CN105752970B - A kind of preparation method of carbon nano tube/graphene compound - Google Patents
A kind of preparation method of carbon nano tube/graphene compound Download PDFInfo
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- CN105752970B CN105752970B CN201610188685.6A CN201610188685A CN105752970B CN 105752970 B CN105752970 B CN 105752970B CN 201610188685 A CN201610188685 A CN 201610188685A CN 105752970 B CN105752970 B CN 105752970B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention discloses a kind of preparation method of carbon nano tube/graphene compound.CNT, additive and surfactant are weighed, CNT, additive and surfactant are 100 in mass ratio:1~100:0.01 ~ 1 mixing, then toward the well mixed rear and distilling off solvent of stirring solvent of 1 ~ 10 times of quality of addition in mixture, it is subsequently placed in baking oven and is dried, then pass through charing and acid cleaning process to prepare carbon nano tube/graphene compound.Using situ study, graphene is made without advance, the specific surface area height of obtained carbon nano tube/graphene compound, good electrical property, specific capacitance is 100~350 F/g, and specific surface area is 150~400 m2/ g, graphite alkylene degree is up to 30%~70%, and abundant raw material, cheap, easily realizes industrialization.
Description
Technical field
The invention belongs to nano-carbon material preparation field, relates generally to a kind of preparation of carbon nano tube/graphene compound
Method.
Background technology
Graphene is from having been become focus to study both at home and abroad since successfully preparing, in the short time.As a kind of excellent
Two-dimentional carbon material, it is excellent that unique electronic structure makes it have high conductivity, high-transmittance, high-specific surface area, high intensity etc.
Physical and chemical performance, mechanical performance and good electrical and thermal conductivity performance, carried in various electrode of electrochemical device materials, catalyst
Body, sensing material and energy storage etc. have good application prospect.And CNT (CNTs) is used as a kind of One-dimensional Quantum material
Material, in addition to the hollow-core construction with uniqueness, its radial dimension is nanometer scale, and axial dimension is micron dimension, the end group of pipe two
All sealed in sheet, this makes it have the premium properties such as very high intensity, pliability, in solar cell, catalysis and biotechnology
The fields such as new industry are widely used, and it has certain similar property to graphene, and single-walled carbon nanotube is seen as one
The graphene film of individual drum.But because graphene is different from the structure of CNT, they in performance and application aspect then
There is some difference.In order to make full use of both advantages and overcome the shortcomings of that two kinds of materials are existing in itself, people generally will
Graphene and CNTs carry out the compound carbon nano tube/graphene compound with obtained tridimensional network, by between them
Cooperative effect, the performance of compound can be substantially improved, it is shown the performance more excellent than any one homogenous material, obtain
To characteristics such as more preferable isotropism thermal conductivity, isotropic conductivities, so as in ultracapacitor, solar cell, display
Device, biological detection, fuel cell etc. have good application prospect.
The main method for preparing carbon nano tube/graphene compound at present has mechanical mixing, chemical vapour deposition technique
（CVD）With LBL self-assembly method (LBL).Mechanical mixing is simply to be mixed graphene and CNT, then to it
Carry out subsequent treatment and obtain graphene/carbon nano-tube compound, generally exist and disperse uneven phenomenon, and be difficult to play the two
Cooperative effect in performance；CVD is then the deposited graphite alkene film in the substrates such as copper foil, and catalysis is coated on graphene film
Agent, then in catalyst surface sedimentary CNT, finally remove substrate and obtained carbon nano tube/graphene laminated film, but
It is low to there is PROCESS FOR TREATMENT temperature height, sedimentation rate, and the influence such as pernicious gas can be produced during the course of the reaction；And LBL methods are main
By the interaction between molecule or ion, in substrate surface alternating deposit graphene and CNT, to obtain multi-layer thin
Membrane material, but the raw material used typically carry active function groups, and in use, free functional group easily occurs irreversible
Redox reaction, so as to have a strong impact on overall performance.Mostly be present the problem of certain in existing technology, need to typically close in advance
Into graphene, and can introduce that impurity, technique are cumbersome, subsequent treatment is complicated unavoidably in building-up process, cost height, environmental pollution,
And it is difficult to industrialized production etc., it greatly limit graphene/CNTs application and popularization.
