CN102832050B - Method for preparing graphene/carbon nanotube hybrid in hierarchical structure - Google Patents
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Abstract
The invention relates to the technical field of new energy resources, in particular to a method for preparing a graphene/carbon nanotube hybrid in a hierarchical structure. The method includes the steps: (1) preparing graphene oxide colloidal solution; (2) preparing carbon nanotube colloidal solution easy in dispersion; (3) mixing the graphene oxide colloidal solution obtained at the step (1) and the preparing carbon nanotube colloidal solution easy in dispersion obtained at the step (2), and adding alcohol solvents to obtain graphene oxide/ carbon nanotube hybrid solution; and (4) under the shielding of inert gases, using a high-energy ray radiation source for irradiation and reduction of products obtained at the step (3) to obtain the graphene/carbon nanotube hybrid in the hierarchical structure. The method for preparing the graphene/carbon nanotube hybrid in the hierarchical structure has the advantages of simplicity in process, low cost, high controllability, environment friendliness and capability of implementing industrial production, and the hybrid prepared by the method is in an surface-line network structure, large in effective specific surface area and beneficial to charge transmission and can be used for electrode materials of high-performance supercapacitors.
Description
Technical field
The present invention relates to novel energy resource material technology field, relate to the preparation of electrode material for super capacitor, specifically, is a kind of preparation method of hierarchy graphene/carbon nano-tube hybrid.
Background technology
Graphene is as a kind of two-dimensional nano material with carbon element, there is due to it features such as unique chemical constitution, large specific area, high conductivity, excellent mechanical performance, show application prospect widely in nano electron device, chemical power source, solar cell, transducer, catalyst carrier and high-performance composite materials field.But, because Graphene is subject to the effect of Van der Waals force that irreversible reunion easily occurs, make single-layer graphene be difficult to play its intrinsic excellent specific property.Therefore, the problem solving the gathering of graphene film interlayer is problem in the urgent need to address at present.
One dimension carbon nano-tube, because have excellent conductivity and chemical stability, enjoys the favor of people in stored energy.Carbon nano-tube is inserted into graphene film interlayer, not only can increases the effective ratio area of Graphene, and the internal resistance of hybrid material can be reduced, improve its charge transport properties.The people such as Yang (
j. Mater. Chem., 2011, Vol.21,2374) and construct classification graphene/carbon nano-tube hybrid by in-situ chemical reducing process, when described hybrid is used as electrode of super capacitor, its energy and power density reach 21.7 Wh kg respectively
-1with 78.3 kW kg
-1.The people such as Yu (
j. Phys. Chem. Lett., 2010, Vol.1,467) and use electrostatic self-assembled method to obtain graphene/carbon nano-tube hybridized film, described hybridized film ratio capacitance can reach 120 F/g.But the deficiency of above technology is: because introducing containing virose reducing agent, can to environment, and also their reduction process also can cause destruction to a certain degree to the structure of Graphene, directly has influence on the performance of hybrid.Chinese patent literature CN102338941A discloses " a kind of cadmium telluride quantum dot graft grapheme-carbon nano-tube coextruded film optical switch material and preparation method thereof ": by graphene oxide with carbon nano-tube solution is ultrasonic mixes, mixed liquor after the drying of miillpore filter suction filtration, at H
2in/Ar mixed atmosphere, 500 DEG C of high-temperature heat treatment 1 hour, obtain three-dimensional network graphene/carbon nano-tube composite membrane.But this technology exists atmospheric condition requirement harsh, the deficiency that energy consumption is high.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of hierarchy graphene/carbon nano-tube hybrid is provided, it has the advantage that technique is simple, controllability strong, environmental friendliness, cost are low, and the composite material prepared in this way has the feature of high energy and power density and good cycling stability.
Thinking of the present invention is: introduce carbon nano-tube by the stacking self-assembling method of π-π at graphene oxide interlayer, forms hierarchy graphene oxide/carbon nano-tube hybridization thing, to suppress the gathering of graphene oxide.Then under an inert gas through high-energy ray irradiation reduction, the graphene/carbon nano-tube hybrid of classification upper thread network configuration is obtained.For avoiding the oxidizability OH free radical produced in irradiation process, introducing alcohols solvent, making oxidative free radical be converted into reductive free radical, improve the efficiency of graphene oxide irradiation reduction.Meanwhile, compared with electronation, the speed of irradiation reduction is comparatively slow, and this also inhibits the gathering of Graphene in irradiation reduction process.Because carbon nano-tube is inserted into the upper thread network configuration that graphene film interlayer forms three-dimensional IPN, graphene/carbon nano-tube hybrid is made to have larger effective ratio area and good conductivity, this is conducive to the transmission performance improving electric charge, also can give the higher ratio capacitance of hybrid, excellent multiplying power property and good cyclical stability simultaneously.
