CN107808779A - CNT/three-dimensional graphene composite material, its preparation method and application - Google Patents
CNT/three-dimensional graphene composite material, its preparation method and application Download PDFInfo
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- CN107808779A CN107808779A CN201610808604.8A CN201610808604A CN107808779A CN 107808779 A CN107808779 A CN 107808779A CN 201610808604 A CN201610808604 A CN 201610808604A CN 107808779 A CN107808779 A CN 107808779A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000007772 electrode material Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000012808 vapor phase Substances 0.000 claims abstract description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 12
- 238000004146 energy storage Methods 0.000 claims abstract description 8
- 229920002521 macromolecule Polymers 0.000 claims abstract description 7
- 239000002041 carbon nanotube Substances 0.000 claims description 44
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 23
- 229920001940 conductive polymer Polymers 0.000 claims description 21
- 239000002322 conducting polymer Substances 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 239000003292 glue Substances 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 14
- -1 paratoluenesulfonic acid sodium salt Chemical class 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000000017 hydrogel Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 150000002081 enamines Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims 1
- 239000011263 electroactive material Substances 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 229940078494 nickel acetate Drugs 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 5
- 239000003708 ampul Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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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- Engineering & Computer Science (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
This application discloses a kind of CNT/three-dimensional graphene composite material and preparation method thereof.The preparation method includes：The three-dimensional grapheme aeroge is placed in chemical vapor-phase growing equipment, and using non-ionic macromolecule compound as carbon source, by chemical vapour deposition technique in three-dimensional grapheme aeroge surface and growth inside CNT, target product is made.The good conductivity of the conductive network of the application CNT/three-dimensional graphene composite material, specific surface area is big, and electroactive material load capacity is high, stable electrochemical property.The invention also discloses the electrode material based on the composite, electrode and energy storage device, such as flexible all solid state Asymmetric Supercapacitor, and such all solid state Asymmetric Supercapacitor of flexibility has very high stability.
Description
Technical field
The application is specifically related to a kind of CNT/three-dimensional graphene composite material, its preparation method and application, such as
The purposes in ultracapacitor is prepared, belongs to field of nano material preparation.
Background technology
The composite of CNT/three-dimensional grapheme (CNTs/3DG) nanostructured is built, gives full play to CNT
With the cooperative effect of graphene, it can not only utilize the high specific surface area of CNT/three-dimensional grapheme and increase electrochemistry work
The load capacity of property material (transition metal oxide, conducting polymer), its conductive network can also be made full use of accelerate electronics,
The conduction of ion.Therefore, the electrode with such nanostructured is often considered as a kind of most potential ultracapacitor
Electrode.The process route of the composite of various CNTs/three-dimensional grapheme nanostructured, example are devised in the prior art
Such as, researcher prepares CNT/three-dimensional foam graphene (CNTs/3DGF) nanostructured of manganese oxide cladding
Electrode, but it is too high to prepare the complex process of the nanostructure composite material, cost, and also foamy graphite alkene has nearly 90%
Hole, CNT is often only grown on the skeleton of foamy graphite alkene, so that greatly reducing subsequent electrochemical activity
The carrying capacity of material thus limits application of such electrode in flexible super capacitor.
The content of the invention
The main purpose of the application be to provide a kind of CNT/three-dimensional graphene composite material, its preparation method and
Using to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical scheme that the application uses includes：
The embodiment of the present application provides a kind of preparation method of CNT/three-dimensional graphene composite material, and it includes：
Three-dimensional grapheme aeroge is provided, and the surface of at least described three-dimensional grapheme aeroge and contained hole is interior
Metal ion of the load with catalytic activity on wall；
The three-dimensional grapheme aeroge is placed in chemical vapor-phase growing equipment, and with non-ionic macromolecule compound
As carbon source, by chemical vapour deposition technique in the three-dimensional grapheme aeroge surface and growth inside CNT, it is made
CNT/the three-dimensional graphene composite material.
In some more preferred embodiment, described preparation method includes：
The first area and carbon source and three-dimensional grapheme aeroge being respectively placed in chemical vapor-phase growing equipment
Two regions, the first area and second area are sequentially distributed along the direct of travel of carrier gas；
By the rise of the temperature of the first area until making the carbon source be decomposed into carbon, and by the temperature of the second area
600 DEG C~900 DEG C are promoted to, while carrier gas is passed through into the chemical vapor-phase growing equipment, so as in the three-dimensional grapheme
Aeroge surface and growth inside CNT.
Further, the non-ionic macromolecule compound is included in polyvinylpyrrolidone, polytetrafluoroethyl-ne enamine
The combination of any one or two kinds, but not limited to this.
