CN110073458A - The preparation method of accordion graphene complex, the complex thus prepared and the supercapacitor comprising complex - Google Patents

The preparation method of accordion graphene complex, the complex thus prepared and the supercapacitor comprising complex Download PDF

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Publication number
CN110073458A
CN110073458A CN201780076905.9A CN201780076905A CN110073458A CN 110073458 A CN110073458 A CN 110073458A CN 201780076905 A CN201780076905 A CN 201780076905A CN 110073458 A CN110073458 A CN 110073458A
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graphene
mentioned
complex
accordion
nano tube
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CN110073458B (en
Inventor
张喜栋
蒋韩权
崔志赫
吉大燮
金亨锡
裵仁国
徐宙范
赵恩姬
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Korea Institute of Geoscience and Mineral Resources KIGAM
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Korea Institute of Geoscience and Mineral Resources KIGAM
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Priority claimed from KR1020160169022A external-priority patent/KR101744122B1/en
Priority claimed from KR1020160174818A external-priority patent/KR101742593B1/en
Priority claimed from KR1020170001353A external-priority patent/KR101753129B1/en
Application filed by Korea Institute of Geoscience and Mineral Resources KIGAM filed Critical Korea Institute of Geoscience and Mineral Resources KIGAM
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/54—Electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/66—Current collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • 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

Abstract

The present invention relates to include the steps that the accordion graphene complex for being spray-dried and being heat-treated the solution comprising graphene oxide and conductive material preparation method, thus the graphene complex for preparing and be applicable in include its electrode supercapacitor.

Description

The preparation method of accordion graphene complex, the complex thus prepared and comprising The supercapacitor of complex
Technical field
The present invention relates to the preparation method of accordion graphene complex, thus the graphene complex for preparing and comprising it Supercapacitor be related to including that spray drying and heat treatment include the molten of graphene oxide and conductive material in more detail The preparation method of the accordion graphene complex of the step of liquid, the graphene complex thus prepared and comprising the super of its Capacitor.
Background technique
As to the increase in demand with high-energy and the energy storage device of high power density, supercapacitor is as a new generation One of environment protection type energy storage device is concerned.Relative to existing secondary cell, the advantages of this supercapacitor, is have High power density and efficiency for charge-discharge, semipermanent cycle lie, and to curent change stabilization and there is no explosion danger.Cause This, it is positively utilized in the portable electronic device or charger baby for needing to provide stable energy, for the moment of electric vehicle Accelerate and store the power supply of backup.Also, supercapacitor uses carbon material as electrode active material, so can be referred to as is tool There are the backup of the energy of environmental protection and strong security characteristic and storage device.
The chemical property of supercapacitor may depend on electrode substance, but need to meet the requirements condition, such as highly conductive Degree, wide specific surface area, high-temperature stability, uniform air hole structure, low cost etc..It mainly will include active carbon, carbon nanometer It manages, the Carbon materials of graphene are used in the electrode material of supercapacitor extensively.Wherein, active carbon is due to its wide specific surface Long-pending and cheap expense and be widely used as supercapacitor material.But even if activated carbon electrodes are with a large amount of micro-/big Gap, electrolyte absorption property at the electrode surface is also very low, there is a problem of that specific capacitance is low.Therefore, there is wide ratio Surface area (theoretical value 2600m2/ g), the graphene of quick electron transfer degree and excellent mechanical performance is used as and is used for energy storage The material of device is concerned.Other than supercapacitor, this graphene is expected to be used in solar battery and electricity The fields such as chemical sensor.
Recently, reported that preparation has multiple researchs of leachy Graphene electrodes, to improve electrolyte and electrode substance Proximity between surface.But due to the blindness of extensive stomata and graphene film be laminated, these every volumes of electrode have than The regular activated lower memory capacity of carbon resistance rod.
In KR published patent the 10-2015-0044359th, graphene layer spacing adjusting method is provided and utilizes it Supercapacitor specifically provide the preparation method of the graphene of the adjusting interlamellar spacing for supercapacitor, comprising: to It include that surfactant is added in the solution of graphene oxide come the step of dispersing above-mentioned graphene oxide；To including the upper of dispersion State the step of graphene oxide of the reducing agent to form reduction is added in the solution of graphene oxide；And to including reduction Two ends are added in the solution of above-mentioned graphene oxide by N2 +The support substance (pillar material) of activation and by the inclusion of So that the above-mentioned graphene oxide of reduction is connected with above-mentioned support substance in the aryl of above-mentioned support substance and adjusts the upper of reduction The step of stating the interlamellar spacing between graphene oxide, according to the quantity of above-mentioned aryl, or according to being connected to more than two virtues The carbon number of alkyl between base adjusts the interlamellar spacing between the above-mentioned graphene oxide of reduction.But above-mentioned preparation method also needs The reducing agents such as the hydrazine of redox graphene are used for, there is the trouble for needing the process through multiple steps, when will thus prepare Structural body when being suitable for capacitor, there are problems that under high current density (2A/g or more) that specific capacitance declines.
On the other hand, as the close method of the specific capacitance for improving supercapacitor, receive with comprising carbon The graphene complex of the Carbon materials such as mitron and active carbon prepares related research.But with the graphene of two-dimensional structure Occur always to be laminated again between piece and coacervation, therefore there are problems that electrolyte is difficult to penetrate into complex electrode.Into one Step ground, due to the Van der Waals'attractive force between carbon nanotube, clustering phenomena occurs between carbon nanotube, thus occur specific capacitance with Current density increase and the tendency of reduction.
Therefore, actually need to carry out by solve when be applicable in two-dimensional graphene and when carbon nanotube, occurs be laminated again and Coagulation problems, to keep specific capacitance at higher current densities and the research for improving the power density based on this.
Summary of the invention
Technical problem
The present invention for solving prior art problem above-mentioned, the object of the present invention is to provide by spray drying and The preparation method of the self assembly accordion graphene complex of heat treatment procedure.
It is a further object of the present invention to provide carbon nanotubes to form physics crosslinking points in graphene and have Gao Bibiao The accordion graphene complex of area.
Another object of the present invention is to provide also effectively keep being applicable in for specific capacitance above-mentioned compound at higher current densities The supercapacitor of body.
Further object of the invention is that providing to prepare with simpler process ensures that the graphene of the fold of stomata is multiple Zoarium, and the preparation method for the electrode being fixed in using graphene on collector.
Solution to problem
In order to realize purpose as described above, in first embodiment of the invention, a kind of accordion graphene-carbon is provided The preparation method of nanometer tube complex, comprising: prepare to mix carbon nanotube, graphene oxide and solvent through acid processing Colloid mixed solution (step 1)；And the above-mentioned mixed solution of spray drying, and it is heat-treated (step 2).
In one embodiment, above-mentioned carbon nanotube can be multi-walled carbon nanotube (MWCNT).
In one embodiment, the acid processing of above-mentioned carbon nanotube can be by dispersing carbon nanotube in comprising sulfuric acid and nitric acid Acid solution in carry out.
In one embodiment, the mixed weight of the carbon nanotube of above-mentioned steps 1 and graphene oxide ratio can be 0.01:1 To 0.4:1.
In one embodiment, the graphene oxide concentration of the mixed solution of above-mentioned steps 1 can be 0.10 weight percent To 0.50 weight percent.
In one embodiment, above-mentioned steps 2 can include: step is stated by upper second fluid nozzle by spraying in the form of aerosol droplets 1 mixed solution (step 2a)；And spraying above-mentioned droplet transfer is dried to heating furnace, and pass through heat treatment Form the accordion graphene-carbon nano tube complex (step 2b) of self assembly.
In one embodiment, the diameter of the second fluid nozzle of above-mentioned steps 2a can be 1.0mm to 3.0mm.
In one embodiment, the heat treatment of above-mentioned steps 2 or step 2b can 200 DEG C to 500 DEG C at a temperature of carry out.
In one embodiment, the heat treatment of above-mentioned steps 2 or step 2b can carry out 1 hour to 10 hours.
In order to realize purpose as described above, the another first embodiment of the present invention, which provides, passes through above-mentioned accordion graphite The accordion graphene-carbon nano tube complex that alkene-Carbon Nanotube preparation method is prepared, above-mentioned accordion stone Black alkene-Carbon Nanotube includes accordion graphene film；And carbon nanotube, above-mentioned carbon nanotube are included in above-mentioned graphite Inside alkene piece, above-mentioned accordion graphene-carbon nano tube complex is spherical shape, and average particle size is 1 μm to 10 μm.
In one embodiment, above-mentioned carbon nanotube can be multi-walled carbon nanotube (MWCNT).
In order to realize purpose as described above, it includes above-mentioned accordion graphite that another first embodiment of the present invention, which provides, Alkene-Carbon Nanotube electrode of super capacitor.
In order to realize purpose as described above, there are also a first embodiments to provide supercapacitor by the present invention, comprising: one It is mutually opposed to electrode, and include active material；Electrolyte is set between above-mentioned a pair of electrodes；And seperation film, setting Between above-mentioned a pair of electrodes, for inhibiting electric short circuit, above-mentioned active material is multiple comprising above-mentioned accordion graphene-carbon nano tube It is fit.
In order to realize that purpose as described above, second embodiment of the invention provide accordion graphene-carbon nano tube-height The preparation method of molecular complex, comprising: prepare the carbon nanotube through acid processing, graphene oxide, electroconductive polymer list Mixed solution (the step i) that body and solvent mix；The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii)；With And it is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction and is heat-treated (step iii).
In one embodiment, the mixed weight of the carbon nanotube of above-mentioned steps i and graphene oxide ratio can be 0.01:1 To 0.5:1.
In one embodiment, the monomer concentration of the mixed solution of above-mentioned steps i can be 5mM to 50mM.
In one embodiment, the electroconductive polymer monomer of above-mentioned steps i can be for selected from by aniline, pyrroles, thiophene, second One or more of alkynes, furans, phenylene and their group of derivative composition.
In one embodiment, above-mentioned steps ii can be by adding polymerization initiator into above-mentioned mixed solution and handling ultrasound Wave carries out.
In one embodiment, above-mentioned steps iii can include: be sprayed through in the form of aerosol droplets by second fluid nozzle poly- Close the above-mentioned mixed solution (step iiia) of reaction；And spraying above-mentioned droplet transfer is dried to heating furnace, And accordion graphene-carbon nano tube-polymer composite (step iiib) of self assembly is formed by heat treatment.
In one embodiment, the diameter of the second fluid nozzle of above-mentioned steps iiia can be 1.0mm to 3.0mm.
In one embodiment, above-mentioned steps iii or step iiib heat treatment can 200 DEG C to 500 DEG C at a temperature of It carries out 1 hour to 10 hours.
In order to realize purpose as described above, the another second embodiment of the present invention, which provides, passes through accordion graphene-carbon Accordion graphene-carbon nano tube-polymer composite that nanotube-polymer composite preparation method is prepared, on Stating accordion graphene-carbon nano tube-polymer composite includes: accordion graphene film；Carbon nanotube is included in above-mentioned stone Black alkene piece；And electroconductive polymer, above-mentioned accordion graphene-carbon nano tube-polymer composite are spherical shape, and averagely grain Sub- size is 1 μm to 10 μm.
In one embodiment, above-mentioned electroconductive polymer can for selected from by polyaniline, polypyrrole, polythiophene, polyacetylene, Poly- furans and poly- one of the group that benzene is formed.
In order to realize purpose as described above, it includes above-mentioned accordion graphite that another second embodiment of the invention, which provides, Alkene-carbon nanotube-polymer composite electrode of super capacitor.
In order to realize that purpose as described above, an also second embodiment of the invention provide accordion graphene-carbon Nanotube-polymer composite, comprising: a pair of electrodes, it is mutually opposed, and include active material；Electrolyte is set to above-mentioned one To between electrode；And seperation film, it is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit, above-mentioned active material includes Above-mentioned accordion graphene-carbon nano tube-polymer composite.
In order to realize purpose as described above, it includes accordion graphene complex that third embodiment of the present invention, which provides, Electrode of super capacitor preparation method, comprising: prepare carbon nanotube, graphene oxide, electric conductivity through acid processing is high Mixed solution (the step i) that molecule monomer and solvent mix；The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii)；It is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction, and prepares accordion graphene complex by being heat-treated (step iii)；And it mixes above-mentioned complex, graphene oxide and solvent and is heat-treated (step after being coated on collector Rapid iv).
In one embodiment, in above-mentioned steps iv, above-mentioned complex: the mixed weight ratio of graphene oxide can be 1: 0.02 to 1:0.5.
In one embodiment, above-mentioned steps iv heat treatment can 200 DEG C to 500 DEG C at a temperature of carry out 1 hour extremely 10 hours.
In order to realize that purpose as described above, another third embodiment of the invention provide electrode of super capacitor, packet Include: accordion graphene-carbon nano tube-polymer composite, including accordion graphene film, be included in above-mentioned graphene film in The carbon nanotube and electroconductive polymer in portion, above-mentioned accordion graphene-carbon nano tube-polymer composite are spherical shape, and Average particle size is 1 μm to 10 μm；Collector is being formed with multiple above-mentioned complexs on one side；And graphene film, for solid Fixed above-mentioned collector and complex, and for fixing above-mentioned complex and complex.