For achieving the above object, invention thinking is converted into practical technique, the technical scheme that the present invention takes is as follows.
A preparation method for hierarchy graphene/carbon nano-tube hybrid, is characterized in that, comprise the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 0.1 ~ 10 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, stirred at ambient temperature 48 ~ 72 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution;
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
Carbon nano-tube is put into the sulfuric acid (H that concentration is 98%
2sO
4) and concentration be 60 ~ 70% nitric acid (HNO
3) nitration mixture in, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 5 ~ 100 mg/mL, mechanical agitation 24 ~ 72 hours at 60 DEG C, wherein ultrasonic process 4 ~ 6 hours, then spend deionized water to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion;
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that the graphene oxide colloidal solution obtain step (1) and step (2) obtain is uniformly mixed 2 ~ 12 hours, add (can remove in solution oxidizing substance) alcohols solvent, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor;
(4) high-energy irradiation reduction
Under inert gas shielding, with high-energy ray radiation source, irradiation reduction is carried out to graphene oxide/carbon nano-tube hybridization thing mixed liquor, obtain target product---hierarchy graphene/carbon nano-tube hybrid.
Further, the graphene oxide colloidal solution described in step (3) is 1: 0.05 ~ 10 mix and blends with the carbon nano-tube colloidal solution easily disperseed by the mass ratio of graphene oxide and carbon nano-tube.
Further, the alcohols solvent described in step (3) is water-soluble monohydric alcohol, comprises the one in methyl alcohol, ethanol, isopropyl alcohol, n-butanol.
Further, the alcohols solvent described in step (3) and the volume ratio of deionized water are 0.2 ~ 4: 1.
Further, the high-energy ray radiation source described in step (4) is the one in cobalt-60 or electron accelerator, and irradiation dose is 20 ~ 500 kGy.
Good effect of the present invention is:
(1) method of the present invention has that technique is simple, cost is low, controllability is strong, environmental friendliness, can realize the advantage of suitability for industrialized production.
(2) compared with the graphene/carbon nano-tube hybrid prepared with methods such as existing electronation, LBL self-assembly, high-temperature heat treatment, the obtained hybrid of method of the present invention is adopted to present upper thread network configuration, there is large effective ratio area, be conducive to the transmission of electric charge, thus give the chemical property that it is more excellent, can be used for high-performance super capacitor electrode material.
Accompanying drawing explanation
Accompanying drawing 1 is the FB(flow block) of the preparation method of hierarchy graphene/carbon nano-tube hybrid of the present invention.
Accompanying drawing 2 is the field emission scanning electron microscope photo of the embodiment of the present invention 1.
Accompanying drawing 3 is the field emission scanning electron microscope photo of comparative example 1 of the present invention.
Accompanying drawing 4 is the field emission scanning electron microscope photo of comparative example 2 of the present invention.
Accompanying drawing 5 is embodiment 1(a) and comparative example 2(b) cyclic voltammetry curve figure under 10 mV/s sweep speeds.
Accompanying drawing 6 is embodiment 1(a) and comparative example 2(b) electrochemical cycle stability linearity curve figure under 50 mV/s sweep speeds.
Embodiment
Introduce the embodiment of the preparation method of hierarchy graphene/carbon nano-tube hybrid of the present invention further below in conjunction with accompanying drawing, but enforcement of the present invention is not limited to following execution mode.
embodiment 1
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 6 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, at room temperature stir 48 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
2 grams of carbon nano-tube are put into the sulfuric acid (H that concentration is 98%
2sO
4) and concentration be 60 ~ 70% nitric acid (HNO
3) nitration mixture in, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 10 mg/mL, mechanical agitation 48 hours at 60 DEG C, wherein ultrasonic process 4 hours, then spends deionized water to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion.
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that graphene oxide colloidal solution step (1) obtained obtains with step (2) mixes 8 hours by graphene oxide with mass ratio 1: 0.25 mechanical agitation of carbon nano-tube, then add isopropyl alcohol (volume ratio of deionized water and isopropyl alcohol is 1: 1), obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2under Buchholz protection, carry out irradiation reduction with cobalt-60 radioactive source to graphene oxide/carbon nano-tube hybridization thing mixed liquor, irradiation dose is 100 kGy, obtains hierarchy graphene/carbon nano-tube hybrid.
the product analysis of embodiment 1:
Field emission scanning electron microscope (FESEM) photo shows, and hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 1 presents a kind of upper thread network configuration, is dispersed in even carbon nanotube graphene film interlayer (see accompanying drawing 2).