Further, the catalytic metal ion includes transition metal ions.
The embodiment of the present application additionally provides a kind of CNT/three-dimensional graphene composite material, and it includes three-dimensional grapheme
And CNT, the CNT is grown directly upon the sheet surfaces of three-dimensional grapheme, and is closely tied with three-dimensional grapheme
Close；Wherein, the mass ratio of the CNT and graphene is 1：9~1：2；CNT/the three-dimensional grapheme simultaneously
The aperture of hole contained by composite is 3~50nm, and specific surface area is in 1300m2g-1More than.
The embodiment of the present application additionally provides a kind of electrode material, and it is included：Described CNT/three-dimensional grapheme is compound
Material；And it is carried on the transition metal oxide of the CNT/three-dimensional graphene composite material surface and inside.
Wherein, the transition metal oxide includes manganese oxide, cobalt oxide or ruthenium-oxide etc., but not limited to this.
The embodiment of the present application additionally provides a kind of method for preparing the electrode material, and it includes：
CNT/three-dimensional graphene composite material is prepared using foregoing method；
The aqueous solution of CNT/three-dimensional graphene composite material and transistion metal compound is subjected to hydro-thermal reaction, made
The CNT/three-dimensional graphene composite material surface and internal load transition metal oxide, form the electrode material.
The embodiment of the present application additionally provides a kind of electrode material, it is characterised in that includes：Described CNT/three-dimensional stone
Black alkene composite；And it is carried on the conducting polymer of the CNT/three-dimensional graphene composite material surface and inside
Thing.
Further, the conducting polymer includes polypyrrole, polythiophene or polyaniline, but not limited to this.
The embodiment of the present application additionally provides a kind of preparation method of electrode material, and it includes：
CNT/three-dimensional graphene composite material is prepared using foregoing any method；
CNT/three-dimensional graphene composite material and conducting polymer monomer, oxidant (while are triggered as polymerizeing
Agent), cosolvent be sufficiently mixed in a solvent, reacted afterwards, make the CNT/three-dimensional graphene composite material surface
And internal load conducting polymer, form the electrode material.
The embodiment of the present application additionally provides the use of the CNT/three-dimensional graphene composite material and the electrode material
On the way, such as the purposes in electrode, energy storage device (such as ultracapacitor) is prepared.
Compared with prior art, it is the advantages of the application：
1) the conductive good and specific surface area of the conductive network of the CNT/three-dimensional graphene composite material provided is big
The advantages that, thus the load capacity of electroactive material is significantly increased, and its preparation method is simple, condition is easily-controllable, and cost is low.
2) preferably, when with electroactive materials such as the CNT/three-dimensional graphene composite material load manganese oxide,
It can not only provide good conductive network for these electroactive materials, be also possible to prevent these electroactive materials in discharge and recharge
During stack and cause resistance to increase, be significant for fake capacitance.
3) job stability by the ultra-capacitor of the CNT/three-dimensional graphene composite material assembling is high, example
Such as, the specific capacitance of the flexible all solid state Asymmetric Supercapacitor based on the composite only declines after 20000 circulations
15.4%, and specific capacitance remains to reach 86.8% after 500 bendings.
Brief description of the drawings
Fig. 1 a-1d be three-dimensional grapheme aeroge (3DGA) in the embodiment of the present application 1, different quality ratio (10wt%,
20wt% and 30wt%) nickel acetate and GO (graphene) prepare CNT/three-dimensional grapheme aeroge (CNTs/3DGA)
SEM figure.
Fig. 2 a-2b are three-dimensional grapheme aeroge (3DGA) and a kind of typical CNT/tri- in the embodiment of the present application 1
Tie up the BET specific surface area figure of graphene aerogel (CNTs/3DGA).
Fig. 3 is three-dimensional grapheme aeroge (3DGA) and a kind of typical CNT/three-dimensional stone in the embodiment of the present application 1
The Raman spectrogram of black alkene aeroge (CNTs/3DGA).