In order to realize that purpose as described above, another third embodiment of the invention provide supercapacitor, comprising: one It is mutually opposed to electrode；Electrolyte is set between above-mentioned a pair of electrodes；And seperation film, be set to above-mentioned a pair of electrodes it Between, for inhibiting electric short circuit, above-mentioned electrode is electrode of super capacitor as described above.
The effect of invention
In first embodiment of the invention, spray drying and heat treated carbon nanotube and graphene complex colloid can be passed through Solution prepares the accordion graphene-carbon nano tube complex of self assembly, and the complex thus prepared can make carbon nanotube exist Physics crosslinking points are formed between graphene and increase graphene face spacing.Also, working as will be comprising prepared above-mentioned complex It when electrode is suitable for capacitor, has the following effects that, that is, can have low interfacial resistance, electrical conductivity good, electric in height with electrolyte Specific capacitance holding capacity is outstanding under current density.
In second embodiment of the invention, to mixed oxidization graphene, carbon nanotube and electroconductive polymer monomer The carbon nanotube put into colloidal solution plays crosslinked action between the graphene film of prepared complex, thus when due to The raising of electric conductivity and the increase of interplanar distance and be applicable in capacitor when, electrolyte proximity can be improved.Also, it is three-dimensional spherical Shape, and accordion graphene-carbon nano tube-polymer composite of uniform stomata is formed with due to its electric conductivity in inside It is close that high molecular highly conductive degree and the capacitor that can be carried out redox reaction, therefore be applicable in it can show simultaneously high power Degree and energy density.
In third embodiment of the present invention, the pleat of uniform stomata will be formed in three-dimensional spherical form and in inside Corrugation graphene-carbon nano tube-polymer composite is fixed on the current collector by graphene, so as in not binder In the case of prepare electrode, when being used in capacitor while showing high power density and energy density.
It should be understood that effect of the invention is not limited to effect as described above, and including can be from the present invention Detailed description or to be recorded in the institute that the structure of the invention for inventing claimed range is derived effective.
Detailed description of the invention
Fig. 1 is the preparation method for showing the accordion graphene-carbon nano tube complex of first embodiment of the invention The brief diagram of an example.
Fig. 2 is the preparation method for showing the accordion graphene-carbon nano tube complex of first embodiment of the invention The schematic diagram of an example.
(a1) of Fig. 3 is partially partially that scanning electron microscope (FE-SEM) is utilized to shoot the embodiment of the present invention 1 to (d1) The photo of the complex prepared into embodiment 3 and comparative example 1.
(a2) of Fig. 3 is partially partially that transmission electron microscope (TEM) is utilized to shoot embodiment of the present invention 1 to reality to (d2) Apply the photo of the complex prepared in example 3 and comparative example 1.
Fig. 4 is to show complex, graphene oxide that the embodiment of the present invention 1 prepared into embodiment 3 and comparative example 1 and more The curve graph of X-ray diffraction (XRD) the analysis result of wall carbon nano tube.
Fig. 5 is the Raman spectrum for showing the complex that the embodiment of the present invention 1 is prepared into embodiment 3 and comparative example 1 The curve graph of (raman spectroscopy) analysis result.
Fig. 6 is the circulation electricity for showing the supercapacitor that the embodiment of the present invention 4 is prepared into embodiment 6 and comparative example 2 The curve graph of current voltage, charge and discharge and analysis of Impedance Characteristic result.
Fig. 7 is the accordion graphene-carbon nano tube-polymer composite preparation for showing second embodiment of the invention The brief diagram of an example of method.
Fig. 8 is the accordion graphene-carbon nano tube-polymer composite preparation for showing second embodiment of the invention Another schematic diagram of method.
Fig. 9 a part to Fig. 9 c part be using scanning electron microscope (FE-SEM) shooting i of the embodiment of the present invention, The photo of the substance prepared in comparative example i and comparative example ii.
The part f of the part d of Fig. 9 to Fig. 9 are using transmission electron microscope (TEM) shooting i of the embodiment of the present invention, compare The photo of the substance prepared in example i and comparative example ii.
The part a of Figure 10 is to show the X-ray of the substance prepared in i of the embodiment of the present invention, comparative example i and comparative example ii to spread out Penetrate the curve graph of (XRD) analysis result.
The part b of Figure 10 is the Raman light for showing the substance prepared in i of the embodiment of the present invention, comparative example i and comparative example ii The curve graph of spectrum analysis result.
Figure 11 is the mercury gaging hole method for showing the substance prepared in i of the embodiment of the present invention, comparative example i and comparative example ii The curve graph of (mercury porosimeter) analysis result.
The part a of Figure 12 to the part d be show prepared in iv of the embodiment of the present invention, comparative example iii and comparative example iv it is super The curve graph of the grade cyclic voltammetry of capacitor, charge and discharge and analysis of Impedance Characteristic result.
The part a of Figure 13 to the part d is the supercapacitor for showing iv of the embodiment of the present invention and preparing into embodiment vi The curve graph of cyclic voltammetry, charge and discharge and analysis of Impedance Characteristic result.
Figure 14 is the electrode of super capacitor comprising accordion graphene complex for showing third embodiment of the invention Preparation method an example brief diagram.
Figure 15 is the electrode of super capacitor comprising accordion graphene complex for showing third embodiment of the invention Preparation method another schematic diagram.
The part f of the part a of Figure 16 to Figure 16 are to shoot i of the embodiment of the present invention using scanning electron microscope (FE-SEM) The photo of+the substance prepared into embodiment iii+.
The part f of the part a of Figure 17 to Figure 17 are to shoot i+ of the embodiment of the present invention extremely using transmission electron microscope (TEM) The photo of the substance prepared in embodiment iii+.
The part a of Figure 18 is to show substance, the accordion graphene that i+ of the embodiment of the present invention is prepared into embodiment iii+ And the curve graph of the X-ray diffraction analysis result of polyaniline.
The part b of Figure 18 is to show substance, the accordion graphene that i+ of the embodiment of the present invention is prepared into embodiment iii+ And the curve graph of the Raman spectrum analysis result of polyaniline.
The part a of Figure 19 to the part c is the circulation for showing the supercapacitor that iv+ of the embodiment of the present invention is prepared into vi+ The curve graph of voltage and current, charge-discharge characteristic analysis result.
The part a of Figure 20 to the part c is to show in iv+ of the embodiment of the present invention, embodiment vii+ and embodiment viii+ to prepare Supercapacitor cyclic voltammetry, charge-discharge characteristic analysis result curve graph.
Specific embodiment
In the following, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
It can be allowed referring to aftermentioned embodiment and advantages of the present invention, feature and realize that the method for these advantages and features is brighter Really.
But the invention is not limited to embodiment as disclosed below, can by it is mutually different it is various in a manner of implement, The present embodiment is for making general technical staff of the technical field of the invention be fully understood by scope of the invention, and the present invention is only It is defined by inventing claimed range.
Further, during illustrating the present invention, thinking that related known technology etc. can obscure purport of the invention In the case where, related be described in detail will be omitted.
First embodiment of the invention provides a kind of preparation method of accordion graphene-carbon nano tube complex, packet It includes: preparing the colloid mixed solution (step 1) for mixing carbon nanotube, graphene oxide and solvent through acid processing (S10)；And the above-mentioned mixed solution of spray drying, and it is heat-treated (step 2) (S20).
In the research of existing graphene-carbon nano tube complex, with a straight hair between the graphene film of two-dimensional structure Life is laminated again and coacervation, therefore there are problems that electrolyte is difficult to penetrate into complex electrode.Also, due to carbon nanotube Between Van der Waals'attractive force, clustering phenomena occurs between carbon nanotube, thus there is specific capacitance as current density increases and The tendency of reduction.
The present inventor in order to solve two-dimensional graphene and carbon nanotube be laminated again and coagulation problems, develop when being suitable for Specific capacitance is kept when capacitor at higher current densities and the accordion graphene-carbon nano tube complex of power density can be improved Preparation method, so as to complete the present invention.
Hereinafter, being pressed to the preparation method of the accordion graphene-carbon nano tube complex of first embodiment of the invention each A step is described in detail.
In the preparation method of the accordion graphene-carbon nano tube complex of first embodiment of the invention, above-mentioned In step 1 (S10), prepare the colloid mixed solution for mixing carbon nanotube, graphene oxide and solvent through acid processing.
The carbon nanotube of above-mentioned steps 1 can be for selected from by single-walled carbon nanotube (SWCNT), double-walled carbon nano-tube (DWCNT) and one of the group carbon nanotube, preferably multi-walled carbon nanotube (multi-walled of multi-walled carbon nanotube composition carbon nanotube；MWCNT).
Carbon nanotube can be by being dispersed in the acid solution comprising sulfuric acid and nitric acid by the cabonic acid processing of above-mentioned steps 1 In come carry out.Specifically, can be by sulfuric acid: nitric acid be with dispersing Nano carbon tubes in the acid solution of the volume ratio mixing of 2:1 to 4:1 And 50 DEG C to 80 DEG C at a temperature of stir 1 hour to 10 hours and carry out.
When carrying out the cabonic acid processing of above-mentioned steps 1, carbon nanotube: the solid-to-liquid ratio (g/mL) of acid solution can be 1:150 to 1:250.
The step that above-mentioned steps 1 may also include the above-mentioned carbon nanotube using hydrochloric acid solution cleaning through acid processing and be dried Suddenly.
Before acid processing, the dispersibility to water is can be improved in the carbon nanotube through acid processing of above-mentioned steps 1.
The carbon nanotube of above-mentioned steps 1 and the mixed weight ratio of graphene oxide can be 0.01:1 to 0.4:1, preferably It can be 0.05:1 to 0.1:1.In the case where the mixed weight of above-mentioned carbon nanotube and graphene oxide ratio is less than 0.01:1, Following problem may be present, that is, in prepared accordion graphene-carbon nano tube complex, carbon nanotube may be insufficient To form physics crosslinking points in graphene, the specific capacitance conservation rate comprising its supercapacitor may decline.In above-mentioned carbon In the case that the mixed weight of nanotube and graphene oxide ratio is greater than 0.4:1, following problem may be present, that is, prepared Accordion graphene-carbon nano tube complex in, carbon nanotube may agglomerate, the electrolyte comprising its supercapacitor and Interface resistance between electrode increases.
The solvent of above-mentioned steps 1 can be for selected from by distilled water, acetone, methyl ethyl ketone, methanol, ethyl alcohol, isopropanol, fourth Alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethyl acetamide, n-methyl-2-pyrrolidone, hexane, Cyclohexanone, toluene, chloroform, dichloro-benzenes, dimethylbenzene, trimethylbenzene, pyridine, methyl naphthalene, nitromethane, acrylonitrile, octadecylamine, benzene One or more of the group of amine and dimethyl sulfoxide composition, preferably can be used distilled water.
The graphene oxide concentration of the mixed solution of above-mentioned steps 1 can be 0.10 weight percent to 0.50 weight percent Than can preferably be 0.15 weight percent to 0.35 weight percent.If the graphene oxide concentration of above-mentioned mixed solution Less than 0.10 weight percent, then since the compound scale of construction generated per unit time in following step is few, preparation efficiency can It can decline, if the graphene oxide concentration of above-mentioned mixed solution is greater than 0.50 weight percent, there may be can not pass through spray Mist step is come the problem of forming accordion graphene-carbon nano tube complex.
Above-mentioned steps 1 may also include through ultrasonication the step of above-mentioned colloid mixed solution for dispersing to be prepared.
In the preparation method of the accordion graphene-carbon nano tube complex of first embodiment of the invention, above-mentioned In step 2 (S20), it is spray-dried above-mentioned mixed solution and is heat-treated.
The spray drying and heat treatment of above-mentioned steps 2 may include specifically following step 2a and step 2b.
Above-mentioned steps 2 can include: pass through the mixed solution of second fluid nozzle spraying above-mentioned steps 1 in the form of aerosol droplets (step 2a)；And spraying above-mentioned droplet transfer is dried to heating furnace, and self assembly is formed by heat treatment Accordion graphene-carbon nano tube complex (step 2b).
The diameter of the second fluid nozzle of above-mentioned steps 2a can be 1.0mm to 3.0mm, can preferably be 1.0mm extremely 2.0mm.If the diameter of above-mentioned second fluid nozzle is less than 1.0mm, there may be drops successfully to ask from what nozzle came out Topic exists if the diameter of above-mentioned second fluid nozzle is greater than 3.0mm and does not allow to be also easy to produce from the mixed solution Jing Guo above-mentioned steps 1 Particle possibility.
The second fluid nozzle of above-mentioned steps 2a can mix dispersion caused by the collision by liquids and gases to keep liquid micro- Granulation.Different from the existing nozzle by direct weighting mode, above-mentioned second fluid nozzle has even if can also protect under low pressure The advantages of holding super-thin spray.
In above-mentioned steps 2b by droplet transfer to heating furnace when, can be by selected from being made of argon gas, helium and nitrogen The gas of one or more of group shifts, and is preferably by argon gas to shift.
In above-mentioned steps 2b by droplet transfer to heating furnace when, the flow of gas can be 5L/min to 15L/min, excellent Selection of land can be 5L/min to 10L/min.