Shown by EDS analysis result, in hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 1, C/O weight ratio is 6.9, and its oxygen content is less than three comparative examples, and this shows, described hybrid has larger reducing degree after radiation treatment.
Use four-point probe records, and the conductivity of hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 1 is up to 1.4 S/cm.
comparative example 1---for the comparative example with embodiment 1
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) technique of embodiment 1 step (1) is adopted;
(2) technique of embodiment 1 step (2) is adopted;
(3) the carbon nano-tube colloidal solution of the easy dispersion obtained with step (2) by the graphene oxide colloidal solution that step (1) obtains mixes 8 hours by graphene oxide with mass ratio 1: 0.25 mechanical agitation of carbon nano-tube, finally obtains graphene oxide/carbon nano-tube hybridization thing.
the product analysis of comparative example 1:
Field emission scanning electron microscope (FESEM) photo shows, there is many homodisperse carbon nano-tube (see accompanying drawing 3) in graphene oxide/carbon nano-tube hybridization thing prepared by comparative example 1 at graphene oxide interlayer, this shows that carbon nano-tube is successfully inserted into graphene oxide sheet interlayer, forms a kind of graphene oxide/carbon nano-tube hybridization thing of upper thread network configuration; Its pattern is similar to the graphene/carbon nano-tube hybrid of embodiment 1.
Shown by EDS analysis result, in graphene oxide/carbon nano-tube hybridization thing prepared by comparative example 1, C/O weight ratio is 2.2.
Use four-point probe records, and the conductivity of graphene oxide/carbon nano-tube hybridization thing prepared by comparative example 1 is 1.3 × 10
-3s/cm.
comparative example 2---for the comparative example with embodiment 1
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) technique of embodiment 1 step (1) is adopted;
(2) technique of embodiment 1 step (2) is adopted;
(3) the carbon nano-tube colloidal solution of the easy dispersion obtained with step (2) by the graphene oxide colloidal solution that step (1) obtains mixes 8 hours by graphene oxide with mass ratio 1: 0.25 mechanical agitation of carbon nano-tube, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor, then at 95 DEG C, 12 hours are reacted with hydrazine hydrate, the mass ratio of controlled oxidization graphite and hydrazine hydrate is 1: 3, finally obtains graphene/carbon nano-tube hybrid.
the product analysis of comparative example 2:
Field emission scanning electron microscope (FESEM) photo shows, in graphene/carbon nano-tube hybrid prepared by comparative example 2, Graphene exists mainly with state of aggregation form greatly, carbon nano-tube only comes across Graphene aggregate surface, and is not intercalation into graphene film interlayer (see accompanying drawing 4).
Shown by EDS analysis result, in graphene/carbon nano-tube hybrid prepared by comparative example 2, C/O weight ratio is 5.8.
Use four-point probe records, and the conductivity of graphene/carbon nano-tube hybrid prepared by comparative example 2 is 7.0 S/cm.
If the graphene/carbon nano-tube hybrid prepared by comparative example 2 is as electrode material, CHI660D electrochemical workstation carries out cyclic voltammetry, as shown in the b in accompanying drawing 5, it is rectangular-shaped that this hybrid cyclic voltammetry curve also presents class, show obvious electric double layer capacitance characteristic, but polarization phenomena is comparatively serious, by calculating, its ratio capacitance is 188 F/g, and after circulation 1000 circle, its capacity retention is for 97.7%(is see shown in the b in accompanying drawing 6).
comparative example 3---for the comparative example with embodiment 1
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) technique of embodiment 1 step (1) is adopted;
(2) technique of embodiment 1 step (2) is adopted;
(3) the carbon nano-tube colloidal solution of the easy dispersion obtained with step (2) by the graphene oxide colloidal solution that step (1) obtains mixes 8 hours by graphene oxide with mass ratio 1: 0.25 mechanical agitation of carbon nano-tube, obtains graphene oxide/carbon nano-tube hybridization thing mixed liquor;
(4) at N
2under Buchholz protection, carry out irradiation reduction with cobalt-60 radioactive source to graphene oxide/carbon nano-tube hybridization thing mixed liquor, irradiation dose is 100 kGy, obtains hierarchy graphene/carbon nano-tube hybrid.
the product analysis of comparative example 3:
Shown by EDS analysis result, in hierarchy graphene/carbon nano-tube hybrid prepared by comparative example 3, C/O weight ratio is 2.6.
Use four-point probe records, and the conductivity of hierarchy graphene/carbon nano-tube hybrid prepared by comparative example 3 is 7.4 × 10
-3s/cm.