Fig. 4 a- Fig. 4 b and Fig. 4 c- Fig. 4 d are a kind of carbon nanometer of typical oxidation manganese cladding in the embodiment of the present application 1 respectively
Pipe/three-dimensional grapheme aeroge (MnO2/ CNTs/3DGA) SEM figure and TEM figure；
Fig. 5 a- Fig. 5 b are when sweep speed is 5mV s respectively in the embodiment of the present application 1~5-1With 50mV s-1When, load
There is the cyclic voltammogram of CNT/three-dimensional grapheme aeroge flexible electrode of varying number active matter；
Fig. 5 c are CNT/three-dimensional grapheme airsettings that varying number active matter is loaded with the embodiment of the present application 1~5
The area capacitance of glue flexible electrode and the graph of a relation for sweeping speed；
Fig. 5 d are when active material carrying capacity is 7.5mg cm in the embodiment of the present application 1~5-2When CNT/three-dimensional graphite
Alkene aeroge flexible electrode sweeps the cyclic voltammogram under speed in difference；
Fig. 5 e are the different CNTs/three-dimensional grapheme airsetting in the embodiment of the present application 1~5 under the conditions of difference sweeps speed
The area capacitance of glue flexible electrode and the graph of a relation of active material carrying capacity；
Fig. 5 f are the active matters of different CNTs in the embodiment of the present application 1~5/three-dimensional grapheme aeroge flexible electrode
The graph of a relation of matter carrying capacity and resistance.
Embodiment
In view of deficiency of the prior art, inventor is able to propose the application's through studying for a long period of time and largely putting into practice
Technical scheme.The technical scheme, its implementation process and principle etc. will be further explained as follows.
The embodiment of the present application, which provides a kind of preparation method of CNT/three-dimensional graphene composite material, to be included：
Three-dimensional grapheme aeroge is provided, and the surface of at least described three-dimensional grapheme aeroge and contained hole is interior
Metal ion of the load with catalytic activity on wall；
The three-dimensional grapheme aeroge is placed in chemical vapor-phase growing equipment, and with non-ionic macromolecule compound
As carbon source, by chemical vapour deposition technique in the three-dimensional grapheme aeroge surface and growth inside CNT, it is made
CNT/the three-dimensional graphene composite material.
In some more preferred embodiment, described preparation method includes：
The first area and carbon source and three-dimensional grapheme aeroge being respectively placed in chemical vapor-phase growing equipment
Two regions, the first area and second area are sequentially distributed along the direct of travel of carrier gas；
By the rise of the temperature of the first area until making the carbon source be decomposed into carbon, and by the temperature of the second area
600 DEG C~900 DEG C are promoted to, while carrier gas is passed through into the chemical vapor-phase growing equipment, so as in the three-dimensional grapheme
Aeroge surface and growth inside CNT.
Further, it is preferably 10~30sccm that the carrier gas, which can use inert gas, the flows such as Ar gas,.
Further, the non-ionic macromolecule compound is included in polyvinylpyrrolidone, polytetrafluoroethyl-ne enamine
The combination of any one or two kinds, but not limited to this.
Further, the catalytic metal ion includes transition metal ions.Preferably, the transition metal ions is selected from
Ni2+、Fe2+Or Co2+, but not limited to this.Especially preferred, the transition metal ions is Ni2+。
More preferable, the distance of foregoing first area and second area is 5~10cm.
Further, the temperature conditionss that the chemical vapour deposition technique uses are preferably 600~900 DEG C, and the time is preferably
5mim~1.5h or longer time, more preferably 5mim or 10min or 1h or 1.5h.
Further, the preparation method includes：After soluble metallic salt is mixed with graphene aqueous solution, 60 DEG C~
250 DEG C, hydro-thermal reaction is preferably carried out, obtains the hydrogel of three-dimensional grapheme, then through drying process, obtain the three-dimensional graphite
Alkene aeroge；The metal ion with catalytic activity derives from the soluble metallic salt.
Further, the soluble metallic salt includes nickel salt.
Further, the mass ratio of the soluble metallic salt and graphene is preferably 0.1:100~80:100.
Further, the mode of the drying process is preferably freeze-drying mode.
In a more typical specific embodiment, the preparation method can include：
By hydro-thermal method, three-dimensional of the metal corsslinking ion synthesis with nickel salt using the nickel ion in nickel acetate as divalence
Graphene aerogel；
Pass through chemical vapor deposition, using polyvinylpyrrolidone as carbon source, the nickel on three-dimensional grapheme aeroge surface
It is catalyst that salt reduction, which becomes nickel particle, and carbon nanometer is grown under certain temperature (600~900 DEG C, preferably 650~900 DEG C)
Pipe.
Wherein, at high temperature, such as at a high temperature of more than 600 DEG C, polyvinylpyrrolidone is decomposed into carbon, passes through carrier gas band
Onto three-dimensional grapheme aeroge.
More specifically, the three-dimensional grapheme aeroge for loading the metal ion with catalytic activity can be positioned over stone
Among English pipe, using polyvinylpyrrolidone as carbon source, place from 5~10cm of three-dimensional grapheme aeroge；Three-dimensional grapheme gas
It is catalyst that the nickel salt reduction of gel surface, which becomes nickel particle, grows CNT under the conditions of 900 DEG C.
