.2%.
Embodiment 2
Mesophase pitch is ground to after 100 mesh and is during 15nm nano alumina particles add ball grinder with particle diameter, it is middle
The mass ratio of asphalt phase and nano aluminium oxide is 2:1；Used as dispersant, mass fraction is 5% to selection Sodium Polyacrylate；Ball milling is molten
Agent is dichloromethane, and volume fraction is 10%；It is 900r/min in rotational speed of ball-mill, after ball milling 1h, is positioned in 40 DEG C of drying boxes,
Dry 4h and remove ball milling solvent.Drying sample is positioned in atmosphere furnace, nitrogen is passed through（Nitrogen flow is 50mL/min）, with 20
DEG C/min is warming up to 1600 DEG C, is incubated 8h, is cooled to room temperature taking-up.Carbonizing production is positioned over oxalic acid solution（Acid solution mole is dense
It is 2mol/L to spend）In, 4h is stirred, mixing speed is 60 revs/min, filters and is washed with deionized water to neutrality.Vacuum is positioned over to do
Dry case（1.0×10-1Pa）80 DEG C of middle drying drying 4 hours, that is, obtain asphaltic base three-dimensional meso-hole Graphene.Prepared mesoporous stone
Black alkene material property is as follows：The number of plies is 1-4 layers, and aperture size is 10nm-15nm, and specific surface area is 1000m2/ g, purity
99.5%。
Embodiment 3
It is 10nm nano aluminium oxide water dispersion pulps by liquid emulsion pitch and average grain diameter（Mass fraction 20wt%）Add ball
In grinding jar, the mass ratio of emulsified asphalt and nano aluminium oxide aqueous dispersions is 4:1；Selection APEO is used as dispersant, matter
Amount fraction is 2%；Ball milling solvent is deionized water, and volume fraction is 3%；It is 300r/min in rotational speed of ball-mill, after ball milling 12h, puts
It is placed in 60 DEG C of drying boxes, dries 10h and remove ball milling solvent.Drying sample is positioned in atmosphere furnace, argon gas is passed through（Argon gas stream
It is 150mL/min to measure）, 1700 DEG C are warming up to 10 DEG C/min, 3h is incubated, it is cooled to room temperature taking-up.Carbonizing production is positioned over
Hydrochloric acid solution（Acid solution molar concentration is 2mol/L）In, 1h is stirred, mixing speed is 80 revs/min, filters and is washed with deionized water
To neutrality.It is positioned over vacuum drying chamber（1.0×10-1Pa）60 DEG C of middle drying drying 10 hours, that is, obtain asphaltic base three-dimensional meso-hole
Graphene.Prepared mesoporous grapheme material performance is as follows：The number of plies is 1-5 layers, and aperture size is 5nm-10nm, specific surface area
It is 1350m2/ g, purity 98.9%.
Embodiment 4
Will bitumen grind 300 mesh after with average grain diameter be 10nm nano alumina particles add ball grinder in, naturally
The mass ratio of pitch and nano aluminium oxide is 5:1；Used as dispersant, mass fraction is 0.1% to selection polyvinyl alcohol -400；Ball milling
Solvent is ethanol, and volume fraction is 50%；It is 800r/min in rotational speed of ball-mill, after ball milling 2h, is positioned in 50 DEG C of drying boxes, does
Dry 12h removes ball milling solvent.Drying sample is positioned in atmosphere furnace, argon gas is passed through（Argon flow amount is 200mL/min）, with 30
DEG C/min is warming up to 1900 DEG C, is incubated 0.5h, is cooled to room temperature taking-up.Carbonizing production is positioned over hydrofluoric acid solution（Acid solution is rubbed
Your concentration is 0.5mol/L）In, 2.5h is stirred, mixing speed is 100 revs/min, filters and is washed with deionized water to neutrality.Place
In vacuum drying chamber（1.0×10-1Pa）80 DEG C of middle drying drying 12 hours, that is, obtain asphaltic base three-dimensional meso-hole Graphene.It is made
Standby mesoporous grapheme material performance is as follows：The number of plies is 1-5 layers, and aperture size is 4nm-10nm, and specific surface area is 1100m2/ g,
Purity 99.6%.