The comparative result of embodiment 1 and comparative example 1 ~ 3
By the result that the product of the product of embodiment 1 and comparative example 1 ~ 3 compares be: if hierarchy graphene/carbon nano-tube hybrid embodiment 1 prepared is as electrode material, cyclic voltammetry is carried out at CHI660D electrochemical workstation, it is rectangular-shaped that this hybrid cyclic voltammetry curve presents class, its area under the curve is greater than comparative example 2, and polarization phenomena also less (shown in a in accompanying drawing 5) simultaneously; As calculated, its ratio capacitance is 285 F/g, apparently higher than comparative example 2; And after 1000 circle circulations, its capacity retention up to 99.7%(see shown in a in accompanying drawing 6), this shows: the electrochemical cycle stability of hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 1 is very excellent
.
embodiment 2
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 10 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, at room temperature stir 72 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
1 gram of carbon nano-tube is put into the sulfuric acid (H that concentration is 98%
2sO
4) and concentration be 60 ~ 70% nitric acid (HNO
3) nitration mixture in, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 5 mg/mL, mechanical agitation 24 hours at 60 DEG C, wherein ultrasonic process 4 hours, then spends deionized water to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion.
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that the graphene oxide colloidal solution obtain step (1) and step (2) obtain is uniformly mixed 12 hours by the mass ratio 1: 0.05 of graphene oxide and carbon nano-tube, then add methyl alcohol (volume ratio of deionized water and methyl alcohol is 1: 1.5), obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2under Buchholz protection, carry out irradiation reduction with cobalt-60 radioactive source to graphene oxide/carbon nano-tube hybridization thing mixed liquor, irradiation dose is 50 kGy, obtains hierarchy graphene/carbon nano-tube hybrid.
the product analysis of embodiment 2:
Shown by EDS analysis result, in hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 2, C/O weight ratio is 5.3.
Use test instrument probe records, and the conductivity of hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 2 is 0.56 S/cm.
embodiment 3
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 0.1 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, at room temperature stir 48 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
5 grams of carbon nano-tube are put into the sulfuric acid (H that concentration is 98%
2sO
4) and concentration be 60 ~ 70% nitric acid (HNO
3) nitration mixture in, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 100 mg/mL, mechanical agitation 72 hours at 60 DEG C, wherein ultrasonic process 6 hours, then spends deionized water to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion.
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that graphene oxide colloidal solution step (1) obtained obtains with step (2) mixes 12 hours by graphene oxide with mass ratio 1: 10 mechanical agitation of carbon nano-tube, then add ethanol (volume ratio of deionized water and ethanol is 1: 4), obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
Under Ar Buchholz protection, carry out irradiation reduction with cobalt-60 radioactive source to graphene oxide/carbon nano-tube hybridization thing mixed liquor, irradiation dose is 20 kGy, obtains hierarchy graphene/carbon nano-tube hybrid.
the product analysis of embodiment 3:
Shown by EDS analysis result, in hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 3, C/O weight ratio is 5.7.
Use test instrument probe records, and the conductivity of hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 3 is 0.32 S/cm.
embodiment 4
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 2 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, at room temperature stir 60 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
2 grams of carbon nano-tube are put into the sulfuric acid (H that concentration is 98%
2sO
4) and concentration be 60 ~ 70% nitric acid (HNO
3) nitration mixture in, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 20 mg/mL, mechanical agitation 48 hours at 60 DEG C, wherein ultrasonic process 4 hours, then spends deionized water to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion.
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that graphene oxide colloidal solution step (1) obtained obtains with step (2) mixes 2 hours by graphene oxide with mass ratio 1: 0.25 mechanical agitation of carbon nano-tube, then add n-butanol (volume ratio of deionized water and n-butanol is 1: 0.2), obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2under Buchholz protection, carry out irradiation reduction with cobalt-60 radioactive source to graphene oxide/carbon nano-tube hybridization thing mixed liquor, irradiation dose is 500 kGy, obtains hierarchy graphene/carbon nano-tube hybrid.
the product analysis of embodiment 4:
Shown by EDS analysis result, in hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 4, C/O weight ratio is 4.8.
Use test instrument probe records, and the conductivity of hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 4 is 0.083 S/cm.
embodiment 5
A preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 6 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, at room temperature stir 48 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
2 grams of carbon nano-tube are put into the sulfuric acid (H that concentration is 98%
2sO
4) and concentration be 60 ~ 70% nitric acid (HNO
3) nitration mixture in, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 10 mg/mL, mechanical agitation 60 hours at 60 DEG C, wherein ultrasonic process 4 hours, then spends deionized water to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion.