The embodiment of the present application additionally provides the CNT/three-dimensional graphene composite material prepared by methods described.
The embodiment of the present application additionally provides a kind of electrode material, and it is included：Described CNT/three-dimensional grapheme is compound
Material；And it is carried on the transition metal oxide of the CNT/three-dimensional graphene composite material surface and inside.
Further, the transition metal oxide includes manganese oxide, cobalt oxide or ruthenium-oxide etc., but not limited to this.
Further, load of the transition metal oxide on the CNT/three-dimensional graphene composite material
Measure as 1.2~8.8mg cm-2, and the transition metal oxide is evenly coated at carbon nano tube surface with nanometer sheet form.
Further, the diameter of the nanometer sheet is preferably 2~nm, and thickness is preferably 5~10nm.
The embodiment of the present application additionally provides a kind of preparation method of electrode material, and it includes：
CNT/three-dimensional graphene composite material is prepared using foregoing any method；
The aqueous solution of CNT/three-dimensional graphene composite material and transistion metal compound is mixed at 50 DEG C~180 DEG C
Reaction is closed, makes the CNT/three-dimensional graphene composite material surface and internal load transition metal oxide, described in formation
Electrode material.
Further, the transistion metal compound includes soluble compound of nickeliferous, manganese or ruthenium etc., preferably solvable
Property nickel salt, manganese salt or ruthenium salt, preferably soluble manganese salt or potassium permanganate etc..
The embodiment of the present application additionally provides a kind of electrode material, and it is included：Described CNT/three-dimensional grapheme is compound
Material；And it is carried on the conducting polymer of the CNT/three-dimensional graphene composite material surface and inside.
Further, load capacity of the conducting polymer on the CNT/three-dimensional graphene composite material is
0.37~2.35mg cm-2, and the conducting polymer is evenly coated at carbon nano tube surface with nanometer sheet form.
Further, the conducting polymer includes polypyrrole, polyaniline, polythiophene or other conducting polymers, but not
It is limited to this.
Further, the diameter of the nanometer sheet is preferably 2-~nm, and thickness is preferably 5~10nm.
The embodiment of the present application additionally provides a kind of preparation method of electrode material, and it includes：
CNT/three-dimensional graphene composite material is prepared using foregoing any method；
CNT/three-dimensional graphene composite material and conducting polymer monomer, oxidant, cosolvent are filled in a solvent
Divide mixing, afterwards in -10 DEG C~50 DEG C reactions, make the CNT/three-dimensional graphene composite material surface and internal load
Conducting polymer, form the electrode material.
Further, the conducting polymer monomer includes pyrroles, aniline or thiophene, but not limited to this.
Further, the oxidant (also as polymerization initiator) includes ammonium persulfate, but not limited to this.
Further, the cosolvent includes paratoluenesulfonic acid sodium salt or other sodium salts.
The embodiment of the present application additionally provides a kind of electrode, and it includes described CNT/three-dimensional graphene composite material
Or described electrode material.
The embodiment of the present application additionally provides described CNT/three-dimensional graphene composite material, described electrode material
Or the purposes of the electrode, such as the purposes in the devices such as ultracapacitor are prepared.
For example, the embodiment of the present application provides a kind of energy storage device, it includes described electrode.
Further, the energy storage device can be ultracapacitor, and the ultracapacitor includes electrolyte and institute
The electrode material or electrode stated.
Further, the ultracapacitor is all solid state asymmetric flexible super capacitor.
The embodiment of the present application first passes through the technologies such as Hydrothermal Synthesiss, chemical vapor deposition and has synthesized CNT/three-dimensional graphite
The conductive network of alkene aeroge, the thing such as load (preferably cladding) manganese oxide, conducting polymer is electroactive on this conductive network
Material, form three-dimension flexible electrode.Because this structural conductive is good and specific surface area is big, thus substantially increase electric active matter
The carrying capacity of matter, and the 3-D nano, structure can be not only that the good conductive networks of offer such as manganese oxide are also possible to prevent to aoxidize
Manganese etc. stacks in charge and discharge process and causes resistance to increase.It is and then flexible all solid state asymmetric based on such electrode assembling
The specific capacitance of ultracapacitor only declines 15.4% after 20000 circulations and specific capacitance remains to reach after 500 bendings
To 86.8%.
The technical scheme of the application is further explained below in conjunction with accompanying drawing and some embodiments.