Embodiment 5
By asphalt grind 50 mesh after with average grain diameter be 15nm nano aluminium oxide water dispersion pulps（Mass fraction 50%）Plus
Enter in ball grinder, the mass ratio of asphalt and nano aluminium oxide water dispersion pulp is 10:1；Selection lauryl sodium sulfate conduct
Dispersant, mass fraction is 2.5%；Ball milling solvent is hexamethylene, and volume fraction is 25%；It is 300r/min, ball in rotational speed of ball-mill
After mill 6h, it is positioned in 70 DEG C of drying boxes, dries 6h and remove ball milling solvent.Drying sample is positioned in atmosphere furnace, argon is passed through
Gas（Argon flow amount is 120mL/min）, 2000 DEG C are warming up to 5 DEG C/min, 0.5h is incubated, it is cooled to room temperature taking-up.Will charing
Product is positioned over sulfuric acid solution（Acid solution molar concentration is 5mol/L）In, 3h is stirred, mixing speed is 60 revs/min, filters and is used in combination
Deionized water is washed till neutrality.It is positioned over vacuum drying chamber（1.0×10-1Pa）80 DEG C of middle drying drying 12 hours, that is, obtain pitch
Base three-dimensional meso-hole Graphene.Prepared mesoporous grapheme material performance is as follows：The number of plies is 2-5 layers, and aperture size is 10nm-
15nm, specific surface area is 900m2/ g, purity 98%.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (5)
1. a kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material, it is characterised in that：Comprise the following steps that：
（1）The ball milling mixing of pitch, additive and dispersant
To grind in pitch, additive and the dispersant addition ball mill of sieving, being subsequently adding ball milling solvent carries out ball-milling treatment,
Taking-up is dried；The mass ratio of pitch and additive is 100:1~100；The mass fraction of dispersant is 0.1%-10%；Ball milling
The volume fraction of solvent is 0.1%-100%；Additive, dispersant and ball milling solvent purity are more than 99%；
（2）Charing
By step（1）The raw material for mixing is put into atmosphere furnace, is incubated after then heating to predetermined temperature, is cooled to room temperature and is taken
Go out；Charring process parameter is：
Heating rate：1 DEG C/min~50 DEG C/min
Predetermined temperature：1100 DEG C~2000 DEG C
Soaking time：0.1 h~10 h
Protective atmosphere：N2Or Ar2
Gas flow：25 mL/min~300 mL/min；
（3）Pickling
By step（2）Gained carbonizing production is placed in acid solution and stirs, and deionized water fully washed to neutrality, it is then placed in 40~
1 ~ 12h is dried in 100 DEG C of vacuum drying ovens, vacuum is 1.0 × 10-1~1.0×105Pa；Acid cleaning process parameter is：
Acid solution：One kind in hydrochloric acid, oxalic acid, sulfuric acid
Acid solution molar concentration：0.05mol/L~6 mol/L
Mixing time：1~5h
Mixing speed：25~200 r/min；
Described additive is the one kind in nano alumina particles, nano aluminium oxide liquid and nano aluminium oxide water dispersion pulp；
Described nano alumina particles particle size range 2nm-50nm；Described nano aluminium oxide liquid particle size range 2nm-20nm, matter
Amount fraction 5-50%；Described nano aluminium oxide water dispersion pulp particle size range 5nm-15nm, mass fraction 5-50%.
2. the preparation method of a kind of asphaltic base three-dimensional meso-hole grapheme material according to claim 1, it is characterised in that：Institute
The pitch stated is selected from coal tar pitch and petroleum asphalt, bitumen, slag oil asphalt, plant asphalt, synthetic asphalts, mesophase pitch, emulsification
One kind in pitch, Aqua-mesophase and wood pitch.
3. method according to claim 1, it is characterised in that：Described dispersant is polyvinyl alcohol, polyethylene glycol, poly- second
Alkene pyrrolidone, polyvinyl acetal, polyvinyl butyral resin, Sodium Polyacrylate, triethyl group hexyl phosphoric acid, alkylsurfuric acid
Salt, alkylsulfonate, alkylbenzenesulfonate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fatty acid polyglycol second
Diol ester, Tissuemat E, OPE, HPMA, sodium glycocholate, glycerin monostearate, paraffin, phosphatide
Hydrochlorate, polyoxyethylene, polyacrylate, cellobiose fat, alkyl polyglycoside, many aldehyde of ring-type, many ketone of ring-type, quaternary ammonium salt, ethoxyquin
One kind in fatty alcohol, diglycollic amide, Macrogol Ester, fatty alcohol, APEO and fat alcohol ethoxyl compound.
4. method according to claim 1, it is characterised in that：Described ball milling solvent is water, ethanol, dichloromethane, third
Ketone, chloroform, methyl alcohol, tetrahydrofuran, carbon tetrachloride, hexamethylene, isopropanol, 1,2- trichloroethanes, triethylamine, toluene, pyridine, second
Diamines, butanol, acetic acid, chlorobenzene, paraxylene, dimethylbenzene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, N, N- dimethyl
In acetamide, N-METHYLFORMAMIDE, phenol, dimethyl sulfoxide, ethylene glycol, 1-METHYLPYRROLIDONE, formamide, sulfolane and glycerine
One kind.
5. method according to claim 1, it is characterised in that：Step（1）Pitch granularity is 50-300 after middle grinding sieving
Mesh；Ball milling parameter is：Rotational speed of ball-mill is 60r/min-1200r/min, and Ball-milling Time is 0.1h-12h；Drying temperature be 40~
120 DEG C, drying time is 1 ~ 12h.
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| CN108163844A (en) * | 2018-03-19 | 2018-06-15 | 程贤甦 | A kind of preparation method that graphene is prepared using waste tire rubber powder |
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| CN106185890B (en) * | 2016-07-04 | 2019-02-15 | 石河子大学 | A kind of preparation method of porous class graphene |
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| CN111269329B (en) * | 2020-02-28 | 2022-10-25 | 上海瑞盛联信息科技有限公司 | Novel asphalt emulsifier and preparation method thereof |
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| CN114408903A (en) * | 2022-01-12 | 2022-04-29 | 华南理工大学 | Method for preparing in-plane porous few-layer graphene material at low temperature in environment-friendly manner |
| CN115010118B (en) * | 2022-06-06 | 2024-01-23 | 武汉理工大学 | Nitrogen and sulfur doped hierarchical macroporous/mesoporous graphene and preparation method and application thereof |
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| US7071258B1 (en) * | 2002-10-21 | 2006-07-04 | Nanotek Instruments, Inc. | Nano-scaled graphene plates |
| CN103395776B (en) * | 2013-08-02 | 2015-07-01 | 福州大学 | Asphalt-based activated graphene sheet and preparation method thereof |
| CN103539103B (en) * | 2013-10-25 | 2015-10-14 | 福州大学 | A kind of Low-cost carbon graphene sheet and preparation method thereof |
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