The temperature of the heating furnace of above-mentioned steps 2b can be 150 DEG C to 250 DEG C, can preferably be 180 DEG C to 220 DEG C. If the temperature of above-mentioned heating furnace less than 150 DEG C, has that solvent is remained because not evaporating partially in drop, cannot be formed The problem of accordion graphene oxide-Carbon Nanotube, is forming pleat if the temperature of above-mentioned heating furnace is greater than 250 DEG C Excessive energy may be wasted when corrugation graphene oxide-Carbon Nanotube.
If because and drying leading to the solvent being present in drop by be transferred to heating furnace progress in above-mentioned steps 2b Evaporation, then graphene oxide sheet forms (capillary molding) phenomenon by capillary and mutually assembles, so as to prepare pleat Corrugation graphene oxide-Carbon Nanotube.
Complex by the drying of above-mentioned steps 2b can be collected in the filter by cyclone, followed by for oxygen The heat treatment of the reduction of graphite alkene.
Above-mentioned steps 2b heat treatment can 200 DEG C to 500 DEG C at a temperature of carry out, preferably can be at 200 DEG C to 300 DEG C At a temperature of carry out.If above-mentioned heat treatment temperature is less than 200 DEG C, there may be what graphene oxide cannot be restored effectively to ask Topic, if above-mentioned heat treatment temperature is greater than 500 DEG C, there may be excessive energy is wasted when redox graphene.
The heat treatment of above-mentioned steps 2b can carry out in Muffle furnace (muffle furnace), can be selected from by argon gas, helium It carries out under the gas atmosphere of one or more of the group of gas and nitrogen composition, can preferably carry out under an argon atmosphere.
The heat treatment of above-mentioned steps 2b can carry out 1 hour to 10 hours, can preferably carry out 1 hour to 3 hours.If above-mentioned Heat treatment time was less than 1 hour, then the problem of cannot effectively be restored there may be graphene oxide, if above-mentioned heat treatment time Greater than 10 hours, then excessive energy may be wasted when redox graphene.
The 1 accordion graphene-carbon nano tube complex finally prepared to step 2 passes through above-mentioned system through the above steps The complementary bonding of Preparation Method, can inhibit the cohesion of graphene being laminated again with carbon nanotube.Also, it is located at graphene surface and side The carbon nanotube of edge can play the crosslinked action between graphene film, will be suitable for electricity comprising the electrode of above-mentioned complex as a result, When container, electrical conductivity can be improved and promote electrolyte proximity by interplanar distance increase.
The another first embodiment of the present invention is provided to be prepared by the above method (step 1 and step 2, S10 and S20) Accordion graphene-carbon nano tube complex, above-mentioned accordion graphene-carbon nano tube complex includes: accordion graphite Alkene piece；And carbon nanotube, it is included in inside above-mentioned graphene film, above-mentioned accordion graphene-carbon nano tube complex is ball Shape, and average particle size is 1 μm to 10 μm.
In the accordion graphene-carbon nano tube complex of first embodiment of the invention, it is preferable that above-mentioned carbon nanometer Pipe is multi-walled carbon nanotube (MWCNT).
It include that carbon nanotube inside above-mentioned accordion graphene-carbon nano tube complex can play between graphene film Physical crosslinking effect.
Above-mentioned accordion graphene-carbon nano tube complex can meet following mathematical expressions 1.
[mathematical expression 1]
0.70<Id/Ig<0.95
(in above-mentioned mathematical expression 1, IdTo show graphene sp in above-mentioned accordion graphene-carbon nano tube complex2Knot The missing of structure, substitution or the Raman spectrum peak intensity of (disorder) of lacking of proper care, IgFor show graphite carbon Raman spectrum peak intensity Degree.)
Above-mentioned accordion graphene-carbon nano tube complex can have graphene face spacing (interlayer spacing) Increased characteristic, this may be as caused by the oxygen functional group remained in the graphene of above-mentioned complex and carbon nanotube etc.. Specifically, the graphene face spacing of above-mentioned accordion graphene-carbon nano tube complex can be 0.35nm to 0.38nm.
Another first embodiment of the present invention provides the super electricity comprising above-mentioned accordion graphene-carbon nano tube complex Container electrode.
When by being suitable for capacitor comprising the electrode of above-mentioned complex, since the graphene face spacing of complex increases and draw The high contact area risen, therefore can have the characteristic of the contact resistance reduction between water-soluble electrolytes.
Above-mentioned electrode may also include the binder for supporting above-mentioned complex, and above-mentioned binder can be for selected from by gathering inclined difluoro Ethylene (PVDF), polyvinylidene fluoride hexafluoropropene (PVDF-HFP), carboxymethyl cellulose (CMC), styrene butadiene ribber (SBR), one or more of the group of polyimides (PI) and polyvinyl alcohol (PVA) composition, but not limited to this.
There are also a first embodiments to provide supercapacitor by the present invention, comprising: a pair of electrodes, it is mutually opposed, and include Active material；Electrolyte is set between above-mentioned a pair of electrodes；And seperation film, it is set between above-mentioned a pair of electrodes, is used for Inhibit electric short circuit, above-mentioned active material includes above-mentioned accordion graphene-carbon nano tube complex.
Above-mentioned a pair of electrodes may also include the collector that each one side is placed in a manner of electrical contact.
Above-mentioned electrolyte can be used selected from by the acids electrolyte comprising sulfuric acid, the bases electrolyte comprising potassium hydroxide and One of the group of neutral electrolyte composition comprising sodium sulphate, but not limited to this.
Above-mentioned collector can be to include the metal selected from one or more of group for being made of copper, nickel, aluminium, stainless steel Metal foil or metallic film can be the porous paper based on the carbon with electrical conductivity, still, as long as have chemical resistance, Electrochemistry corrosion resistance, it's not limited to that.
Above-mentioned seperation film can be used non-woven fabrics, polytetrafluoroethylene (PTFE) (PTFE), perforated membrane, brown paper, cellulose family electrolyte, Rayon fiber etc., but not limited to this.
The supercapacitor of first embodiment of the invention can be by due to the graphene face spacing of above-mentioned complex increases Caused high contact area, to reduce the interface resistance between above-mentioned electrode and electrolyte, so as to increase specific capacitance.Specifically Ground, the specific capacitance of the supercapacitor of first embodiment of the invention can be for 130F/g extremely under the current density of 0.1A/g 200F/g, even if at higher current densities, above-mentioned specific capacitance can also be kept substantially.Specifically, relative to 0.1A/g's Specific capacitance under current density, the specific capacitance under the current density of 4A/g can be 70% to 90%.
Second embodiment of the invention provides accordion graphene-carbon nano tube-polymer composite preparation method, packet It includes: it is molten to prepare the mixing for mixing the carbon nanotube through acid processing, graphene oxide, electroconductive polymer monomer and solvent Liquid (step i) (S100)；The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii) (S200)；And spray drying warp The above-mentioned mixed solution of polymerization reaction is crossed, and is heat-treated (step iii) (S300).
Hereinafter, to accordion graphene-carbon nano tube-polymer composite preparation side of second embodiment of the invention Method is described in detail by step.
In accordion graphene-carbon nano tube-polymer composite preparation method of second embodiment of the invention, In above-mentioned steps i (S100), prepare the carbon nanotube through acid processing, graphene oxide, electroconductive polymer monomer and molten The mixed solution that agent mixes.
The carbon nanotube of above-mentioned steps i can be for selected from by single-walled carbon nanotube, double-walled carbon nano-tube and multi-wall carbon nano-tube One or more of the group of pipe composition carbon nanotube, preferably multi-walled carbon nanotube.
Carbon nanotube can be by being dispersed in the acid solution comprising sulfuric acid and nitric acid by the cabonic acid processing of above-mentioned steps i It is carried out in coming.
Specifically, can be by sulfuric acid: nitric acid be with dispersing Nano carbon tubes in the acid solution of the volume ratio mixing of 2:1 to 4:1 And 50 DEG C to 80 DEG C at a temperature of stir 1 hour to 10 hours and carry out.
When carrying out the cabonic acid processing of above-mentioned steps i, carbon nanotube: the solid-to-liquid ratio (g/mL) of acid solution can be 1:150 to 1:250.
The step that above-mentioned steps i may also include the above-mentioned carbon nanotube using hydrochloric acid solution cleaning through acid processing and be dried Suddenly.
Before acid processing, the dispersibility to water is can be improved in the carbon nanotube through acid processing of above-mentioned steps i.
The carbon nanotube of above-mentioned steps i and the mixed weight ratio of graphene oxide can be 0.01:1 to 0.5:1, preferably It can be 0.05:1 to 0.1:1.In the case where the mixed weight of above-mentioned carbon nanotube and graphene oxide ratio is less than 0.01:1, Following problem may be present, that is, in prepared accordion graphene-carbon nano tube-polymer composite, carbon nanotube can It can be not enough to form physics crosslinking points in graphene, the specific capacitance conservation rate comprising its supercapacitor may decline.? In the case that the mixed weight of above-mentioned carbon nanotube and graphene oxide ratio is greater than 0.5:1, following problem may be present, that is, In prepared accordion graphene-carbon nano tube-polymer composite, carbon nanotube may agglomerate, and include its super electricity Interface resistance between the electrolyte and electrode of container increases.
The solvent of above-mentioned steps i can be for selected from by distilled water, acid solution, acetone, methyl ethyl ketone, methanol, ethyl alcohol, different Propyl alcohol, butanol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethyl acetamide, N- methyl -2- pyrrolidines Ketone, hexane, cyclohexanone, toluene, chloroform, dichloro-benzenes, dimethylbenzene, trimethylbenzene, pyridine, methyl naphthalene, nitromethane, acrylonitrile, One or more of octadecylamine, aniline and group of dimethyl sulfoxide composition, preferably can be used hydrochloric acid solution.
The graphene oxide concentration of the mixed solution of above-mentioned steps i can be 0.10 weight percent to 0.50 weight percent Than can preferably be 0.15 weight percent to 0.35 weight percent.If the graphene oxide concentration of above-mentioned mixed solution Less than 0.10 weight percent, then since the compound scale of construction generated per unit time in following step is few, preparation efficiency can It can decline, if the graphene oxide concentration of above-mentioned mixed solution is greater than 0.50 weight percent, there may be can not pass through spray Mist step is come the problem of forming accordion graphene-carbon nano tube-polymer composite.
The monomer concentration of the mixed solution of above-mentioned steps i can be 5mM to 50mM, can preferably be 10mM to 30mM. It is applicable in if above-mentioned monomer concentration is less than 5mM since the content of electroconductive polymer in prepared complex is few There may be the hidden danger of specific capacitance decline when capacitor, if above-mentioned monomer concentration is greater than 50mM, in prepared complex Excessive electroconductive polymer is generated, therefore by it is suitable for the contact resistance between electrolyte may occur when capacitor to increase The problem of.
The electroconductive polymer monomer of above-mentioned steps i can be for selected from by aniline, pyrroles, thiophene, acetylene, furans, sub- benzene One or more of the group of base and their derivative composition, is used to form selected from by polyaniline, polypyrrole, poly- thiophene The high molecular monomer of one of pheno, polyacetylene, poly- furans and the poly- group that benzene is formed.
In accordion graphene-carbon nano tube-polymer composite preparation method of second embodiment of the invention, In above-mentioned steps ii (S200), make above-mentioned mixed solution monomer carry out polymerization reaction the step of.
Above-mentioned steps ii can pass through the addition polymerization initiator into above-mentioned mixed solution and handle ultrasonic wave to carry out.
The ultrasonication of above-mentioned steps ii can carry out 0.5 hour to 10 hours, can preferably carry out 1 hour to 3 hours. If above-mentioned ultrasonic treatment time was less than 0.5 hour, there may be the mixed solutions prepared in above-mentioned steps i to be unable to fully The problem of polymerization of the problem of dispersion, monomer can not carry out completely may if above-mentioned ultrasonic treatment time is greater than 10 hours Excessive energy is wasted in the dispersion and polymerization process of above-mentioned mixed solution.
The polymerization initiator of above-mentioned steps ii can for can in above-mentioned monomer polymerization used well known initiator.
In above-mentioned steps ii, in the case where above-mentioned monomer is aniline, when making its polymerization it is used commonly Initiator, it is preferable that can be used selected from one of the group being made of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, persulfuric acid lithium Above polymerization initiator.
Relative to the monomer of 100 parts by weight, the polymerization initiator additive amount of above-mentioned steps ii is 10 parts by weight to 100 weight Part, 20 parts by weight can be preferably added to 80 parts by weight.
Ii can be formed in above-mentioned mixed solution selected from by polyaniline, polypyrrole, polythiophene, poly- second through the above steps One of alkynes, poly- furans and the poly- group that benzene is formed electroconductive polymer.
In accordion graphene-carbon nano tube-polymer composite preparation method of second embodiment of the invention, In above-mentioned steps iii (S300), it is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction, and be heat-treated.
Specifically, the spray drying and heat treatment of above-mentioned steps iii may include following step iiia and step iiib.
Above-mentioned steps iii can include: be sprayed through the above-mentioned of polymerization reaction in the form of aerosol droplets by second fluid nozzle Mixed solution (step iiia)；And spraying above-mentioned droplet transfer is dried to heating furnace, and pass through heat treatment Form accordion graphene-carbon nano tube-polymer composite (step iiib) of self assembly.
