CN102832050A - Method for preparing graphene/carbon nanotube hybrid in hierarchical structure - Google Patents
Method for preparing graphene/carbon nanotube hybrid in hierarchical structure Download PDFInfo
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- CN102832050A CN102832050A CN201210310341XA CN201210310341A CN102832050A CN 102832050 A CN102832050 A CN 102832050A CN 201210310341X A CN201210310341X A CN 201210310341XA CN 201210310341 A CN201210310341 A CN 201210310341A CN 102832050 A CN102832050 A CN 102832050A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 293
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 148
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 127
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 6
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- 238000009396 hybridization Methods 0.000 claims description 78
- 238000002360 preparation method Methods 0.000 claims description 60
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000006396 nitration reaction Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 2
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- 238000005516 engineering process Methods 0.000 description 11
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- 239000011229 interlayer Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 230000002285 radioactive effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
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- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
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- 239000011149 active material Substances 0.000 description 1
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- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 carbon nano-tube compound Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000006378 damage Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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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 the new energy materials technical field, relate to the preparation of electrode material for super capacitor, specifically, is the preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing.
Background technology
Graphene is as a kind of two-dimensional nano material with carbon element; Because it has unique chemical structure, big specific area, high conductivity, excellent characteristics such as mechanical performance, shows application prospects in nano electron device, chemical power source, solar cell, transducer, catalyst carrier and high-performance composite materials field.Yet,, make single-layer graphene be difficult to bring into play its intrinsic excellent specific property because Graphene receives the effect of Van der Waals force to be prone to irreversible reunion takes place.Therefore, the problem of solution graphene film interlayer gathering is the problem that presses for solution at present.
The one dimension CNT is because have excellent conductivity and chemical stability, in the favor that enjoys people aspect the energy storage.CNT is inserted into the graphene film interlayer, not only can increases the effective ratio area of Graphene, and can reduce the internal resistance of hybrid material, improve its charge transport properties.People such as Yang (
J. Mater. Chem., 2011, Vol.21,2374) constructed classification Graphene/carbon nano-tube hybridization thing through the in-situ chemical reducing process, when said hybrid was used as electrode of super capacitor, its energy and power density reached 21.7 Wh kg respectively
-1With 78.3 kW kg
-1People such as Yu (
J. Phys. Chem. Lett., 2010, Vol.1,467) use the static self-assembling method to obtain Graphene/carbon nano-tube hybridization film, said hybridized film can reach 120 F/g than electric capacity.But, more than the deficiency of technology be: because of introducing contains toxic reducing agent, can pollute, and their reduction process also can cause destruction to a certain degree to the structure of Graphene, directly have influence on the performance of hybrid environment.Chinese patent document CN102338941A discloses " a kind of cadmium telluride quantum dot graft grapheme-carbon nano-tube coextruded film optical switch material and preparation method thereof ": with graphene oxide with carbon nano-tube solution is ultrasonic mixes; Mixed liquor is after miillpore filter suction filtration drying, at H
2In/Ar the mixed atmosphere, 500 ℃ of high-temperature heat treatment 1 hour obtain three-dimensional network Graphene/carbon nano-tube compound film.But this technology exists the atmospheric condition requirement harsh, the deficiency that energy consumption is high.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing is provided; It has that technology is simple, controllability is strong, environmental friendliness, advantage that cost is low, has the characteristics of high energy and power density and good cycling stability with the composite material of this method preparation.
Thinking of the present invention is: pile up self-assembling method through π-π and introduce CNT at the graphene oxide interlayer, form hierarchy graphene oxide/carbon nano-tube hybridization thing, to suppress the gathering of graphene oxide.Under inert gas, reduce then, obtain the Graphene/carbon nano-tube hybridization thing of classification upper thread network configuration through high-energy ray irradiation.Be the oxidizability OH free radical of avoiding in the irradiation process, producing, introduce alcohols solvent, make oxidative free radical be converted into reductive free radical, improve the efficient of graphene oxide irradiation reduction.Simultaneously, compare with electronation, the speed of irradiation reduction is comparatively slow, and this has also suppressed the gathering of Graphene in the irradiation reduction process.Because CNT is inserted into the upper thread network configuration that the graphene film interlayer forms three-dimensional IPN; Make Graphene/carbon nano-tube hybridization thing have bigger effective ratio area and good electrical conductivity; This helps improving the transmission performance of electric charge, also can give the higher ratio electric capacity of hybrid, the multiplying power property of excellence and good cyclical stability simultaneously.