The content of the invention
It is an object of the invention to provide a kind of preparation method of carbon nano tube/graphene compound, obtained carbon is received
The specific surface area of mitron/graphene complex is high, good electrical property, and specific capacitance be 100~350 F/g, specific surface area for 150~
400 m2/ g, graphite alkylene degree is up to the % of 30 %~70, and abundant raw material, cheap, easily realizes industrialization.
To achieve the above object, the present invention adopts the following technical scheme that：
（1）The mixing of raw material
CNT, additive and surfactant are weighed, CNT, additive and surfactant are in mass ratio
1~100: 100:0.01 ~ 1 mixing, then the stirring solvent toward 1 ~ 10 times of quality of addition in mixture is well mixed rear and distills
Go out solvent, be subsequently placed in baking oven and be dried；Whipping temp is 25~150 DEG C, and mixing time is 1~5h；Drying temperature is
35~100 DEG C, drying time is 1 ~ 12h；
Used CNT is single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube, the more wall carbon of functionalization
Nanotube, short MWCNTs, industrial multi-walled carbon nano-tube, graphite multi-walled carbon nano-tube, the thin wall carbon nano-tube of large diameter
One or more of mixing of pipe and carbon nano-tube fibre；
Used additive be aluminium chloride, aluminum sulfate, aluminium carbonate, aluminum acetate, aluminum nitrate, aluminium hydroxide, sodium metaaluminate,
Aluminum phosphate, alumina silicate, aluminium carbide, ten sulfate dihydrate aluminium ammoniums, metasilicic acid aluminium, trifluoromethanesulfonic acid aluminium, trialkylaluminium, dialkyl group chlorination
Aluminium, an alkyl al dichloride, the aluminium of trialkyl tri-chlorination two, aluminium isopropoxide, butyl aluminium, aluminium acetate, aluminium triformate, oxalic acid aluminium, propionic acid
Aluminium, polyaluminium chloride, alumina silicate, fluoric acid aluminium, aluminium secondary butylate, praseodynium aluminium, triisobutyl aluminium, 8-hydroxyquinoline aluminium, high chlorine
Sour aluminium, aluminum monostearate, aluminium distearate, basic aluminium acetate, ethyl aluminum dichloride, aliette, aluminium acetylacetonate, biphosphate
One kind in aluminium, aluminum oleate, aluminium bromide, silver iodide, aluminium ethylate, aluctyl, isooctyl acid aluminium and trioctylaluminum；
Used surfactant is dodecyl sodium sulfate, poly-methyl pyrrole alkanone, polyvinylpyrrolidone, fat
Alcohol APEO, lauryl sodium sulfate, sodium hexadecyl sulfate, sodium stearyl sulfate, cetyl trimethyl chlorination
Ammonium, cetyl trimethylammonium bromide, DTAB, the one of octyl sodium sulfonate and octyl sodium sulphate
Kind；
Used solvent is water, ethanol, dichloromethane, acetone, chloroform, methanol, tetrahydrofuran, carbon tetrachloride, hexamethylene
Alkane, isopropanol, 1,2- trichloroethanes, triethylamine, toluene, pyridine, ethylenediamine, butanol, acetic acid, chlorobenzene, dimethylbenzene, N, N- diformazans
Base formamide, cyclohexanone, cyclohexanol, DMAC N,N' dimethyl acetamide, N-METHYLFORMAMIDE, phenol, dimethyl sulfoxide, ethylene glycol, N-
Methyl pyrrolidone, one kind in formamide, sulfolane and glycerine；
（2）Charing
By step（1）The raw material mixed 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：The h of 0.1 h~10
Protective atmosphere：N2Or Ar2
Gas flow：The mL/min of 25 mL/min~300；
（3）Pickling
By step（2）Gained carbonizing production, which is placed in acid solution, to be stirred, and deionized water is fully washed to neutrality, is then placed in 35
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 and sulfuric acid
Acid solution molar concentration：The mol/L of 0.05mol/L~6
Mixing time：1~5h
Mixing speed：25~200 revs/min.