Embodiment 1
Three-dimensional grapheme aeroge is prepared first, and step includes：
By nickel acetate (Ni (AC)2) and graphene aqueous solution (GO) and according to different mass ratio (mNi/mGO=1wt%,
2wt%, 3wt%) ultrasonic mixing is carried out, three-dimensional grapheme water-setting is then obtained by the method (100 DEG C, 5h) of Hydrothermal Synthesiss
Glue.
Foregoing three-dimensional grapheme hydrogel is freeze-dried 6h under conditions of -30 DEG C, 2Pa and obtains three-dimensional grapheme airsetting
Glue.
With polyvinylpyrrolidone (PVP) for solid carbon source, the carbon source and the three-dimensional grapheme aeroge are respectively implanted
In the quartz ampoule of chemical vapor-phase growing equipment, and make both distance about 5~10cm, reaction start before be first passed through carrier gas (10~
30min) remove the air in growth apparatus and whole course of reaction air-flow keeps identical speed (about 10~30sccm)；Then will
Carbon source is heated to about 600 DEG C and being incubated 1h makes it decompose completely；The three-dimensional grapheme aeroge is finally heated to about 600~
650 DEG C, about 1h is grown by chemical vapour deposition technique, obtains CNT/three-dimensional grapheme airsetting of different proportion structure
Glue composite (CNTs/3DGA), its pattern and specific surface area test result see Fig. 2 a- Fig. 2 b and Fig. 3.
Thereafter, (concentration is 0.1mM~1.0mM KMnO to potassium permanganate respectively in varing proportions4Solution) it is used as forerunner
Body, hydro-thermal reaction obtains MnO under conditions of 100 DEG C, 1h with foregoing CNTs/3DGA2/ CNTs/3DGA flexible electrodes.
And with deionized water and ethanol (0.1:1, v/v) it is solvent, paratoluenesulfonic acid sodium salt (pTSNa) and ammonium persulfate
(APS,(NH4)2S2O8) and pyridine be solute (mass ratio pTSNa:APS is 0.1:2) it is -10~5 DEG C, 2min conditions in temperature
Ppy (polypyridine)/CNTs/3DGA flexible electrodes are obtained under reaction.
Finally, based on MnO derived above2/ CNTs/3DGA flexible electrodes, Ppy/CNTs/3DGA flexible electrodes and PVA/
Na2SO4Gel is all solid state asymmetric flexible super capacitor of electrolyte design and tests its chemical property.
Embodiment 2
The aeroge of three-dimensional grapheme is prepared first, is concretely comprised the following steps：
By nickel acetate (Ni (AC)2) and graphene aqueous solution (GO) and according to different mass ratio (mNi/mGO=4wt%,
6wt%, 8wt%) ultrasonic mixing is carried out, three-dimensional grapheme water-setting is then obtained by the method (120 DEG C, 8h) of Hydrothermal Synthesiss
Glue.
Foregoing three-dimensional grapheme hydrogel is freeze-dried 8h under conditions of -10 DEG C, 5Pa and obtains three-dimensional grapheme airsetting
Glue.
With polyvinylpyrrolidone (PVP) for solid carbon source, the carbon source and the three-dimensional grapheme aeroge are respectively implanted
In the quartz ampoule of chemical vapor-phase growing equipment, and make both distance about 5~10cm, reaction start before be first passed through carrier gas (10~
30min) remove the air in growth apparatus and whole course of reaction air-flow keeps identical speed (about 10~30sccm)；Then will
Carbon source is heated to about 600 DEG C and being incubated 1h makes it decompose completely；The three-dimensional grapheme aeroge is finally heated to about 700 DEG C,
About 1.5h is grown by chemical vapour deposition technique, the CNT/three-dimensional grapheme aeroge for obtaining different proportion structure is answered
Condensation material (CNTs/3DGA), obtain CNT/three-dimensional grapheme aerogel composite (CNTs/ of different proportion structure
3DGA)。
Then, potassium permanganate (0.2mM~20mM KMnO respectively in varing proportions4) be used as presoma, 50 DEG C,
Under the conditions of 30min MnO is obtained with foregoing CNTs/3DGA hydro-thermal reactions2/ CNTs/3DGA flexible electrodes.
And with deionized water and ethanol (0.1:10, v/v) it is solvent, paratoluenesulfonic acid sodium salt (pTSNa) and ammonium persulfate
(APS,(NH4)2S2O8) and pyridine be solute (mass ratio pTSNa:APS=0.1:20) it is -10~50 DEG C, 10min bars in temperature
Reaction obtains Ppy/CNTs/3DGA flexible electrodes under part.