For realizing above-mentioned purpose, will invent thinking and be converted into practical technique, the technical scheme that the present invention takes is following.
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing is characterized in that, may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 0.1～10 mg/mL, drips less ammonia regulator solution pH value between 9～11, stirs under the room temperature 48～72 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution;
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is 98% sulfuric acid (H that CNT is put into concentration
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 CNT in mixed acid solution is controlled to be 5～100 mg/mL, and 60 ℃ of following mechanical agitation 24～72 hours, wherein sonicated was 4～6 hours; Extremely neutral with deionized water wash then, obtain being prone to dispersed carbon nano tube colloidal solution;
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The easy dispersed carbon nano tube colloidal solution that graphene oxide colloidal solution that step (1) is obtained and step (2) obtain mixed 2～12 hours; Add (can remove in the 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 the high-energy ray radiation source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, obtain target product---hierarchy Graphene/carbon nano-tube hybridization thing.
Further, the described graphene oxide colloidal solution of step (3) and easy dispersed carbon nano tube colloidal solution are 1: 0.05～10 to mix stirring by the graphene oxide and the mass ratio of CNT.
Further, the described alcohols solvent of step (3) is water-soluble monohydric alcohol, comprises a kind of in methyl alcohol, ethanol, isopropyl alcohol, the n-butanol.
Further, the volume ratio of described alcohols solvent of step (3) and deionized water is 0.2～4: 1.
Further, the described high-energy ray radiation source of step (4) is a kind of in cobalt-60 or the electron accelerator, and irradiation dose is 20～500 kGy.
Good effect of the present invention is:
(1) method of the present invention has that technology is simple, cost is low, controllability is strong, environmental friendliness, can realize the advantage of suitability for industrialized production.
(2) compare with the Graphene/carbon nano-tube hybridization thing of existing electronation, method such as self assembly, high-temperature heat treatment preparation layer by layer; The hybrid that adopts method of the present invention to make presents the upper thread network configuration; Has big effective ratio area; Help the transmission of electric charge, thereby give its excellent more chemical property, can be used for the high-performance electrode material for super capacitor.
Description of drawings
Accompanying drawing 1 is the preparation method's of hierarchy Graphene of the present invention/carbon nano-tube hybridization thing FB(flow block).
Accompanying drawing 2 is the field emission scanning electron microscope photo of the embodiment of the 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 the cyclic voltammetry curve figure of comparative example 2 (b) under 10 mV/s sweep speeds.
Accompanying drawing 6 is embodiment 1 (a) and the electrochemistry cyclical stability curve chart of comparative example 2 (b) under 50 mV/s sweep speeds.
Embodiment
Further introduce the preparation method's of hierarchy Graphene of the present invention/carbon nano-tube hybridization thing embodiment below in conjunction with accompanying drawing, still, enforcement of the present invention is not limited to following execution mode.
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 6 mg/mL, drips less ammonia regulator solution pH value between 9～11, at room temperature stirs 48 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is 98% sulfuric acid (H that 2 gram CNTs are put into concentration
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 CNT in mixed acid solution is controlled to be 10 mg/mL, 60 ℃ of following mechanical agitation 48 hours, wherein sonicated was 4 hours, then with deionized water wash to neutral, obtain being prone to dispersed carbon nano tube colloidal solution.
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The graphene oxide colloidal solution that step (1) is obtained mixed 8 hours with 1: 0.25 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains; Add isopropyl alcohol (volume ratio of deionized water and isopropyl alcohol is 1: 1) then, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2Under the Buchholz protection, with cobalt-60 radioactive source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, irradiation dose is 100 kGy, obtains hierarchy Graphene/carbon nano-tube hybridization thing.
The product analysis of embodiment 1:
Field emission scanning electron microscope (FESEM) photo shows that the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 1 preparation demonstrates a kind of upper thread network configuration, is dispersed in to even carbon nanotube graphene film interlayer (referring to accompanying drawing 2).
Shown that by the EDS analysis result C/O weight ratio is 6.9 in the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 1 preparation, its oxygen content is less than three comparative examples, and this shows that said hybrid has bigger reducing degree after radiation treatment.
Use the four point probe tester to record, the conductivity of the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 1 preparation is up to 1.4 S/cm.