The beneficial effects of the present invention are：
（1）The specific surface area of carbon nano tube/graphene compound produced by the present invention is high, good electrical property, specific capacitance 100
~350 F/g, specific surface area are 150~400 m2/ g, graphite alkylene degree is up to the % of 30 %~70；
（2）It is uneven to solve carbon nano tube/graphene mixing, can be achieved by situ study, without graphene conduct
Raw material, technique is simple, safe operation；
（3）Abundant raw material, it is cheap, easily realize industrialization.
Brief description of the drawings
Fig. 1 is the scanning electron microscopic picture of the carbon nano tube/graphene compound prepared using the technique of embodiment 1；
Fig. 2 is the scanning electron microscopic picture of the carbon nano tube/graphene compound prepared using the technique of embodiment 2；
Fig. 3 is the scanning electron microscopic picture of the carbon nano tube/graphene compound prepared using the technique of embodiment 3；
Fig. 4 is the scanning electron microscopic picture of the carbon nano tube/graphene compound prepared using the technique of embodiment 4.
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
By single-walled carbon nanotube, aluminum sulfate and poly-methyl pyrrole alkanone according to mass ratio 50:100:0.05 weighs and mixes,
Ethanol is used as solvent, the mass ratio of mixture and solvent is 1:4.Both are well mixed by mechanical agitation, whipping temp
For 80 DEG C, mixing time is 2 h.It is to be mixed uniformly after, be evaporated under reduced pressure out solvent, be positioned over 80 DEG C of vacuum drying ovens（1.0×
10-1Pa）Dry 8 hours, be cooled to room temperature.Drying sample is positioned in atmosphere furnace, is passed through nitrogen（Nitrogen flow is 100mL/
min）, 2000 DEG C are warming up to 10 DEG C/min, is incubated 0.5 h, is cooled to room temperature taking-up.Carbonizing production is positioned over hydrochloric acid solution
（Acid solution molar concentration is 2mol/L）In, stir 1.5 h, mixing speed be 80 revs/min, be washed with deionized water after being separated by filtration to
It is neutral.It is positioned over vacuum drying chamber（1.0×10-1Pa）Middle 80 DEG C of drying drying 12 hours, that is, obtain carbon nano tube/graphene
Compound.
Prepared carbon nano tube/graphene composite properties are as follows：Specific capacitance is 350F/g, specific surface area 400
m2/ g, graphite alkylene degree are 70 %.
Embodiment 2
By industrial multi-walled carbon nano-tube, aluminum nitrate and dodecyl sodium sulfate according to mass ratio 100:100:0.1 weighs
And mix, N-METHYLFORMAMIDE is used as solvent, and the mass ratio of mixture and solvent is 1:10.Both are mixed by mechanical agitation
Close uniformly, whipping temp is 100 DEG C, and mixing time is 3 h.It is to be mixed uniformly after, be evaporated under reduced pressure out solvent, be positioned over 70 DEG C
Vacuum drying oven（1.0×102Pa）Dry 6 hours, be cooled to room temperature.Drying sample is positioned in atmosphere furnace, is passed through argon gas（Argon
Throughput is 200mL/min）, 1800 DEG C are warming up to 15 DEG C/min, is incubated 4h, is cooled to room temperature taking-up.Carbonizing production is put
It is placed in hydrochloric acid solution（Acid solution molar concentration is 4mol/L）In, 3h is stirred, mixing speed is 90 revs/min, is spent after being separated by filtration
Ion is washed to neutrality.It is positioned over vacuum drying chamber（1.0×10-1Pa）Middle 60 DEG C of drying drying 12 hours, that is, obtain carbon nanometer
Pipe/graphene complex.
Prepared carbon nano tube/graphene composite properties are as follows：Specific capacitance is 200 F/g, specific surface area 250
m2/ g, graphite alkylene degree are 50 %.