The diameter of the second fluid nozzle of above-mentioned steps iiia can be 1.0mm to 3.0mm, can preferably be 1.0mm extremely 2.0mm.If the diameter of above-mentioned second fluid nozzle is less than 1.0mm, there may be drops successfully to ask from what nozzle came out Topic exists if the diameter of above-mentioned second fluid nozzle is greater than 3.0mm and does not allow to be also easy to produce from by the mixed solution of above-mentioned steps ii Particle possibility.
The second fluid nozzle of above-mentioned steps iiia can mix dispersion caused by the collision by liquids and gases to make liquid Micronized.Different from the existing nozzle by direct weighting mode, above-mentioned second fluid nozzle has even if under low pressure may be used The advantages of keeping super-thin spray.
In above-mentioned steps iiib by droplet transfer to heating furnace when, can be by selected from being made of argon gas, helium and nitrogen The gas of one or more of group shift, be preferably by argon gas to shift.
In above-mentioned steps iiib by droplet transfer to heating furnace when, the flow of gas can be 5L/min to 15L/min, 5L/min be can preferably be to 10L/min.
The temperature of the heating furnace of above-mentioned steps iiib can be 150 DEG C to 250 DEG C, can preferably be 180 DEG C to 220 ℃.If above-mentioned heating furnace temperature less than 150 DEG C if there are problems that in drop that solvent remains because not evaporating partially, is unable to shape The problem of drape graphene oxide-carbon nanotube-polymer composite, if the temperature of above-mentioned heating furnace is greater than 250 DEG C, Excessive energy may be wasted in the presence of when forming accordion graphene oxide-carbon nanotube-polymer composite.
If molten in drop because causing to be present in and being transferred to drying for heating furnace progress in above-mentioned steps iiib Agent evaporation, then graphene oxide sheet is mutually assembled by capillary formation phenomena, so as to prepare accordion graphene oxide-carbon Nanotube-polymer composite.
Complex by the drying in above-mentioned steps iiib can be collected by cyclone in the filter, followed by with In the heat treatment of the reduction of graphene oxide.
Above-mentioned steps iiib heat treatment can 200 DEG C to 500 DEG C at a temperature of carry out, preferably can be at 200 DEG C to 300 It is carried out at a temperature of DEG C.If above-mentioned heat treatment temperature cannot be restored effectively less than 200 DEG C there may be graphene oxide Problem, if above-mentioned heat treatment temperature is greater than 500 DEG C, there may be excessive energy is wasted when redox graphene.
The heat treatment of above-mentioned steps iiib can carry out in Muffle furnace, can be selected from being made of argon gas, helium and nitrogen It carries out under the gas atmosphere of one or more of group, can preferably carry out under an argon atmosphere.
The heat treatment of above-mentioned steps iiib can carry out 1 hour to 10 hours, can preferably carry out 1 hour to 3 hours.On if Heat treatment time is stated less than 1 hour, then the problem of cannot effectively be restored there may be graphene oxide, if when above-mentioned heat treatment Between be greater than 10 hours, then may redox graphene when waste excessive energy.
Accordion graphene-carbon nano tube-polymer composite that i is finally prepared to step iii through the above steps By the complementation bonding of above-mentioned preparation method, the cohesion of graphene being laminated again with carbon nanotube can inhibit.Also, it is located at graphite The carbon nanotube at alkene surface and edge can play the crosslinked action between graphene film, as a result, by the electricity comprising above-mentioned complex When pole is suitable for capacitor, electrical conductivity can be improved and promote electrolyte proximity by interplanar distance increase.Also, packet can be passed through The electroconductive polymer in above-mentioned complex is contained in improve the power density and energy density of capacitor.
The another second embodiment of the present invention, which provides, passes through the above method (step i to step iii, step S100 to step S300 the accordion graphene-carbon nano tube-polymer composite) being prepared, above-mentioned accordion graphene-carbon nano tube- Polymer composite includes: accordion graphene film；Carbon nanotube is included in inside above-mentioned graphene film；And electric conductivity is high Molecule, above-mentioned accordion graphene-carbon nano tube-polymer composite is spherical shape, and average particle size is 1 μm to 10 μm.
Above-mentioned carbon nanotube can be for selected from by single-walled carbon nanotube (SWCNT), double-walled carbon nano-tube (DWCNT) and multi wall One of the group of carbon nanotube (MWCNT) composition carbon nanotube, preferably multi-walled carbon nanotube.
Above-mentioned electroconductive polymer can be for selected from by polyaniline, polypyrrole, polythiophene, polyacetylene, poly- furans and poly- pair One of the group of benzene composition, can preferably be polyaniline.
Above-mentioned accordion graphene-carbon nano tube-polyaniline complex can have the increased characteristic of graphene face spacing, this It may be as caused by oxygen functional group, carbon nanotube and electroconductive polymer for remaining in the graphene of above-mentioned complex etc..
Another second embodiment of the invention provides compound comprising above-mentioned accordion graphene-carbon nano tube-macromolecule The electrode of super capacitor of body.
When by being suitable for capacitor comprising the electrode of above-mentioned complex, since the graphene face spacing of complex increases and draw The high contact area risen, therefore can have the characteristic of the contact resistance reduction between water-soluble electrolytes, due in complex Electroconductive polymer may have high power density and specific capacitance.
Above-mentioned electrode may also include the binder for supporting above-mentioned complex, and above-mentioned binder can be for selected from by gathering inclined difluoro Ethylene, polyvinylidene fluoride hexafluoropropene, carboxymethyl cellulose, styrene butadiene ribber, polyimides and polyvinyl alcohol group At one or more of group, but not limited to this.
An also second embodiment of the invention provides supercapacitor, comprising: a pair of electrodes, it is mutually opposed, and wrap Containing active material；Electrolyte is set between above-mentioned a pair of electrodes；And seperation film, it is set between above-mentioned a pair of electrodes, uses In inhibiting electric short circuit, above-mentioned active material includes above-mentioned accordion graphene-carbon nano tube-polymer composite.
Above-mentioned a pair of electrodes may also include the collector that each one side is placed in a manner of electrical contact.
Above-mentioned electrolyte can be used selected from by the acids electrolyte comprising sulfuric acid, the bases electrolyte comprising potassium hydroxide and One of the group of neutral electrolyte composition comprising sodium sulphate, but not limited to this.
Above-mentioned collector can be to include the metal selected from one or more of group for being made of copper, nickel, aluminium, stainless steel Metal foil or metallic film, can be the porous paper based on the carbon with electrical conductivity, still, as long as have chemistry it is anti-corrosion Property, electrochemistry corrosion resistance, it's not limited to that.
Non-woven fabrics, polytetrafluoroethylene (PTFE), perforated membrane, brown paper, cellulose family electrolyte, artificial silk can be used in above-mentioned seperation film Fiber etc., but not limited to this.
It is prepared using polyaniline is grown in the reduced graphene prepared by simple liquid phase reactor-Carbon Nanotube Polyaniline-carbon nanotube-graphene oxide and reduced graphene-carbon naotube-polyaniline complex supercapacitor, with Polyaniline be grown on reduced graphene-carbon nanotube surface, since electrode inner air vent volume is reduced, electrolyte proximity has It may be decreased, also, since the redox reaction in polyaniline causes active surface area to reduce, specific capacitance may have 50% Low value below.
At the same time, in liquid phase reactor, polystyrene (PS) can be used as organic formwork by being grown on polyaniline Including the active material electrode for having leachy complex to prepare in porous graphene-carbon nanotube for preparing.But The shortcomings that this process, is, organic to remove the polystyrene for being used to form stomata and using due to needing to carry out high-temperature heat treatment Template, therefore some are complicated.
In contrast, the supercapacitor of second embodiment of the invention can be by between the graphene face because of above-mentioned complex Away from high contact area caused by increase, to reduce the interface resistance between above-mentioned electrode and electrolyte, so as to increase than electricity Hold.Also, since the electroconductive polymer in complex can have electric double layer and performance of the supercapacitor simultaneously.Specifically, on The specific capacitance for stating supercapacitor can be 200F/g to 350F/g under the current density of 0.1A/g, even if in high current density Under, above-mentioned specific capacitance can also be kept substantially.Specifically, relative to the specific capacitance under the current density of 0.1A/g, in 4A/ Specific capacitance under the current density of g can be 70% to 90%.
Third embodiment of the present invention provides the preparation of the electrode of super capacitor comprising accordion graphene complex Method, comprising: prepare to mix carbon nanotube, graphene oxide, electroconductive polymer monomer and solvent through acid processing Mixed solution (step i) (S100)；The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii) (S200)；It is spraying dry The dry above-mentioned mixed solution by polymerization reaction, and accordion graphene complex (step iii) is prepared by being heat-treated (S300)；And it mixes above-mentioned complex, graphene oxide and solvent and is heat-treated (step after being coated on collector iiii)(S400)。
Hereinafter, the system of the electrode of super capacitor comprising accordion graphene complex to third embodiment of the invention Preparation Method is described in detail by step.
In the preparation side of the electrode of super capacitor comprising accordion graphene complex of third embodiment of the invention In method, above-mentioned steps i to step iii can be identical to step iii as the step i of above-mentioned second embodiment.
In third embodiment of the invention, electrode for capacitors is prepared in the case where not using binder, in order to prepare Pass through raising electronics rate travel and increases the super electricity that activity substance content shows high specific capacitance and specific capacitance conservation rate Container carries out following step.
In the preparation side of the electrode of super capacitor comprising accordion graphene complex of third embodiment of the invention In method, in above-mentioned steps iv (S400), above-mentioned complex, graphene oxide and solvent are mixed and coated on laggard on collector Row heat treatment.
In above-mentioned steps iv, above-mentioned complex: the mixed weight ratio of graphene oxide can be 1:0.02 to 1:0.5, Preferably, above-mentioned complex: the weight ratio of graphene oxide can be 1:0.05 to 1:0.3.In above-mentioned complex: graphite oxide In the case that the weight ratio of alkene is less than 1:0.02, there is a problem of that above-mentioned complex cannot be effectively fixed on collector, nothing Method realizes the problem of immobilization between part complex and complex, and in above-mentioned complex: the weight ratio of graphene oxide is big In the case where 1:0.5, the active surface area of prepared electrode is reduced, therefore there are the hidden of the specific capacitance of capacitor reduction Suffer from.
Above-mentioned steps iv heat treatment can 200 DEG C to 500 DEG C at a temperature of carry out, preferably can be at 200 DEG C to 300 DEG C At a temperature of carry out.It is mixed in above-mentioned steps iv if above-mentioned heat treatment temperature less than 200 DEG C, exists effectively to restore Graphene oxide the problem of, if above-mentioned heat treatment temperature is greater than 500 DEG C, restore the oxidation stone that mixes in above-mentioned steps iv Excessive energy may be wasted when black alkene.
The heat treatment of above-mentioned steps iv can carry out 1 hour to 10 hours, can preferably carry out 1 hour to 3 hours.If above-mentioned Heat treatment time then there are problems that effectively restoring the graphene oxide mixed in above-mentioned steps iv less than 1 hour, If above-mentioned heat treatment time is greater than 10 hours, may be wasted when restoring the graphene oxide mixed in above-mentioned steps iv excessive Energy.
The collector of above-mentioned steps iv can be for comprising selected from one or more of the group being made of copper, nickel, aluminium, stainless steel The metal foil or metallic film of metal, can be the porous paper based on the carbon with electrical conductivity, still, as long as having chemistry resistance to Corrosion, electrochemistry corrosion resistance, it's not limited to that.
The solvent of above-mentioned steps iv can for selected from by distilled water, acid solution, acetone, methyl ethyl ketone, methanol, ethyl alcohol, Isopropanol, butanol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethyl acetamide, N- methyl -2- pyrroles Alkanone, hexane, cyclohexanone, toluene, chloroform, dichloro-benzenes, dimethylbenzene, trimethylbenzene, pyridine, methyl naphthalene, nitromethane, propylene One or more of nitrile, octadecylamine, aniline and group of dimethyl sulfoxide composition, preferably can be used n-methyl-2-pyrrolidone Solvent.
The coating of above-mentioned steps iv can be executed by way of applying 50 μm to 200 μm of thickness on above-mentioned collector, Can preferably it make with a thickness of 75 μm to 125 μm.If above-mentioned applied thickness, less than 50 μm, there are prepared electrodes and water solubility Prepared electrode is suitable for by the increased hidden danger of interface resistance between electrolyte if above-mentioned applied thickness is greater than 200 μm When capacitor, the waste that may cause complex and graphene while can not increasing specific capacitance may be present.
The electrode that through the above steps prepared by i to step iv can have swift electron mobility, due to without using bonding Agent and increase activity substance content, therefore, when be suitable for capacitor when specific capacitance and specific capacitance conservation rate can be improved.
The another third embodiment of the present invention provides electrode of super capacitor, comprising: accordion graphene-carbon nano tube- Polymer composite, including accordion graphene film, include that carbon nanotube inside above-mentioned graphene film and electric conductivity are high Molecule, above-mentioned accordion graphene-carbon nano tube-polymer composite is spherical shape, and average particle size is 1 μm to 10 μm； Collector is being formed with multiple above-mentioned complexs on one side；And graphene film, for fixing above-mentioned collector and complex, and For fixing above-mentioned complex and complex.