Comparative example 1---For with the comparative example of embodiment 1
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) technology of employing embodiment 1 step (1);
(2) technology of employing embodiment 1 step (2);
(3) the graphene oxide colloidal solution that step (1) is obtained mixed 8 hours with 1: 0.25 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains, and finally obtained graphene oxide/carbon nano-tube hybridization thing.
The product analysis of comparative example 1:
Field emission scanning electron microscope (FESEM) photo shows; Graphene oxide/carbon nano-tube hybridization the thing of comparative example 1 preparation many homodisperse CNTs (referring to accompanying drawing 3) occur at the graphene oxide interlayer; This shows that CNT successfully has been 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 with Graphene/carbon nano-tube hybridization thing of embodiment 1.
Show that by the EDS analysis result C/O weight ratio is 2.2 in the graphene oxide/carbon nano-tube hybridization thing of comparative example 1 preparation.
Use the four point probe tester to record, the conductivity of the graphene oxide/carbon nano-tube hybridization thing of comparative example 1 preparation is 1.3 * 10
-3S/cm.
Comparative example 2---For with the comparative example of embodiment 1
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) technology of employing embodiment 1 step (1);
(2) technology of employing embodiment 1 step (2);
(3) the graphene oxide colloidal solution that step (1) is obtained mixed 8 hours with 1: 0.25 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains; Obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor; Reacted 12 hours down at 95 ℃ then with hydrazine hydrate; The mass ratio of controlled oxidation graphite and hydrazine hydrate is 1: 3, finally obtains Graphene/carbon nano-tube hybridization thing.
The product analysis of comparative example 2:
Field emission scanning electron microscope (FESEM) photo shows; Graphene exists with the state of aggregation form mostly in the Graphene/carbon nano-tube hybridization thing of comparative example 2 preparations; CNT only comes across the Graphene aggregate surface, and not intercalation to graphene film interlayer (referring to accompanying drawing 4).
Show that by the EDS analysis result C/O weight ratio is 5.8 in the Graphene/carbon nano-tube hybridization thing of comparative example 2 preparations.
Use the four point probe tester to record, the conductivity of the Graphene/carbon nano-tube hybridization thing of comparative example 2 preparations is 7.0 S/cm.
If the Graphene/carbon nano-tube hybridization thing of comparative example 2 preparation as electrode material, is carried out the cyclic voltammetric test, shown in the b in the accompanying drawing 5 on the CHI660D electrochemical workstation; Also type of demonstrating is rectangular-shaped for this hybrid cyclic voltammetry curve, show tangible electric double layer capacitance characteristic, but polarization phenomena is comparatively serious; Through calculating; It is 188 F/g than electric capacity, and behind circulation 1000 circles, its electric capacity conservation rate is 97.7% (shown in the b in the accompanying drawing 6).
Comparative example 3---For with the comparative example of embodiment 1
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) technology of employing embodiment 1 step (1);
(2) technology of employing embodiment 1 step (2);
(3) the graphene oxide colloidal solution that step (1) is obtained mixed 8 hours with 1: 0.25 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains, and obtained graphene oxide/carbon nano-tube hybridization thing mixed liquor;
(4) at N
2Under the Buchholz protection, with cobalt-60 radioactive source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, irradiation dose is 100 kGy, obtains hierarchy Graphene/carbon nano-tube hybridization thing.
The product analysis of comparative example 3:
Show that by the EDS analysis result C/O weight ratio is 2.6 in the hierarchy Graphene/carbon nano-tube hybridization thing of comparative example 3 preparations.
Use the four point probe tester to record, the conductivity of the hierarchy Graphene/carbon nano-tube hybridization thing of comparative example 3 preparations is 7.4 * 10
-3S/cm.
The comparative result of embodiment 1 and comparative example 1～3
The result that the product of the product of embodiment 1 and comparative example 1～3 is compared is: if with the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 1 preparation as electrode material; Carry out the cyclic voltammetric test at the CHI660D electrochemical workstation; This hybrid cyclic voltammetry curve type of appearing is rectangular-shaped; Its area under the curve is greater than comparative example 2, simultaneously polarization phenomena also less (shown in a in the accompanying drawing 5); Through calculating, it is 285 F/g than electric capacity, apparently higher than comparative example 2; And after 1000 circle circulations, its electric capacity conservation rate is up to 99.7% (shown in a in the accompanying drawing 6), and this shows: the electrochemistry cyclical stability very excellent
of the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 1 preparation.