Embodiment 3
By double-walled carbon nano-tube, aluminium chloride and poly-methyl pyrrole alkanone according to mass ratio 70:100:0.03 weighs, using third
Ketone is solvent, and the mass ratio of raw material and solvent is 1:6.Both are well mixed by mechanical agitation, whipping temp is 30 DEG C,
Mixing time is 1.5 h.It is to be mixed uniformly after, be evaporated under reduced pressure out solvent, be positioned over 35 DEG C of vacuum drying ovens（1.0×10-1Pa）It is dry
Dry 2 h, is cooled to room temperature.Drying sample is positioned in atmosphere furnace, is passed through nitrogen（Nitrogen flow is 80 mL/min）, with 5
DEG C/min is warming up to 1500 DEG C, 2 h are incubated, are cooled to room temperature taking-up.Carbonizing production is positioned over sulfuric acid solution（Acid solution mole
Concentration is 1 mol/L）In, 2 h are stirred, mixing speed is 60 revs/min, is washed with deionized water after being separated by filtration to neutrality.Place
In vacuum drying chamber（1.0×10-1 Pa）Middle 80 DEG C of 4 h of drying of drying, that is, obtain carbon nano tube/graphene compound.
Prepared carbon nano tube/graphene composite properties are as follows：Specific capacitance is 120 F/g, specific surface area 200
m2/ g, graphite alkylene degree are 30 %.
Embodiment 4
By single-walled carbon nanotube and the mixture of double-walled carbon nano-tube（The quality of single-walled carbon nanotube and double-walled carbon nano-tube
Than for 1:2）, aluminium hydroxide and dodecyl sodium sulfate be according to mass ratio 30:100:0.01 weighs and mixes, and uses toluene to be molten
The mass ratio of agent, mixture and solvent is 1:3.Both are well mixed by mechanical agitation, whipping temp is 80 DEG C, stirring
Time is 4 h.It is to be mixed uniformly after, be evaporated under reduced pressure out solvent, be positioned over 60 DEG C of vacuum drying ovens（1.0×10-1Pa）3 h are dried,
It is cooled to room temperature.Drying sample is positioned in atmosphere furnace, is passed through nitrogen（Nitrogen flow is 80 mL/min）, with 4 DEG C/min liters
Temperature is incubated 3 h to 1300 DEG C, is cooled to room temperature taking-up.Carbonizing production is positioned over hydrochloric acid solution（Acid solution molar concentration is
0.5mol/L）In, 5 h are stirred, mixing speed is 40 revs/min, is washed with deionized water after being separated by filtration to neutrality.It is positioned over true
Empty drying box（1.0×105Pa）Middle 100 DEG C of 2 h of drying of drying, that is, obtain carbon nano tube/graphene compound.
Prepared carbon nano tube/graphene composite properties are as follows：The F/g of specific capacitance 100, the m of specific surface area 1502/ g,
Graphite alkylene degree is 30 %.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (5)
- A kind of 1. preparation method of carbon nano tube/graphene compound, it is characterised in that：Described preparation method includes raw material Mixing, charing and acid cleaning process, are comprised the following steps that：（1）The mixing of raw materialWeigh CNT, additive and surfactant, CNT, additive and surfactant in mass ratio for 1 ~ 100: 100:0.01 ~ 1 mixing, then the stirring solvent toward 1 ~ 10 times of quality of addition in mixture is well mixed rear and distills out Solvent, it is subsequently placed in baking oven and is dried；（2）CharingBy step（1）The raw material mixed 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/minPredetermined temperature：1100 DEG C~2000 DEG CSoaking time：The h of 0.1 h~10Protective atmosphere：N2Or Ar2Gas flow：The mL/min of 25 mL/min~300；（3）PicklingBy step（2）Gained carbonizing production, which is placed in acid solution, to be stirred, and deionized water is fully washed to neutrality, it is then placed in 35~ 