Above-mentioned carbon nanotube can be selected from being made of single-walled carbon nanotube, double-walled carbon nano-tube and multi-walled carbon nanotube One of group carbon nanotube, preferably multi-walled carbon nanotube.
Above-mentioned electroconductive polymer can be for selected from by polyaniline, polypyrrole, polythiophene, polyacetylene, poly- furans and poly- pair One of the group of benzene composition, can preferably be polyaniline.
Above-mentioned accordion graphene-carbon nano tube-polyaniline complex can have the increased characteristic of graphene face spacing, this It may be as caused by oxygen functional group, carbon nanotube and electroconductive polymer for remaining in the graphene of above-mentioned complex etc..
When by being suitable for capacitor comprising the electrode of above-mentioned complex, since the graphene face spacing of complex increases and draw The high contact area risen, therefore can have the characteristic of the contact resistance reduction between water-soluble electrolytes.Also, in above-mentioned electrode In, replace the binder for supporting above-mentioned complex that above-mentioned complex is fixed on collector with graphene, to can be improved The specific capacitance and specific capacitance conservation rate of capacitor.
Another third embodiment of the present invention provides supercapacitor, comprising: a pair of electrodes, it is mutually opposed；Electrolyte, if It is placed between above-mentioned a pair of electrodes；And seperation film, it is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit, above-mentioned electricity Electrode of super capacitor extremely as described above.
Above-mentioned electrolyte can be used selected from by the acids electrolyte comprising sulfuric acid, the bases electrolyte comprising potassium hydroxide and One of the group of neutral electrolyte composition comprising sodium sulphate, but not limited to this.
Non-woven fabrics, polytetrafluoroethylene (PTFE), perforated membrane, brown paper, cellulose family electrolyte, artificial silk can be used in above-mentioned seperation film Fiber etc., but not limited to this.
The supercapacitor of third embodiment of the invention can be by due to the graphene face spacing of above-mentioned complex increases Caused high contact area, to reduce the interface resistance between above-mentioned electrode and electrolyte, so as to increase specific capacitance.Also, Since the electroconductive polymer in complex can have electric double layer and performance of the supercapacitor simultaneously.Further, it is not gluing Complex is fixed on collector to prepare electrode by graphene in the case where knot agent, thus will it is suitable for capacitors When, can have higher specific capacitance and specific capacitance conservation rate.Specifically, the ratio of the supercapacitor of third embodiment of the invention Capacitor can be 250F/g to 500F/g under the current density of 0.1A/g, or 400F/g to 500F/g.Even if in height Under current density, above-mentioned specific capacitance can also be kept substantially.Specifically, relative to the ratio electricity under the current density of 0.1A/g Hold, the specific capacitance under the current density of 4A/g can be 85% to 95%.
Hereinafter, passing through embodiment and experimental example present invention be described in more detail first embodiment.But following implementations Example and experimental example are only used for illustrating first embodiment of the invention, and it's not limited to that for the range of first embodiment of the invention.
The preparation 1 of<embodiment 1>accordion graphene-carbon nano tube complex
Graphene oxide (GO) as the raw material for being used to prepare graphene is according to improved HumMer's method (HumMer's Method after) being prepared by graphite, prepared by being dispersed in distilled water.
Step 1: in order to improve multi-walled carbon nanotube (95% purity, NANOLAB) to the dispersibility of water, having carried out sour place Reason.The multi-walled carbon nanotube of 1g is dispersed in the sulfuric acid (H of 150mL2SO4, 99.5%) and 50mL nitric acid (HNO3) mixed solution In after, 70 DEG C at a temperature of stir 2 hours.Then, it is cleaned with 5% hydrochloric acid (HCl) solution filtering and is carried out in air It is dry.It is with the mixed weight ratio (weight ratio) through the sour above-mentioned multi-walled carbon nanotube handled and graphene oxide 0.01:1, and mixed solution is prepared by solvent of distilled water.At this point, making 0.25 weight of graphene oxide concentration of mixed solution Percentage.
Step 2a: in order to prepare multi-walled carbon nanotube-graphene oxide complex, being utilized the molten reactor of gas, reaction Schematic diagram is as shown in Figure 2.It is by diameter by the mixed solution comprising multi-walled carbon nanotube and graphene oxide through acid processing The second fluid nozzle of 1.4mm forms drop in a manner of the molten injection of gas.
Step 2b: by the argon gas of the flow velocity of 8L/min by the droplet transfer sprayed to 200 DEG C of heating furnace, to make Solvent evaporation.By cyclone by prepared sample collection in the filter, thus to obtain the more of three-dimensional corrugated are prepared into Wall carbon nano tube-graphene oxide complex.In order to restore prepared above-mentioned multi-walled carbon nanotube-graphene oxide complex Graphene oxide, it is final to make after being heat-treated 2 hours under argon atmosphere (1L/min) in Muffle furnace with 250 DEG C of temperature For accordion graphene-multi-walled carbon nanotube (MWCNT-GR) complex.
(the multi-walled carbon nanotube: graphene oxide weight of preparation 2 of<embodiment 2>accordion graphene-carbon nano tube complex Amount is than being 0.05:1)
In the step 1 of above-described embodiment 1, in addition to by multi-walled carbon nanotube: graphene oxide weight ratio is changed to 0.05:1 It prepares except mixed solution, accordion graphene-multi-walled carbon nanotube is prepared in a manner of identical with above-described embodiment 1 multiple It is fit.
(the multi-walled carbon nanotube: graphene oxide weight of preparation 3 of<embodiment 3>accordion graphene-carbon nano tube complex Amount is than being 0.1:1)
In the step 1 of above-described embodiment 1, in addition to by multi-walled carbon nanotube: graphene oxide weight ratio is changed to 0.1:1 It prepares except mixed solution, it is compound that accordion graphene-multi-walled carbon nanotube is prepared in a manner of identical with above-described embodiment 1 Body.
(the multi-walled carbon nanotube: graphene oxide weight of preparation 4 of<comparative example 1>accordion graphene-carbon nano tube complex Amount is than being 0.5:1)
In the step 1 of above-described embodiment 1, in addition to by multi-walled carbon nanotube: graphene oxide weight ratio is changed to 0.5:1 It prepares except mixed solution, it is compound that accordion graphene-multi-walled carbon nanotube is prepared in a manner of identical with above-described embodiment 1 Body.
<the preparation 1 of embodiment 4>supercapacitor
In order to prepare active material, the accordion graphene-prepared in above-described embodiment 1 is blended in the weight ratio of 9:1 (polyvinylidene difluoride, PVDF, Japan can Li Hua company for Carbon Nanotube and polyvinylidene fluoride (KUREHA Co., Japan)) binder, utilize blender and n-methyl-2-pyrrolidone (n-methyl-2- Pyrrolidone, NMP, Micropure-EG) solvent is sufficiently stirred 20 minutes together.It will complete the active substance solution of stirring It is coated on using 100 μm of thickness as on the carbon paper (AvCarb P50, FuelCellsEtc, USA) of collector.It will be coated Active material 80 DEG C at a temperature of it is 2 hours dry, and be cut into 2cm2Area, the weight for measuring per unit electrode is about 5mg.Filter paper (Filter paper, Whatman 1822-110 Grade GF/C) is cut into diameter to be 14mm and be used as separation Film (separator), electrolyte have used the potassium hydroxide of the concentration of 5M.Finally, using as the HS FLAT of two electrodes CELL (HOHSEN Corp., Japan) is prepared for supercapacitor.
<the preparation 2 of embodiment 5>supercapacitor
In above-described embodiment 4, other than using the complex prepared in above-described embodiment 2 in active material preparation, Supercapacitor is prepared in a manner of identical with above-described embodiment 4.
<the preparation 3 of embodiment 6>supercapacitor
In above-described embodiment 4, other than using the complex prepared in above-described embodiment 3 in active material preparation, Supercapacitor is prepared in a manner of identical with above-described embodiment 4.
<the preparation 4 of comparative example 2>supercapacitor
In above-described embodiment 4, other than using the complex prepared in above-mentioned comparative example 1 in active material preparation, Supercapacitor is prepared in a manner of identical with above-described embodiment 4.
The surface of<experimental example 1>graphene-multi-wall carbon nano-tube tube complex and morphometric evaluation
Pass through field emission scanning electron microscope (FE-SEM, Sirion, FEI) and transmission electron microscope (TEM, JEM- ARM200F, JEOL) shoot accordion graphene-multi-wall carbon nano-tube that above-described embodiment 1 is prepared into embodiment 3 and comparative example 1 Structure, the shape of pipe, (a1) of result such as Fig. 3 partially to (d1) part, Fig. 3 (a2) partially to shown in the part (d2).
If (a1) of Fig. 3 is partially to shown in the part (d1), prepared all complexs are in the graphene film of 3D shape By the form of gauffer (crumped), diameter is about 4 μm to 6 μm.
By transmission electron microscope observation as a result, can confirm multi wall carbon if (a2) of Fig. 3 is partially to shown in the part (d2) Nanotube is present in the graphene film of corrugated, it is known that, when preparation, with multi-walled carbon nanotube/graphene oxide weight Than more increasing, the multi-walled carbon nanotube content for being present in graphene film also increases.It can confirm with multi-walled carbon nanotube: oxidation stone Black alkene weight ratio is in graphene-multi-wall carbon nano-tube tube complex prepared by 0.01:1 to 0.1:1, and multi-walled carbon nanotube is equably It is dispersed between graphene film.But with multi-walled carbon nanotube: graphene oxide weight ratio is the graphene-of 0.5:1 preparation In the case where multi-wall carbon nano-tube tube complex, it can confirm and be sent out since the multi-walled carbon nanotube amount being present in graphene film is more Raw cohesion, so that pockets of (bundles) multi-walled carbon nanotube be made to increase.
The X-ray diffraction analysis of<experimental example 2>graphene-multi-wall carbon nano-tube tube complex
Using X-ray diffraction (SmartLab, Rigaku Co.) analysis above-described embodiment 1 into embodiment 3 and comparative example 1 The graphene of preparation-multi-wall carbon nano-tube tube complex, result are as shown in Figure 4.
As shown in figure 4, prepared all graphenes-multi-wall carbon nano-tube tube complex X-ray diffraction peak (peak) is big It appears in range near about 23.5 ° and 42.9 °.This is because the graphene oxide peak for being present in 10 ° is reduced and is moved to stone Black alkene peak.Also, graphene-multi-wall carbon nano-tube tube complex X-ray diffraction peak of reduction is to movement on the left of the peak of graphite Form, this is because due to the introducing of a variety of the oxygen functional groups and multi-walled carbon nanotube that remain in graphene, complex Graphene face spacing (interlayer spacing) increases.According to Bragg's equation (Bragg's law) formula (following mathematical expressions 2) interplanar distance is calculated the results show that embodiment 1, embodiment 2, graphene-multi-walled carbon nanotube of embodiment 3 and comparative example 1 are multiple Fit interplanar distance is respectively 0.37nm, 0.37nm, 0.36nm, 0.34nm, and the interplanar distance of the graphite relative to 0.33nm owns Sample all increases.On the other hand, the ratio that weight ratio (multi-walled carbon nanotube: graphene oxide) is 0.5:1 when prepared by complex In the case where compared with example 1, it is seen that relative to other graphenes-multi-wall carbon nano-tube tube complex, interplanar distance reduces, this is because due to Multi-walled carbon nanotube injection rate increases, and the cohesion between multi-walled carbon nanotube causes the interplanar distance of complex to reduce.
[mathematical expression 2]
d002=n λ/2sin θ
The Raman spectroscopy of<experimental example 3>graphene-multi-wall carbon nano-tube tube complex
To the graphene prepared in above-described embodiment 1 to embodiment 3 and comparative example 1-multi-wall carbon nano-tube tube complex into Raman spectrum (Lambda Ray, LSI Dimension P1) analysis is gone, result is as shown in Figure 5.
As shown in figure 5, confirming from prepared graphene-multi-wall carbon nano-tube tube complex Raman analysis result, respectively In 1350cm-1、1600cm-1In observe indicate graphene the peak D and the peak G.Wherein, the peak G is the peak for indicating the carbon of graphite, the peak D To indicate graphene sp2The missing (defect) of structure and the peak of substitution or imbalance (disorder).It therefore, can be from the peak D and the peak G Intensity than confirm graphene defect level.Prepared graphene-multi-wall carbon nano-tube tube complex D/G band (band) compares It is reduced as multi-walled carbon nanotube in the preparation/graphene oxide weight ratio increases.This shows due to introducing defect level It is relatively lower than the multi-walled carbon nanotube of graphene film, the defect level of complex reduces.
<i of experimental example 4>supercapacitor) cyclic voltammetry, ii) charge and discharge and iii) impedance operator evaluation
It is detected by potentiostat (Potentiostat) (VSP, Bio-logics) in above-described embodiment 4 to embodiment 6 And cyclic voltammetry, charge and discharge and the impedance operator of the supercapacitor prepared in comparative example 2, portion (a) of result such as Fig. 6 Divide to shown in the part (d).
In general, potassium hydroxide aqueous solution is used to have as the double-layer capacitor of electrolyte due to the absorption of surface ion There is electric double layer effect and there is the graphics shape close to rectangle, specific capacitance increases as rectangular area increases.