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that graphene oxide colloidal solution step (1) obtained obtains with step (2) mixes 8 hours by graphene oxide with mass ratio 1: 1 mechanical agitation of carbon nano-tube, then add isopropyl alcohol (volume ratio of deionized water and isopropyl alcohol is 1: 1), obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2under Buchholz protection, carry out irradiation reduction with electron accelerator to graphene oxide/carbon nano-tube hybridization thing mixed liquor, irradiation dose is 200 kGy, obtains hierarchy graphene/carbon nano-tube hybrid.
the product analysis of embodiment 5:
Shown by EDS analysis result, in hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 5, C/O weight ratio is 7.1.
Use test instrument probe records, and the conductivity of hierarchy graphene/carbon nano-tube hybrid prepared by embodiment 5 is 3.2 S/cm.
The hierarchy graphene/carbon nano-tube hybrid obtained by preparation method of the present invention can be used for the active electrode material making ultracapacitor: by the dispersed one-tenth solution of described hierarchy graphene/carbon nano-tube hybrid, drop to graphite plate electrode surface, after its drying, drip a small amount of Nafion solution again, after vacuumize, make work electrode.Cyclic voltammetry completes on CHI660D electrochemical workstation, adopt three-electrode system, platinum electrode is to electrode, silver/silver chloride electrode is reference electrode, work electrode is the graphite plate electrode being coated with active material, electrolyte is 1 mol/L sulfuric acid solution, and scanning voltage scope is 0 ~ 0.8 V, and sweep speed is 1 ~ 100 mV/s.The ratio capacitance of hybrid passes through formula:
c=(∫
idV)/(
υ mV) calculate, in formula,
c(F/g) be ratio capacitance;
i(A) be electric current;
v(V) be voltage;
υ(mV/s) be sweep speed;
mg () is the quality of hybrid on work electrode.
Claims (4)
1. a preparation method for hierarchy graphene/carbon nano-tube hybrid, comprises the following steps:
(1) graphene oxide colloidal solution is prepared
Graphite oxide is scattered in deionized water, the concentration of controlled oxidization graphite is 0.1 ~ 10 mg/mL, drips a small amount of ammoniacal liquor and regulates solution ph between 9 ~ 11, stirred at ambient temperature 48 ~ 72 hours, remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution;
(2) the carbon nano-tube colloidal solution of the easy dispersion of preparation
Carbon nano-tube is put into concentration be 98% sulfuric acid and concentration be the nitration mixture of the nitric acid of 60 ~ 70%, H
2sO
4with HNO
3volume ratio be 3: 1, the concentration of carbon nano-tube in mixed acid solution is controlled to be 5 ~ 100 mg/mL, mechanical agitation 24 ~ 72 hours at 60 DEG C, wherein ultrasonic process 4 ~ 6 hours, then use deionized water cyclic washing to neutral, obtain the carbon nano-tube colloidal solution of easily dispersion;
It is characterized in that:
(3) mixed oxidization Graphene colloidal solution and the carbon nano-tube colloidal solution easily disperseed
The carbon nano-tube colloidal solution of the easy dispersion that the graphene oxide colloidal solution obtain step (1) and step (2) obtain is uniformly mixed 2 ~ 12 hours, interpolation can remove the alcohols solvent of oxidizing substance in solution, obtains graphene oxide/carbon nano-tube hybridization thing mixed liquor;
Described graphene oxide colloidal solution and the carbon nano-tube colloidal solution easily disperseed are 1: 0.05 ~ 10 to be uniformly mixed by the mass ratio of graphene oxide and carbon nano-tube;
(4) high-energy irradiation reduction
Under inert gas shielding, with high-energy ray radiation source, irradiation reduction is carried out to graphene oxide/carbon nano-tube hybridization thing mixed liquor, obtain target product---hierarchy graphene/carbon nano-tube hybrid.
2. the preparation method of hierarchy graphene/carbon nano-tube hybrid according to claim 1, is characterized in that, the alcohols solvent described in step (3) is water-soluble monohydric alcohol, comprises the one in methyl alcohol, ethanol, isopropyl alcohol, n-butanol.
3. according to claim
2the preparation method of described hierarchy graphene/carbon nano-tube hybrid, is characterized in that, the alcohols solvent described in step (3) and the volume ratio of deionized water are 0.2 ~ 4: 1.
4. the preparation method of hierarchy graphene/carbon nano-tube hybrid according to claim 1, is characterized in that, the high-energy ray radiation source described in step (4) is the one in cobalt-60 or electron accelerator, and irradiation dose is 20 ~ 500 kGy.
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