Finally, based on MnO derived above2/ CNTs/3DGA flexible electrodes, Ppy/CNTs/3DGA electrodes and PVA/
Na2SO4Gel is that electrolyte constructs all solid state asymmetric flexible super capacitor and tests its chemical property.
Embodiment 3
The aeroge of three-dimensional grapheme is prepared first, and step is：
By nickel acetate (Ni (AC)2) and graphene aqueous solution (GO) and according to different mass ratio (mNi/mGO=0.4wt%,
0.6wt%, 0.8wt%) ultrasonic mixing is carried out, three-dimensional grapheme water-setting is then obtained by hydrothermal synthesis method (60 DEG C, 3h)
Glue.
Foregoing three-dimensional grapheme hydrogel is freeze-dried 8h under conditions of -0 DEG C, 5Pa and obtains three-dimensional grapheme airsetting
Glue.
With polyvinylpyrrolidone (PVP) for solid carbon source, the carbon source and the three-dimensional grapheme aeroge are respectively implanted
In the quartz ampoule of chemical vapor-phase growing equipment, and make both distance about 5~10cm, reaction is first passed through carrier gas (Ar, about 10 before starting
~30min) remove air in growth apparatus and whole course of reaction air-flow keeps identical speed (about 10~30sccm)；Then
Carbon source is heated to about 600 DEG C and being incubated 1h makes it decompose completely；The three-dimensional grapheme aeroge is finally heated to about 750
DEG C, about 1.5h is grown by chemical vapour deposition technique, obtains CNT/three-dimensional grapheme aeroge of different proportion structure
Composite (CNTs/3DGA).
Then, potassium permanganate (200mM~500mM KMnO respectively in varing proportions4) be used as presoma, 60 DEG C,
Under conditions of 30min MnO is obtained with foregoing CNTs/3DGA hydro-thermal reactions2/ CNTs/3DGA flexible electrodes.
And with deionized water and ethanol (1:0, v/v) it is solvent, paratoluenesulfonic acid sodium salt (pTSNa) and ammonium persulfate
(APS,(NH4)2S2O8) and pyridine be solute (mass ratio pTSNa:APS is 1:0, APS dosage be more than 0) temperature be -0
~10 DEG C, reaction obtains Ppy/CNTs/3DGA flexible electrodes under the conditions of 50min.
Finally, based on above MnO2/ CNTs/3DGA flexible electrodes, Ppy/CNTs/3DGA flexible electrodes and PVA/Na2SO4
Gel is that electrolyte constructs all solid state asymmetric flexible super capacitor and tests its chemical property.
Embodiment 4
The aeroge of three-dimensional grapheme is prepared first, is concretely comprised the following steps：
By nickel acetate (Ni (AC)2) and graphene aqueous solution (GO) and according to different mass ratio (mNi/mGO=40wt%,
60wt%, 80wt%) ultrasonic mixing is carried out, three-dimensional grapheme water-setting is then obtained by the method (220 DEG C, 8h) of Hydrothermal Synthesiss
Glue；
Foregoing three-dimensional grapheme hydrogel is freeze-dried 8h under conditions of -0 DEG C, 5Pa and obtains three-dimensional grapheme airsetting
Glue.
With polyvinylpyrrolidone (PVP) for solid carbon source, the carbon source and the three-dimensional grapheme aeroge are respectively implanted
In the quartz ampoule of chemical vapor-phase growing equipment, and make both distance about 5~10cm, reaction start before be first passed through carrier gas (10~
30min) remove the air in growth apparatus and whole course of reaction air-flow keeps identical speed (about 10~30sccm)；Then will
Carbon source is heated to about 600 DEG C and being incubated 1h makes it decompose completely；The three-dimensional grapheme aeroge is finally heated to about 800 DEG C,
CNT/three-dimensional grapheme aeroge that different proportion structure is obtained by chemical vapour deposition technique growth about 5min is compound
Material (CNTs/3DGA).
Then, potassium permanganate (1M-20M KMnO respectively in varing proportions4) it is used as presoma, in 80 DEG C, 30min
Under the conditions of with foregoing CNTs/3DGA hydro-thermal reactions obtain MnO2/ CNTs/3DGA flexible electrodes.
And with deionized water and ethanol (10:1, v/v) it is solvent, paratoluenesulfonic acid sodium salt (pTSNa) and ammonium persulfate
(APS,(NH4)2S2O8) and pyridine be solute (mass ratio pTSNa:APS is 10:2) it is -10~20 DEG C, 30min conditions in temperature
Lower reaction obtains Ppy/CNTs/3DGA flexible electrodes.