I) therefore, as shown in part (a) of Fig. 6, it is known that prepared for evaluating by graphene-multi-wall carbon nano-tube tube complex The cyclic voltammetry test result of performance of supercapacitor show, there is ideal Electric double-layer capacitor in all electrodes Device driving.Also, as multi-walled carbon nanotube/graphene oxide weight ratio from 0.01 increases to 0.1 when preparing complex, circulation The area of i-v curve also increases, but area is reduced under conditions of 0.5.This may be because introducing the more of graphene The increase of wall carbon nano tube injection rate increases the interplanar distance of highly conductive degree and graphene, so that electrolyte ion is not felt as Big resistance and it is arranged in electrode substance interface well.On the other hand, multi-walled carbon nanotube/oxidation stone when preparing complex In the case that black alkene weight ratio is 0.5 or more, the agglomerating interplanar distance for leading to graphene between multi-walled carbon nanotube reduces and subtracts The slow ion transport speed of electrolyte.
Ii) the letter of (b) of Fig. 6 charge and discharge test result shown partially and the specific capacitance thus calculated as scanning speed Number.Charge and discharge test indicates reversible symmetrical charging and discharging curve the results show that all electrodes are all shown, at this point, than electricity Appearance can be found out by following mathematical expressions 3.
[mathematical expression 3]
Cp=4I Δ t/m Δ V
Wherein, I is discharge current, Δ t is discharge time, m is the quality of active material, Δ V is measurement voltage range.Such as Shown in part (c) of Fig. 6, electric current of the specific capacitance comprising graphene-multi-wall carbon nano-tube tube complex capacitor in 0.1A/g Under density, embodiment 4, embodiment 5, embodiment 6 and comparative example 2 respectively 137F/g, 144F/g, 192F/g, 109F/g, with Multi-walled carbon nanotube/graphene oxide weight ratio increases to 0.1 from 0.01 when preparing complex, and specific capacitance also increases, still, when When multi-walled carbon nanotube/graphene oxide weight ratio is 0.5, specific capacitance is reduced instead.The multi-wall carbon nano-tube when preparing complex In the case where the embodiment 6 that pipe/graphene oxide weight ratio is 0.1, while high specific capacitance is presented, as scanning speed increases Also high specific capacitance is kept.It follows that there are the optimum conditions of the mixing ratio of multi-walled carbon nanotube and graphene oxide.This be because To improve electrolysis due to introducing interplanar distance increase caused by multi-walled carbon nanotube as described in above-mentioned cyclic voltammetry result Matter ion permeates to electrode interior and improves electrical conductivity, to be able to maintain specific capacitance under high scanning speed.It is another Aspect, when preparing complex multi-walled carbon nanotube/graphene oxide weight ratio be 0.5 in the case where, although specific capacitance with Current density increase and reduce be not obvious, however, one will appreciate that specific capacitance is a bit low under all current densities.It is thought that because For relative to graphene, since excessive introducing has the multi-walled carbon nanotube of low specific capacitance and sees under transmission electron microscope Electrolyte interface resistance increase caused by the coacervation for the multi-walled carbon nanotube examined causes the specific capacitance of complex to reduce.
Iii) as shown in part (d) of Fig. 6, implement the interface resistance impedance experiments knot institute for investigating electrode and electrolyte Show, as multi-walled carbon nanotube/graphene oxide weight ratio increases when preparing complex, bulk resistor (bulk resistance, The values of intercept of the Z' axis of part (d) corresponding to Fig. 6) it is substantially similar other than in comparative example 2, but interface resistance (interfacial resistance, semicircle in the nyquist diagram (nyquist plot) of part (d) corresponding to Fig. 6 Diameter) it is reduced with the increase of multi-walled carbon nanotube injection rate.This may be because not only the quick of multi-walled carbon nanotube is led Resistance reduces caused by electrical property, and causes the contact area between electrolyte to increase since the interplanar distance of graphene increases Add, so as to reduce the interface resistance based on ionic conductance.
Therefore, by graphene-multi-walled carbon nanotube (graphene-multi wall of the embodiment of first embodiment of the invention Carbon nanotube) complex is prepared into the spherical 3D shape that average particle size is 1 μm to 10 μm, multi-walled carbon nanotube dispersion Between graphene film.Evaluation comprising graphene-multi-wall carbon nano-tube tube complex supercapacitor performance the results show that In the case that when preparing complex, multi-walled carbon nanotube/graphene oxide weight ratio is 0.1, specific capacitance 192F/g, for most Height can also keep specific capacitance well at higher current densities.Thus, it is believed that introducing multi-walled carbon nanotube to graphene can be improved The characteristics such as electrical conductivity, ionic conductance, the increase of graphene face spacing.In particular, also can be fine at high current density (4A/g) It is because while multi-walled carbon nanotube is additionally formed physical crosslinking point in graphene, being prepared into three-dimensional that ground, which keeps specific capacitance, Stomata in the graphene of shape-multi-wall carbon nano-tube tube complex makes the interface resistance between electrode and electrolyte.
Hereinafter, passing through embodiment and experimental example present invention be described in more detail second embodiment.But following implementations Example and experimental example are only used for illustrating second embodiment of the invention, and the range of second embodiment of the present invention is not limited to This.
<embodiment i>accordion graphene-carbon nano tube-polymer composite preparation 1
After graphene oxide as the raw material for preparing graphene is prepared by improved HumMer's method by graphite, point It dissipates in distilled water and prepares.
Step i: in order to improve multi-walled carbon nanotube (95% purity, NANOLAB) to the dispersibility of water, sour place has been carried out Reason.The multi-walled carbon nanotube of 1g is dispersed in the sulfuric acid (H of 150mL2SO4, 99.5%) and 50mL nitric acid (HNO3) mixed solution Afterwards, 70 DEG C at a temperature of stir 2 hours.Then, it is cleaned with 5% hydrochloric acid (HCl) solution filtering and is done in air It is dry.With the mixed weight ratio of multi-walled carbon nanotube and graphene oxide through acid processing for 0.01:1, the hydrochloric acid solution of 1M is added. At this point, making 0.25 weight percent of graphene oxide concentration of hydrochloric acid solution.Also, it will be as electroconductive polymer monomer Aniline, which is added in above-mentioned hydrochloric acid solution, makes its concentration become 20mM, to be prepared for mixed solution.
Step ii: ammonium persulfate (APS is added as initiator；98% purity, Sigma-Aldrich) so that above-mentioned The aniline monomer of mixed solution: initiator weight ratio is 4:1, and the ultrasonication carried out 1 hour to above-mentioned mixed solution is come It is polymerize.
Step iiia: in order to prepare multi-walled carbon nanotube-graphene oxide-polyaniline complex, the molten reaction of gas is utilized Device, reaction schematic diagram are as shown in Figure 8.Dispersed in a manner of the molten injection of gas the second fluid nozzle that diameter is 1.4mM comprising warp The multi-walled carbon nanotube of acid processing, graphene oxide and polyaniline mixed solution form drop.
Step iiib: by the argon gas of the flow velocity of 8L/min by the droplet transfer of injection to 200 DEG C of heating furnace, to make Solvent evaporation.By cyclone by prepared sample collection in the filter, thus to obtain the more of three-dimensional corrugated are prepared into Wall carbon nano tube-graphene oxide-polyaniline complex.In order to restore prepared above-mentioned multi-walled carbon nanotube-graphite oxide Alkene-polyaniline complex graphene oxide, is heat-treated under argon atmosphere (1L/min) in Muffle furnace with 250 DEG C of temperature After 2 hours, it is finally prepared for accordion graphene-multi-walled carbon nanotube-polyaniline (MWCNT-GR-PANI) complex.
<embodiment ii>accordion graphene-carbon nano tube-polymer composite preparation 2 (multi-walled carbon nanotube: oxidation Graphene weight ratio is 0.05:1)
In the step i of above-described embodiment i, in addition to by multi-walled carbon nanotube: graphene oxide weight ratio is changed to 0.05:1 It prepares except mixed solution, is prepared for accordion graphene-multi-wall carbon nano-tube in a manner of identical with upper above-described embodiment i Pipe-polyaniline complex.
(the multi-walled carbon nanotube: graphene oxide of preparation 3 of<embodiment iii>accordion graphene-carbon nano tube complex Weight ratio is 0.1:1)
In the step i of above-described embodiment i, in addition to by multi-walled carbon nanotube: graphene oxide weight ratio is changed to 0.1:1 It prepares except mixed solution, it is poly- that accordion graphene-multi-walled carbon nanotube-is prepared in a manner of identical with above-described embodiment i Aniline complex.
The preparation of<comparative example i>accordion graphene ball
In the step i of above-described embodiment i, in addition to not adding carbon nanotube and electroconductive polymer monomer and omitting step Except ii, accordion graphene ball (corrugated graphene (CGR)) is prepared in a manner of identical with above-described embodiment i.
The preparation of<comparative example ii>accordion graphene-carbon nano tube
In the step i of above-described embodiment i, other than not adding electroconductive polymer monomer and omitting step ii, with Mode identical with above-described embodiment i is prepared for accordion graphene-carbon nano tube complex.
<the preparation 1 of embodiment iv>supercapacitor
In order to prepare active material, the accordion graphene-prepared in above-described embodiment 1 is blended in the weight ratio of 9:1 Carbon nanotube-polymer composite and polyvinylidene fluoride (KUREHA Co., Japan) binder, utilize blender and N- first Base -2-Pyrrolidone (Micropure-EG) solvent is sufficiently stirred 20 minutes together.Will complete stirring active substance solution with 100 μm of thickness is coated on as on the carbon paper (AvCarb P50, FuelCellsEtc, USA) of collector.By coated work Property substance 80 DEG C at a temperature of it is 2 hours dry, and be cut into 2cm2Area, the weight for measuring per unit electrode is about 5mg. Filter paper (Whatman 1822-110 Grade GF/C) is cut into diameter as 14mM and is used as seperation film, electrolyte has used 5M Dense potassium hydroxide.Finally, it is prepared for surpassing using the HS FLAT CELL (HOHSEN Corp., Japan) as two electrodes Grade capacitor.
<the preparation 2 of embodiment v>supercapacitor
In above-described embodiment iv, in addition in active material preparation using the complex prepared in above-described embodiment ii it Outside, supercapacitor is prepared in a manner of identical with above-described embodiment iv.
<the preparation 3 of embodiment vi>supercapacitor
In above-described embodiment iv, in addition in active material preparation using the complex prepared in above-described embodiment iii it Outside, supercapacitor is prepared in a manner of identical with above-described embodiment iv.
<the preparation 4 of comparative example iii>supercapacitor
In above-described embodiment iv, in addition to using the accordion graphite prepared in above-mentioned comparative example i in active material preparation Except alkene, supercapacitor is prepared in a manner of identical with above-described embodiment iv.
<the preparation 5 of comparative example vi>supercapacitor
In above-described embodiment iv, in addition in active material preparation using the complex prepared in above-mentioned comparative example ii it Outside, supercapacitor is prepared in a manner of identical with above-described embodiment iv.
The surface of<experimental example i>graphene-multi-walled carbon nanotube-polyaniline complex and morphometric evaluation
By field emission scanning electron microscope and transmission electron microscope shooting in above-described embodiment i, comparative example i and ratio Compared with structure, the shape of the substance prepared in example ii, a of result such as Fig. 9 is partially to the part c, the part d to the part the f institute of Fig. 9 Show.
If the part a of Fig. 9 is to shown in the part c, prepared all complexs are in the graphene film of 3D shape by gauffer Form, diameter is about 4 μm to 6 μm.At this point, shape does not change with the addition of carbon nanotube and aniline, recognize It is present between graphene film for carbon nanotube and polyaniline.
The part d of Fig. 9 can be confirmed, corrugated graphene film to shown in the part f by transmission electron microscope observation result In there are multi-walled carbon nanotubes, also, can confirm addition aniline after, in the Surface Creation polyaniline of carbon nanotube and graphene.
The X-ray diffraction analysis of<experimental example ii>graphene-multi-walled carbon nanotube-polyaniline complex
To the substance that is prepared in above-described embodiment i, comparative example i and comparative example ii carry out X-ray diffraction (SmartLab, Rigaku Co.) analysis, result is as shown in the part a of Figure 10.
As shown in the part a of Figure 10, graphene-carbon nanometer of the corrugated graphene (CGR) of comparative example i, comparative example ii Pipe, embodiment i graphene-carbon nano tube-polyaniline complex X-ray diffraction analysis as a result, prepared corrugated stone Black alkene, carbon nano tube/graphene sample have graphene and carbon nanotube peak under 23.5 °, 26.4 °.On the other hand, graphite Alkene-carbon naotube-polyaniline complex has 19.7 ° and 25.3 ° of polyaniline peak together with graphene and carbon nanotube peak.Cause This, can confirm in prepared corrugated graphene, graphene-carbon nano tube complex, graphene-carbon nano tube-polyaniline Graphene, carbon nanotube, polyaniline are successfully prepared in complex.
The Raman spectroscopy of<experimental example iii>graphene-multi-walled carbon nanotube-polyaniline complex
To above-described embodiment i, the graphene-multi-walled carbon nanotube-polyaniline prepared in comparative example i and comparative example ii is compound Body has carried out Raman spectrum (Lambda Ray, LSI Dimension P1) analysis, and result is as shown in the part b of Figure 10.