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 and sulfuric acidAcid solution molar concentration：The mol/L of 0.05mol/L~6Mixing time：1~5hMixing speed：25~200 revs/min；Step（1）Employed in additive for aluminium chloride, aluminum sulfate, aluminium carbonate, aluminum acetate, aluminum nitrate, aluminium hydroxide, inclined aluminium Sour sodium, aluminium nitride, aluminum phosphate, alumina silicate, aluminium carbide, ten sulfate dihydrate aluminium ammoniums, metasilicic acid aluminium, trifluoromethanesulfonic acid aluminium, trialkyl Aluminium, dialkylaluminum chloride, an alkyl al dichloride, the aluminium of trialkyl tri-chlorination two, aluminium isopropoxide, butyl aluminium, aluminium acetate, formic acid Aluminium, oxalic acid aluminium, propionic acid aluminium, polyaluminium chloride, fluoric acid aluminium, aluminium secondary butylate, praseodynium aluminium, triisobutyl aluminium, 8-hydroxyquinoline Aluminium, aluminum perchlorate, aluminum monostearate, aluminium distearate, basic aluminium acetate, ethyl aluminum dichloride, aliette, aluminium acetylacetonate, phosphorus One kind in acid dihydride aluminium, aluminum oleate, aluminium bromide, silver iodide, aluminium ethylate, aluctyl, isooctyl acid aluminium and trioctylaluminum.
- A kind of 2. preparation method of carbon nano tube/graphene compound according to claim 1, it is characterised in that：Step （1）Employed in CNT be single-walled carbon nanotube, multi-walled carbon nanotube and carbon nano-tube fibre it is one or more of Mixing.
- 3. according to the method for claim 1, it is characterised in that：Step（1）Employed in surfactant be dodecane Base sodium sulfonate, poly-methyl pyrrole alkanone, polyvinylpyrrolidone, AEO, lauryl sodium sulfate, hexadecane Base sodium sulphate, sodium stearyl sulfate, hexadecyltrimethylammonium chloride, cetyl trimethylammonium bromide, dodecyl three One kind of methyl bromide ammonium, octyl sodium sulfonate and octyl sodium sulphate.
- 4. according to the method for claim 1, it is characterised in that：Step（1）Employed in solvent for water, ethanol, dichloro Methane, acetone, chloroform, methanol, tetrahydrofuran, carbon tetrachloride, hexamethylene, isopropanol, 1,2- trichloroethanes, triethylamine, toluene, Pyridine, ethylenediamine, butanol, acetic acid, chlorobenzene, dimethylbenzene, N,N-dimethylformamide, cyclohexanone, cyclohexanol, N, N- dimethyl second Acid amides, N-METHYLFORMAMIDE, phenol, dimethyl sulfoxide, ethylene glycol, 1-METHYLPYRROLIDONE, in formamide, sulfolane and glycerine It is a kind of.
- 5. according to the method for claim 1, it is characterised in that：Step（1）Middle whipping temp is 25~150 DEG C, during stirring Between be 1~5h；Drying temperature is 35~100 DEG C, and drying time is 1 ~ 12h.
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| CN107640758B (en) * | 2017-10-30 | 2019-10-15 | 福州大学 | A kind of preparation method of mesoporous carbon/graphene oxide compound |
| CN108579771A (en) * | 2018-03-23 | 2018-09-28 | 福州大学 | A kind of Catalyzed by Modified Bentonite agent of synthesis of dimmer acid |
| CN109181492A (en) * | 2018-08-03 | 2019-01-11 | 无锡泰科纳米新材料有限公司 | A kind of graphene heat radiation coating for electronic component |
| CN112723339A (en) * | 2020-12-11 | 2021-04-30 | 深圳市德方纳米科技股份有限公司 | Array type doped multi-walled carbon nanotube, preparation method thereof and electrode material |
| CN114735676B (en) * | 2022-04-11 | 2023-10-20 | 暨南大学 | Method for preparing carbon nano tube by taking waste snack box as raw material |
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| WO2014120162A1 (en) * | 2013-01-30 | 2014-08-07 | Empire Technology Development, Llc | Carbon nanotube-graphene composite |
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