Finally, based on MnO derived above2/ CNTs/3DGA flexible electrodes, Ppy/CNTs/3DGA flexible electrodes and PVA/
Na2SO4Gel is that electrolyte constructs all solid state asymmetric flexible super capacitor and tests its chemical property.
Embodiment 5
The aeroge of three-dimensional grapheme is prepared first, is concretely comprised the following steps：
By nickel acetate (Ni (AC)2) and graphene aqueous solution (GO) and according to different mass ratio (mNi/mGO=45wt%,
50wt%, 70wt%) ultrasonic mixing is carried out, three-dimensional grapheme water is then obtained by the method (250 DEG C, 10h) of Hydrothermal Synthesiss
Gel.
Foregoing three-dimensional grapheme hydrogel is freeze-dried 2h under conditions of 0 DEG C, 5Pa and obtains three-dimensional grapheme airsetting
Glue.
With polyvinylpyrrolidone (PVP) for solid carbon source, the carbon source and the three-dimensional grapheme aeroge are respectively implanted
In the quartz ampoule of chemical vapor-phase growing equipment, and make both distance about 5~10cm, reaction start before be first passed through carrier gas (10~
30min) remove the air in growth apparatus and whole course of reaction air-flow keeps identical speed (about 10~30sccm)；Then will
Carbon source is heated to about 600 DEG C and being incubated 1h makes it decompose completely；The three-dimensional grapheme aeroge is finally heated to about 850~
900 DEG C, CNT/three-dimensional grapheme airsetting of different proportion structure is obtained by chemical vapour deposition technique growth about 5min
Glue composite (CNTs/3DGA).
Then, potassium permanganate (5M~20M KMnO respectively in varing proportions4) it is used as presoma, in 180 DEG C, 2min
Under the conditions of hydro-thermal reaction obtain MnO2/ CNTs/3DGA flexible electrodes.
And with deionized water and ethanol (10:1, v/v) it is solvent, paratoluenesulfonic acid sodium salt (pTSNa) and ammonium persulfate
(APS,(NH4)2S2O8) and pyridine be solute (mass ratio pTSNa:APS is 1:2) it is 10~20 DEG C, under the conditions of 30min in temperature
Reaction obtains Ppy/CNTs/3DGA flexible electrodes.
Finally, based on MnO derived above2/ CNTs/3DGA flexible electrodes, Ppy/CNTs/3DGA flexible electrodes and PVA/
Na2SO4Gel is that electrolyte constructs all solid state asymmetric flexible super capacitor and tests its chemical property.
It should be appreciated that above-described embodiment is only the technical concepts and features for illustrating the application, its object is to allow be familiar with this
The personage of item technology can understand present context and implement according to this, and the protection domain of the application can not be limited with this.It is all
The equivalent change or modification made according to the application Spirit Essence, it should all cover within the protection domain of the application.
Claims (21)
- A kind of 1. preparation method of CNT/three-dimensional graphene composite material, it is characterised in that including：Three-dimensional grapheme aeroge is provided, and on the surface of at least described three-dimensional grapheme aeroge and the inwall of contained hole Metal ion of the load with catalytic activity；The three-dimensional grapheme aeroge is placed in chemical vapor-phase growing equipment, and using non-ionic macromolecule compound as Carbon source, by chemical vapour deposition technique in the three-dimensional grapheme aeroge surface and growth inside CNT, it is made described CNT/three-dimensional graphene composite material.
- 2. preparation method according to claim 1, it is characterised in that including：The first area and the secondth area carbon source and three-dimensional grapheme aeroge being respectively placed in chemical vapor-phase growing equipment Domain, the first area and second area are sequentially distributed along the direct of travel of carrier gas；By the temperature rise of the first area until making the carbon source be decomposed into carbon, and the temperature of the second area is lifted To 600 DEG C~900 DEG C, while carrier gas is passed through into the chemical vapor-phase growing equipment, so as in the three-dimensional grapheme airsetting Glue surface and growth inside CNT.
- 3. preparation method according to claim 1, it is characterised in that：The distance of first area and second area be 5~ 10cm。
- 4. preparation method according to claim 1 or 2, it is characterised in that：The non-ionic macromolecule compound includes The combination of any one or two kinds in polyvinylpyrrolidone, polytetrafluoroethyl-ne enamine；And/or the carrier gas includes Ar gas；It is excellent Choosing, the carrier gas flux is 10~30sccm.
- 5. preparation method according to claim 1, it is characterised in that including：By soluble metallic salt and graphene aqueous solution After mixing, hydro-thermal reactions are carried out at 60 DEG C~250 DEG C, obtain the hydrogel of three-dimensional grapheme, then through drying process, described in acquisition Three-dimensional grapheme aeroge；The metal ion with catalytic activity derives from the soluble metallic salt.