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 10 mg/mL, drips less ammonia regulator solution pH value between 9～11, at room temperature stirs 72 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is 98% sulfuric acid (H that 1 gram CNT is put into concentration
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 CNT in mixed acid solution is controlled to be 5 mg/mL, 60 ℃ of following mechanical agitation 24 hours, wherein sonicated was 4 hours, then with deionized water wash to neutral, obtain being prone to dispersed carbon nano tube colloidal solution.
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The easy dispersed carbon nano tube colloidal solution that graphene oxide colloidal solution that step (1) is obtained and step (2) obtain mixed 12 hours by the mass ratio of graphene oxide and CNT at 1: 0.05; Add methyl alcohol (volume ratio of deionized water and methyl alcohol is 1: 1.5) then, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2Under the Buchholz protection, with cobalt-60 radioactive source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, irradiation dose is 50 kGy, obtains hierarchy Graphene/carbon nano-tube hybridization thing.
The product analysis of embodiment 2:
Show that by the EDS analysis result C/O weight ratio is 5.3 in the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 2 preparations.
The use test instrument probe records, and the conductivity of the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 2 preparations is 0.56 S/cm.
Embodiment 3
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 0.1 mg/mL, drips less ammonia regulator solution pH value between 9～11, at room temperature stirs 48 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is 98% sulfuric acid (H that 5 gram CNTs are put into concentration
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 CNT in mixed acid solution is controlled to be 100 mg/mL, 60 ℃ of following mechanical agitation 72 hours, wherein sonicated was 6 hours, then with deionized water wash to neutral, obtain being prone to dispersed carbon nano tube colloidal solution.
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The graphene oxide colloidal solution that step (1) is obtained mixed 12 hours with 1: 10 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains; Add ethanol (volume ratio of deionized water and ethanol is 1: 4) then, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
Under the Ar Buchholz protection, with cobalt-60 radioactive source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, irradiation dose is 20 kGy, obtains hierarchy Graphene/carbon nano-tube hybridization thing.
The product analysis of embodiment 3:
Show that by the EDS analysis result C/O weight ratio is 5.7 in the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 3 preparations.
The use test instrument probe records, and the conductivity of the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 3 preparations is 0.32 S/cm.
Embodiment 4
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 2 mg/mL, drips less ammonia regulator solution pH value between 9～11, at room temperature stirs 60 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is 98% sulfuric acid (H that 2 gram CNTs are put into concentration
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 CNT in mixed acid solution is controlled to be 20 mg/mL, 60 ℃ of following mechanical agitation 48 hours, wherein sonicated was 4 hours, then with deionized water wash to neutral, obtain being prone to dispersed carbon nano tube colloidal solution.
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The graphene oxide colloidal solution that step (1) is obtained mixed 2 hours with 1: 0.25 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains; Add n-butanol (volume ratio of deionized water and n-butanol is 1: 0.2) then, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2Under the Buchholz protection, with cobalt-60 radioactive source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, irradiation dose is 500 kGy, obtains hierarchy Graphene/carbon nano-tube hybridization thing.
The product analysis of embodiment 4:
Show that by the EDS analysis result C/O weight ratio is 4.8 in the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 4 preparations.
The use test instrument probe records, and the conductivity of the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 4 preparations is 0.083 S/cm.
The preparation method of a kind of hierarchy Graphene/carbon nano-tube hybridization thing may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 6 mg/mL, drips less ammonia regulator solution pH value between 9～11, at room temperature stirs 48 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution.
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is 98% sulfuric acid (H that 2 gram CNTs are put into concentration
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 CNT in mixed acid solution is controlled to be 10 mg/mL, 60 ℃ of following mechanical agitation 60 hours, wherein sonicated was 4 hours, then with deionized water wash to neutral, obtain being prone to dispersed carbon nano tube colloidal solution.
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The graphene oxide colloidal solution that step (1) is obtained mixed 8 hours with 1: 1 mechanical agitation of mass ratio of CNT by graphene oxide with the easy dispersed carbon nano tube colloidal solution that step (2) obtains; Add isopropyl alcohol (volume ratio of deionized water and isopropyl alcohol is 1: 1) then, obtain graphene oxide/carbon nano-tube hybridization thing mixed liquor.