As shown in the part b of Figure 10, in all samples for being prepared in above-described embodiment i, comparative example i and comparative example ii, Respectively in 1350cm-1、1600cm-1In observe the peak D and the peak G as graphene peak, at this point, the peak G is the carbon for indicating graphite Peak, the peak D are to indicate graphene sp2The missing of structure and substitution or imbalance peak.On the other hand, in graphene-carbon nano tube-polyphenyl Amine complex is in 1163cm-1、1250cm-1、1478cm-1Under observe indicate polyaniline c h bond close peak, can from these knot Fruit can confirm, successfully generate polyaniline in prepared complex.
The mercury gaging hole method of<experimental example iv>graphene-multi-walled carbon nanotube-polyaniline complex measures
It is compound to the graphene-multi-walled carbon nanotube-polyaniline prepared in above-described embodiment i, comparative example i and comparative example ii Body has carried out mercury gaging hole (AutoPore IV, Micromeritics) analysis, and result is as shown in figure 11.
As shown in figure 11, it measures the corrugated graphene of comparative example i, the graphene-carbon nano tube of comparative example ii, implement Graphene-multi-walled carbon nanotube-polyaniline complex average pore size (average pore diameter) (nm) point of example i It Wei not 340nm, 657nm, 824nm.At this time, it is believed that carbon nanotube and being introduced into for polyaniline cause pore opening in complex to increase Add, increased pore opening improve proximity of the electrolyte to complex electrode.
<i of experimental example v>supercapacitor) cyclic voltammetry, ii) charge and discharge and iii) impedance operator evaluation
Through potentiostat (VSP, Bio-logics) detection in above-described embodiment iv, comparative example iii and comparative example iv Cyclic voltammetry, charge and discharge and the impedance operator of the supercapacitor of preparation, (a) of result such as Figure 12 is partially to the portion (d) Shown in point.
In general, potassium hydroxide aqueous solution is used to have as the double-layer capacitor of electrolyte due to the absorption of surface ion There is electric double layer effect and there is the graphics shape close to rectangle, specific capacitance increases as rectangular area increases.
I) 2 part a referring to Fig.1, by the circulating current voltage test result of prepared sample it is found that in all electrodes In have ideal double-layer capacitor driving.Also, this rectangular area presses corrugated graphene, graphene-carbon nano tube, stone Black alkene-carbon naotube-polyaniline sequentially increases, it is believed that this is because leading to electrode due to introducing carbon nanotube and polyaniline The diffusion of middle electrolyte increases and mobile resistance is reduced.This can pass through the presence of the redox peaks of cyclic voltammetry result And occurs weak areas of congestion (Plateau) in the charging and discharging curve of the part b of Figure 12 to confirm.These results indicate that graphene- Carbon naotube-polyaniline complex has electric double layer and pseudocapacitors simultaneously.
Ii) function of the c of Figure 12 specific capacitance shown partially calculated by charge and discharge test result as scanning speed.Wrinkle Pleated graphene, graphene-carbon nano tube, graphene-carbon nano tube-polyaniline sample are respectively provided under conditions of 0.1A/g The specific capacitance of 121F/g, 192F/g, 294F/g.At this point, graphene-carbon nano tube-polyaniline complex spherical form, by drawing Enter that surface area caused by carbon nanotube increases and outstanding electrical conductivity characteristic improves the infiltration of electrode surface electrolyte ion, when drawing There is highest specific capacitance when entering pseudocapacitors characteristic caused by polyaniline.
Iii) as shown in the part d of Figure 12, impedance experiments are executed under the frequency range of 100kHz to 0.01Hz, and investigate Spherical graphene-carbon nano tube-polyaniline electrode intermediate ion diffusion.Referring to corrugated graphene, graphene-carbon nano tube, Graphene-carbon nano tube-polyaniline sample nyquist diagram, compared with other electrodes, graphene-carbon nano tube-polyaniline Electrode is in low-frequency region linearly and in high-frequency region in semicircle.It is generated as a result, in the inside of graphene and carbon nanotube Also quick extension is kept after polyaniline.
<experimental example vi>is according to the i of the supercapacitor of content of carbon nanotubes) cyclic voltammetry, ii) charge and discharge and Iii) impedance operator is evaluated
The supercapacitor prepared in above-described embodiment iv into vi is detected by potentiostat (VSP, Bio-logics) Cyclic voltammetry, charge and discharge and impedance operator, result such as Figure 13 a part to shown in the part d.
I) as shown in the part a of Figure 13, can be confirmed by cyclic voltammetry test result, cyclic voltammetry curvilinear plane Product increases as carbon nanotube additive amount increases.This is because the increase of the additive amount of the carbon nanotube introduced in graphene Inhibit highly conductive degree and graphene film in conjunction with to improve the ion transport speed of electrolyte in prepared electrode.
Ii) b and the c charge and discharge test shown partially of Figure 13 and the specific capacitance thus calculated are as scanning speed function.It is logical Crossing charge and discharge test result can confirm, have electric double layer and pseudocapacitors characteristic in all electrodes, specific capacitance is 0.1A/g's It is respectively 250F/g, 266F/g, 294F/g under current density.It is found that this is because specific capacitance increases with carbon nanotube additive amount Add and increases, as current density increases, specific capacitance multi-walled carbon nanotube/graphene oxide when additive amount is to prepare complex Weight ratio also has highest conservation rate when being 0.1.
Iii) as shown in the part d of Figure 13, implement the interface resistance impedance experiments result for investigating electrode and electrolyte It is shown, as carbon nanotube additive amount increases, linearly and in high-frequency region in semicircle in low-frequency region.This show by The resistance of the carbon nanotube caused by quick conductivity reduces, at the same between graphene film in conjunction with inhibition increase electricity The contact area for solving matter, thus greatly reduces the interface resistance due to caused by ionic conduction.
The present inventor passes through real by above-mentioned second using molten injection (Aerosol Spray Pyrolysis, the ASP) process of gas It applies multi-walled carbon nanotube (Multi-Wall Carbon Nanotube, CNT), graphene oxide in the embodiment of mode The colloidal solution that (Graphene Oxide, GO), aniline mix is prepared for the graphite of three-dimensional structure by single process Alkene-multi-walled carbon nanotube-polyaniline spherical shape complex.The multi-walled carbon nanotube in the mixed colloidal solution of step i is put into stone Crosslinked action is played between black alkene piece, to improve electrical conductivity and increase interplanar distance, so that electrolyte proximity is improved, by adding Enter the complex that polyaniline is prepared for three-dimensional spherical form, by forming uniform stomata inside complex and by polyphenyl The highly conductive degree and redox reaction of amine come while improving power density and energy density.
Hereinafter, passing through embodiment and experimental example third embodiment of the invention detailed further.But following embodiments And experimental example is only used for illustrating third embodiment of the invention, it's not limited to that for the range of third embodiment of the present invention.
<embodiment i+>accordion graphene-carbon nano tube-polymer composite preparation 1
After graphene oxide as the raw material for preparing graphene is prepared by improved HumMer's method by graphite, point It dissipates in distilled water and prepares.
Step i: in order to improve multi-walled carbon nanotube (95% purity, NANOLAB) to the dispersibility of water, sour place has been carried out Reason.The multi-walled carbon nanotube of 1g is dispersed in the sulfuric acid (H of 150mL2SO4, 99.5%) and 50mL nitric acid (HNO3) mixed solution Afterwards, 70 DEG C at a temperature of stir 2 hours.Then, it is cleaned with 5% hydrochloric acid (HCl) solution filtering and is done in air It is dry.With the mixed weight ratio of multi-walled carbon nanotube and graphene oxide through acid processing for 0.1:1, the hydrochloric acid solution of 1M is added. At this point, hydrochloric acid solution makes graphene oxide concentration be 0.25 weight percent.Also, electroconductive polymer monomer will be used as Aniline be added in above-mentioned hydrochloric acid solution make its concentration become 20mM, to be prepared for mixed solution.
Step ii: ammonium persulfate (APS is added as initiator；98% purity, Sigma-Aldrich), above-mentioned mixing The aniline monomer of solution: initiator weight ratio is 4:1, and carries out 1 hour ultrasonication to above-mentioned mixed solution to carry out Polymerization.
Step iiia: in order to prepare multi-walled carbon nanotube-graphene oxide-polyaniline complex, the molten reaction of gas is utilized Device, reaction schematic diagram such as Figure 15 disperse to include through at acid in a manner of the molten injection of gas the second fluid nozzle that diameter is 1.4mm The mixed solution of the multi-walled carbon nanotube of reason, graphene oxide and polyaniline forms drop.
Step iiib: by the argon gas of the flow velocity of 8L/min by the droplet transfer of injection to 200 DEG C of heating furnace, to make Solvent evaporation.By cyclone by prepared sample collection in the filter, thus to obtain the more of three-dimensional corrugated are prepared into Wall carbon nano tube-graphene oxide-polyaniline complex.In order to restore prepared above-mentioned multi-walled carbon nanotube-graphite oxide Alkene-polyaniline complex graphene oxide, is heat-treated under argon atmosphere (1L/min) in Muffle furnace with 250 DEG C of temperature After 2 hours, it is finally prepared for accordion graphene-multi-walled carbon nanotube-polyaniline complex.
<embodiment ii+>accordion graphene-carbon nano tube-polymer composite preparation 2 (concentration of aniline 10mM)
In the step i of above-described embodiment i+, in addition to make mixed solution concentration of aniline become 10mM other than, with it is above-mentioned The identical mode of embodiment i+ is prepared for accordion graphene-multi-walled carbon nanotube-polyaniline complex.
<embodiment iii+>accordion graphene-carbon nano tube-polymer composite preparation 3 (concentration of aniline 40mM)
In the step i of above-described embodiment i+, in addition to make mixed solution concentration of aniline become 40mM other than, with it is above-mentioned The identical mode of embodiment i+ is prepared for accordion graphene-multi-walled carbon nanotube-polyaniline complex.
<the preparation 1 of embodiment iv+>supercapacitor
Step iv: it in order to prepare electrode, is blended in above-described embodiment i+ and is made with the weight ratio of 9.5:0.5 (1:0.053) Standby accordion graphene-carbon nano tube-polymer composite and graphene oxide utilize blender and N- methyl -2- pyrroles Alkanone (Micropure-EG) solvent is sufficiently stirred 20 minutes together.The solution for completing stirring is coated on 100 μm of thickness As on the carbon paper (AvCarb P50, FuelCellsEtc, USA) of collector.By coated substance 250 DEG C at a temperature of Heat treatment 2 hours, and it is cut into 2cm2Area, the weight for measuring per unit electrode is about 1.5mg.
Filter paper (Whatman 1822-110Grade GF/C) is cut into diameter as 14mm and is used as seperation film, electrolyte makes With the dense potassium hydroxide of 5M.Finally, it is made using the HS FLAT CELL (HOHSEN Corp., Japan) as two electrodes For supercapacitor.
<the preparation 2 of embodiment v+>supercapacitor
In the step iv of above-described embodiment iv+, other than using the complex prepared in above-described embodiment ii+, Supercapacitor is prepared in a manner of identical with above-described embodiment iv+.
<the preparation 3 of embodiment vi+>supercapacitor
In the step iv of above-described embodiment iv+, other than using the complex prepared in above-described embodiment iii+, Supercapacitor is prepared in a manner of identical with above-described embodiment iv+.
<the preparation 4 of embodiment vii+>supercapacitor
In the step iv of above-described embodiment iv+, in addition to make complex and graphene oxide weight ratio become 9:1 (1: 0.111) except, supercapacitor is prepared in a manner of identical with above-described embodiment iv+.
<the preparation 5 of embodiment viii+>supercapacitor
In the step iv of above-described embodiment iv+, in addition to make complex and graphene oxide weight ratio become 8:2 (1: 0.25) except, supercapacitor is prepared in a manner of identical with above-described embodiment iv+.
The surface of<experimental example i+>graphene-multi-walled carbon nanotube-polyaniline complex and morphometric evaluation
Pass through field emission scanning electron microscope (FE-SEM, Sirion, FEI) and transmission electron microscope (JEM- ARM200F, JEOL) shooting prepared into embodiment iii+ in above-described embodiment i+ complex structure, shape, result is as schemed 16 part a to the part f and the part a of Figure 17 are to shown in the part f.
If the part a of Figure 16 is to shown in the part f, field emission scanning electron microscope observation the results show that embodiment 1 to The graphene-carbon nano tube prepared in embodiment 3-polyaniline complex be three-dimensional spherical (spherical) particle and diameter about It is 5 μm.At this point, shape does not change with the variation of aniline injection rate, it is believed that in graphene film when preparing electrode Between there are carbon nanotubes.Also, it is found that, with the increase of aniline injection rate, being seen on the surface of graphene when preparing electrode Also increase like the increment of the protrusion of polyaniline.
If the part a of Figure 17 is to shown in the part f, seen from transmission electron microscope and mapping image (mapping image) It observes with the presence or absence of carbon nanotube and polyaniline in prepared sample, and confirms that carbon nanotube is evenly dispersed in graphene In piece.Also, when preparing electrode, with the increase of aniline injection rate, in the polyaniline of carbon nanotube and the surface of graphene Production quantity increase.