- 6. preparation method according to claim 5, it is characterised in that：The soluble metallic salt includes nickel salt；And/or The mass ratio of the soluble metallic salt and graphene is 0.1:100~80:100；And/or the mode bag of the drying process Include freeze-drying mode.
- 7. the preparation method of CNT/three-dimensional graphene composite material according to claim 1 or 5, it is characterised in that： The catalytic metal ion includes transition metal ions；Preferably, the transition metal ions is selected from Ni2+、Fe2+Or Co2+；Especially It is preferable, and the transition metal ions is Ni2+。
- 8. CNT/three-dimensional graphene composite material prepared by the method as any one of claim 1-7.
- 9. CNT/three-dimensional graphene composite material, it is characterised in that including three-dimensional grapheme and CNT, the carbon Nanotube is grown directly upon the sheet surfaces of three-dimensional grapheme, and is combined closely with three-dimensional grapheme；Wherein, the CNT Mass ratio with graphene is 1：9~1：2；The hole of hole contained by the CNT/three-dimensional graphene composite material simultaneously Footpath is 3~50nm, and specific surface area is in 1300m2g-1More than.
- 10. a kind of electrode material, it is characterised in that include：CNT/three-dimensional grapheme described in claim 8 or 9 is compound Material；And it is carried on the transition metal oxide of the CNT/three-dimensional graphene composite material surface and inside；Its In, load capacity of the transition metal oxide on the CNT/three-dimensional graphene composite material is 1.2~8.8mg cm-2, and the transition metal oxide is evenly coated at carbon nano tube surface with nanometer sheet form.
- 11. electrode material according to claim 10, it is characterised in that：The transition metal oxide include manganese oxide, Cobalt oxide or ruthenium-oxide；And/or a diameter of 2-~nm of the nanometer sheet, thickness are 5~10nm.
- A kind of 12. preparation method of electrode material, it is characterised in that including：CNT/three-dimensional graphene composite material is prepared using method any one of claim 1-7；CNT/three-dimensional graphene composite material is mixed instead with the aqueous solution of transistion metal compound at 50 DEG C~180 DEG C Should, make the CNT/three-dimensional graphene composite material surface and internal load transition metal oxide, form the electrode Material.
- 13. preparation method according to claim 12, it is characterised in that：The transistion metal compound includes nickeliferous, manganese Or the soluble compound of ruthenium, preferably soluble nickel salt, manganese salt or ruthenium salt, preferably soluble manganese salt or potassium permanganate.
- 14. a kind of electrode material, it is characterised in that include：CNT/three-dimensional grapheme described in claim 8 or 9 is compound Material；And it is carried on the conducting polymer of the CNT/three-dimensional graphene composite material surface and inside；Wherein, institute It is 0.37~2.35mg cm to state load capacity of the conducting polymer on the CNT/three-dimensional graphene composite material-2, and The conducting polymer is evenly coated at carbon nano tube surface with nanometer sheet form.
- 15. electrode material according to claim 14, it is characterised in that：The conducting polymer includes polypyrrole, poly- thiophene Fen or polyaniline；And/or a diameter of 2-~nm of the nanometer sheet, thickness are 5~10nm.
- A kind of 16. preparation method of electrode material, it is characterised in that including：CNT/three-dimensional graphene composite material is prepared using method any one of claim 1-7；CNT/three-dimensional graphene composite material and conducting polymer monomer, oxidant, cosolvent is fully mixed in a solvent Close, afterwards in -10 DEG C~50 DEG C reactions, make the CNT/three-dimensional graphene composite material surface and internal load conductive Polymer, form the electrode material.
- 17. preparation method according to claim 16, it is characterised in that：The conducting polymer monomer includes pyrroles, benzene Amine or thiophene；And/or the oxidant includes ammonium persulfate；And/or the cosolvent includes paratoluenesulfonic acid sodium salt.
- A kind of 18. electrode, it is characterised in that comprising CNT/three-dimensional graphene composite material described in claim 8 or 9, Electrode material described in claim 10 or 11, or, the electrode material described in claims 14 or 15.
- 19. energy storage device, it is characterised in that include the electrode described in claim 18.
- 20. energy storage device according to claim 19, it is characterised in that：The energy storage device is ultracapacitor, described Ultracapacitor includes electrolyte and described electrode.
- 21. energy storage device according to claim 20, it is characterised in that：The ultracapacitor is all solid state asymmetric soft Property ultracapacitor.
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