(4) high-energy irradiation reduction
At N
2Under the Buchholz protection, with electron accelerator graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, irradiation dose is 200 kGy, obtains hierarchy Graphene/carbon nano-tube hybridization thing.
The product analysis of embodiment 5:
Show that by the EDS analysis result C/O weight ratio is 7.1 in the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 5 preparations.
The use test instrument probe records, and the conductivity of the hierarchy Graphene/carbon nano-tube hybridization thing of embodiment 5 preparations is 3.2 S/cm.
Hierarchy Graphene/carbon nano-tube hybridization the thing that obtains with preparation method of the present invention can be used for making the active electrode material of ultracapacitor: said hierarchy Graphene/carbon nano-tube hybridization thing evenly is dispersed into solution; Drop to the graphite plate electrode surface; Treat to drip little amount of N afion solution again after its drying, after vacuumize, process work electrode.The cyclic voltammetric test is accomplished on the CHI660D electrochemical workstation; Adopt three-electrode system, platinum electrode is to electrode, and silver/silver chloride electrode is a reference electrode; Work electrode is the graphite plate electrode that is coated with active material; Electrolyte is 1 mol/L sulfuric acid solution, and the scanning voltage scope is 0～0.8 V, and sweep speed is 1～100 mV/s.The ratio electric capacity of hybrid passes through formula:
C=(∫
IDV)/(
υ mV) calculate, in the formula,
C(F/g) be to compare electric capacity;
I(A) be electric current;
V(V) be voltage;
υ(mV/s) be sweep speed;
m(g) be the quality of hybrid on the work electrode.
Claims (5)
1. the preparation method of hierarchy Graphene/carbon nano-tube hybridization thing is characterized in that, may further comprise the steps:
(1) preparation graphene oxide colloidal solution
Graphite oxide is scattered in the deionized water; The concentration of controlled oxidation graphite is 0.1～10 mg/mL, drips less ammonia regulator solution pH value between 9～11, stirs under the room temperature 48～72 hours; Remove unstripped graphite oxide through low-speed centrifugal, obtain graphene oxide colloidal solution;
(2) preparation is prone to dispersed carbon nano tube colloidal solution
It is that 98% sulfuric acid and concentration are the nitration mixture of 60～70% nitric acid that CNT is put into concentration, H
2SO
4With HNO
3Volume ratio be 3: 1; The concentration of CNT in mixed acid solution is controlled to be 5～100 mg/mL, and 60 ℃ of following mechanical agitation 24～72 hours, wherein sonicated was 4～6 hours; Use the deionized water cyclic washing to neutral then, obtain being prone to dispersed carbon nano tube colloidal solution;
(3) mixed oxidization Graphene colloidal solution and easy dispersed carbon nano tube colloidal solution
The easy dispersed carbon nano tube colloidal solution that graphene oxide colloidal solution that step (1) is obtained and step (2) obtain mixed 2～12 hours; Interpolation can be removed the alcohols solvent of oxidizing substance in the solution, obtains graphene oxide/carbon nano-tube hybridization thing mixed liquor;
(4) high-energy irradiation reduction
Under inert gas shielding, with the high-energy ray radiation source graphene oxide/carbon nano-tube hybridization thing mixed liquor is carried out the irradiation reduction, obtain target product---hierarchy Graphene/carbon nano-tube hybridization thing.
2. the preparation method of hierarchy Graphene according to claim 1/carbon nano-tube hybridization thing; It is characterized in that the described graphene oxide colloidal solution of step (3) and easy dispersed carbon nano tube colloidal solution are 1: 0.05～10 to mix stirring by the graphene oxide and the mass ratio of CNT.
3. the preparation method of hierarchy Graphene according to claim 1/carbon nano-tube hybridization thing is characterized in that, the described alcohols solvent of step (3) is water-soluble monohydric alcohol, comprises a kind of in methyl alcohol, ethanol, isopropyl alcohol, the n-butanol.
4. the preparation method of hierarchy Graphene according to claim 3/carbon nano-tube hybridization thing is characterized in that the volume ratio of described alcohols solvent of step (3) and deionized water is 0.2～4: 1.
5. the preparation method of hierarchy Graphene according to claim 1/carbon nano-tube hybridization thing is characterized in that, the described high-energy ray radiation source of step (4) is a kind of in cobalt-60 or the electron accelerator, and irradiation dose is 20～500 kGy.
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