The X-ray diffraction analysis of<experimental example ii+>graphene-multi-walled carbon nanotube-polyaniline complex
To the complex prepared in above-described embodiment i+ into embodiment iii+ carried out X-ray diffraction (SmartLab, Rigaku Co.) analysis, result is as shown in the part a of Figure 18.
As shown in the part a of Figure 18, can confirm the complex that is prepared into embodiment iii+ in embodiment i+ 23.5 °, There are polyaniline peaks under 19.7 ° and 25.3 ° together with graphene and carbon nanotube peak under 26.4 °.Therefore, can confirm made Graphene, carbon nanotube, polyaniline are successfully prepared in standby complex.
The Raman spectroscopy of<experimental example iii+>graphene-multi-walled carbon nanotube-polyaniline complex
To the complex prepared in above-described embodiment i+ into embodiment iii+ carried out Raman spectrum (Lambda Ray, LSI Dimension P1) analysis, result is as shown in the part b of Figure 18.
As shown in the part b of Figure 18, in the complex that above-described embodiment i+ is prepared into embodiment iii+ in 1350cm-1、 1600cm-1In observe the peak D and the peak G as graphene peak.Also, in 1163cm-1、1250cm-1、1478cm-1Under observe It indicates the peak that the c h bond of polyaniline closes, to confirm from these results, polyaniline is successfully generated in sample.
<experimental example iv+>is according to the i of the supercapacitor of concentration of aniline) cyclic voltammetry and ii) charge-discharge characteristic comments Valence
Measured by potentiostat (VSP, Bio-logics) prepare in above-described embodiment iv+ to embodiment vi+ it is super The cyclic voltammetry and charge-discharge characteristic of capacitor, the part a of result such as Figure 19 is to shown in the part c.
I) 9 part a referring to Fig.1, can confirm and drive and deposit there are double-layer capacitor in prepared all electrodes In the redox peaks of electrode.Also, when preparing electrode, there is widest cyclic voltammetry face when concentration of aniline is 20mM Product.But when preparing electrode, in the case where aniline has the high concentration of 40mM, cyclic voltammetry area is reduced instead, It is thought that since the content increase of polyaniline in complex causes electrolyte ion to increase to the diffusion length of electrode interior, from And influence capacitor performance.
Ii) as shown in the part b of Figure 19, curve areas of congestion can be confirmed with benzene when in charging and discharging curve prepared by electrode Amine injection rate increases and more obvious, these results indicate that graphene-carbon nano tube-polyaniline-graphite alkene complex indicates same When have electric double layer and pseudocapacitors characteristic.9 part c referring to Fig.1, when preparing electrode, concentration of aniline 10mM, 20mM, The electrode of 40mM is respectively provided with the specific capacitance of 354F/g, 456F/g, 256F/g under the current density of 0.1A/g.At this point, implementing The electrode of example i+ has highest specific capacitance, and as current density increase also keeps high specific capacitance.It is being prepared known to as a result, There are the optimum conditions of concentration of aniline when complex electrode.Also, as the introducing of carbon nanotube in complex electrode is in graphite Crosslinked action is played between alkene piece, also raising electrical conductivity, and help to improve the specific capacitance based on this.However, it is recognized that when preparation When electrode, it is useful in that there are the graphene-carbon nano tubes-of the embodiment iv+ prepared under conditions of the aniline of high concentration (40mM) The supercapacitor of the embodiment vi+ of polyaniline-graphite alkene electrode, specific capacitance is relatively low under all current densities.Think this It is that polyaniline growth caused by due to injecting excessive aniline when preparing electrode leads to that electrolyte ion is inhibited to move to electrode interior It is dynamic, it is reduced according to the active surface area of the electrode of redox reaction, influences specific capacitance.
<experimental example v+>is according to the i of the supercapacitor of graphene oxide additive amount) cyclic voltammetry and ii) charge and discharge Evaluating characteristics
It is measured by potentiostat (VSP, Bio-logics) in above-described embodiment iv+, embodiment vii+ and embodiment The cyclic voltammetry and charge-discharge characteristic of the supercapacitor prepared in viii+, the part a to the part c of result such as Figure 20 It is shown.
I) as shown in the part a of Figure 20, it can confirm that there is prepared all electrodes double-layer capacitor to drive and exist Redox peaks caused by being introduced by polyaniline.At this point, knowing the curve area of pictural surface by graphene-carbon nanometer when preparing electrode The mixed weight ratio of pipe-polyaniline complex and graphene oxide be 9.5:0.5,9:1,8:2 sequence reduce, it is believed that this be because To increase since graphene oxide injects, the active surface area of the sample of preparation is reduced.
Ii) can be confirmed by the part b, the charge and discharge test of the part c and the non-memory amount calculated result of Figure 20, when preparation electricity It, will when graphene-carbon nano tube-polyaniline complex and graphene oxide mixed weight ratio are 9.5:0.5,9:1,8:2 when pole When prepared complex electrode is suitable for capacitor, specific capacitance is respectively 471F/g, 456F/ under the current density of 0.1A/g g,432F/g.Also, be useful in prepare electrode when graphene-carbon nano tube-polyaniline complex mix with graphene oxide Weight ratio be 9.5:0.5 electrode capacitor in the case where, relative to be useful in prepare electrode when graphene-carbon nano tube- Capacitor of the polyaniline complex with graphene oxide mixed weight than the electrode for 9:1, specific capacitance conservation rate are close with electric current Degree increases and reduces.Confirm that, when preparing electrode, there are graphene-carbon nano tube-polyaniline complex and oxygen from these results The optimum condition of graphite alkene ratio.Therefore, in the case where no binder, introduce the complex electrode of graphene film due to The quick electronics of electrode is mobile and activity substance content increases, and leads to the specific capacitance of supercapacitor and the conservation rate of specific capacitance It is improved.
The present inventor is by utilizing molten injection (Aerosol Spray Pyrolysis, the ASP) process of gas by third embodiment party By multi-walled carbon nanotube (Multiwall-carbon nanotube, CNT), graphene oxide (Graphene in the embodiment of formula Oxide, GO), the colloidal solution that mixes of aniline be prepared for graphene-carbon nano tube-polyaniline complex, add herein Graphene oxide is prepared for graphene-carbon nano tube-polyaniline-graphite alkene complex electrode of three-dimensional structure.At this point, according to The performance of the supercapacitor and graphene oxide injection rate of concentration of aniline variation are adjusted, and have investigated prepared complex electricity respectively Extremely to the influence of performance of the supercapacitor.Confirm graphene-carbon nano tube-polyaniline-graphite alkene complex electrode due to electrode Internal smoothly electronics is mobile and the increase of electrode active material content and improves the specific capacity of supercapacitor.By sweeping Electron microscope, transmission electron microscope, X-ray diffraction, Raman analysis are retouched, investigation is when preparing electrode as concentration of aniline becomes Graphene-carbon nano tube-polyaniline physical property (shape, crystalloid, defect) of change, and carried out the electrode prepared by complex Super capacitor characteristics.
Although the accordion graphene complex in relation to first embodiment of the invention to third embodiment has been described Preparation method, the complex that thus prepares and the supercapacitor comprising complex specific embodiment, but it is clear that , various modifications can be carried out without departing from the scope of the invention.
Therefore, the scope of the present invention should not be construed as limited to described embodiment, and should require to protect by appended invention The equivalent for protecting range and the claimed range of appended invention determines.
, it should be understood that embodiment above-mentioned be all in all respects it is illustrative, be not necessarily to be construed as it is restrictive, Range is claimed by the invention to indicate in the scope of the present invention, rather than is described in detail, and invents claimed model The meaning and range enclosed and the derived form for having altered or deforming of its equivalent should be included within the scope of the invention.
Claims (according to the 19th article of modification of treaty)
1. a kind of preparation method of accordion graphene-carbon nano tube complex characterized by comprising
Prepare the colloid mixed solution (step 1) for mixing carbon nanotube, graphene oxide and solvent through acid processing；With And
It is spray-dried above-mentioned mixed solution, and is heat-treated (step 2).
2. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on Stating carbon nanotube is multi-walled carbon nanotube (MWCNT).
3. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on The cabonic acid processing for stating step 1 is carried out by dispersing carbon nanotube in the acid solution comprising sulfuric acid and nitric acid.
4. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on The mixed weight ratio of the carbon nanotube and graphene oxide of stating step 1 is 0.01:1 to 0.4:1.
5. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on The graphene oxide concentration for stating the mixed solution of step 1 is 0.10 weight percent to 0.50 weight percent.
6. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on Stating step 2 includes:
Pass through the mixed solution (step 2a) of second fluid nozzle spraying above-mentioned steps 1 in the form of aerosol droplets；And
Spraying above-mentioned droplet transfer is dried to heating furnace, and forms the accordion stone of self assembly by heat treatment Black alkene-Carbon Nanotube (step 2b).
7. the preparation method of accordion graphene-carbon nano tube complex according to claim 6, which is characterized in that on The diameter for stating the second fluid nozzle of step 2a is 1.0mm to 3.0mm.
8. the preparation method of accordion graphene-carbon nano tube complex according to claim 1 or 6, which is characterized in that The heat treatment of above-mentioned steps 2 or step 2b 200 DEG C to 500 DEG C at a temperature of carry out.
9. the preparation method of accordion graphene-carbon nano tube complex according to claim 1 or 6, which is characterized in that The heat treatment of above-mentioned steps 2 or step 2b carry out 1 hour to 10 hours.
10. a kind of accordion graphene-carbon nano tube complex, which is characterized in that
It is prepared by the preparation method of accordion graphene-carbon nano tube complex described in claim 1,
Above-mentioned accordion graphene-carbon nano tube complex includes:
Accordion graphene film；And
Carbon nanotube is included in inside above-mentioned graphene film,
Above-mentioned accordion graphene-carbon nano tube complex is spherical shape, and average particle size is 1 μm to 10 μm.
11. accordion graphene-carbon nano tube complex according to claim 10, which is characterized in that above-mentioned carbon nanometer Pipe is multi-walled carbon nanotube (MWCNT).
12. a kind of electrode of super capacitor, which is characterized in that include accordion graphene-carbon nanometer described in any one of claim 10 Tube complex.
13. a kind of supercapacitor, which is characterized in that
Include:
A pair of electrodes, it is mutually opposed, and include active material；
Electrolyte is set between above-mentioned a pair of electrodes；And
Seperation film is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit,
Above-mentioned active material includes accordion graphene-carbon nano tube complex described in any one of claim 10.
14. a kind of preparation method of accordion graphene-carbon nano tube-polymer composite characterized by comprising
Prepare the mixing for mixing the carbon nanotube through acid processing, graphene oxide, electroconductive polymer monomer and solvent Solution (step i)；
The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii)；And
It is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction and is heat-treated (step iii).
15. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that the carbon nanotube of above-mentioned steps i and the mixed weight ratio of graphene oxide are 0.01:1 to 0.5:1.
16. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that the monomer concentration of the mixed solution of above-mentioned steps i is 5mM to 50mM.
17. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is, the electroconductive polymer monomer of above-mentioned steps i be selected from by aniline, pyrroles, thiophene, acetylene, furans, phenylene and it Derivative composition one or more of group.
18. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that above-mentioned steps ii passes through the addition polymerization initiator into above-mentioned mixed solution and handles ultrasonic wave to carry out.
19. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that above-mentioned steps iii includes:
The above-mentioned mixed solution (step iiia) of polymerization reaction is sprayed through in the form of aerosol droplets by second fluid nozzle；And
Spraying above-mentioned droplet transfer is dried to heating furnace, and forms the accordion stone of self assembly by heat treatment Black alkene-carbon nanotube-polymer composite (step iiib).
20. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 19, special Sign is that the diameter of the second fluid nozzle of above-mentioned steps iiia is 1.0mm to 3.0mm.
21. the graphene-carbon nano tube of accordion described in 4 or 19-polymer composite preparation method according to claim 1, It is characterized in that, the heat treatment of above-mentioned steps iii or step iiib are 1 hour to 10 small in 200 DEG C to 500 DEG C of at a temperature of progress When.
22. a kind of accordion graphene-carbon nano tube-polymer composite, which is characterized in that
It is prepared by accordion graphene-carbon nano tube-polymer composite preparation method described in claim 14,
Above-mentioned accordion graphene-carbon nano tube-polymer composite includes:
Accordion graphene film；
Carbon nanotube is included in inside above-mentioned graphene film；And
Electroconductive polymer,
Above-mentioned accordion graphene-carbon nano tube-polymer composite is spherical shape, and average particle size is 1 μm to 10 μm.
23. accordion graphene-carbon nano tube-polymer composite according to claim 22, which is characterized in that above-mentioned Electroconductive polymer is selected from by one in polyaniline, polypyrrole, polythiophene, polyacetylene, poly- furans and the poly- group formed to benzene Kind.
24. a kind of electrode of super capacitor, which is characterized in that include accordion graphene-carbon nanometer described in claim 22 Pipe-polymer composite.
25. a kind of supercapacitor, which is characterized in that
Include:
A pair of electrodes, it is mutually opposed, and include active material；
Electrolyte is set between above-mentioned a pair of electrodes；And
Seperation film is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit,
Above-mentioned active material includes accordion graphene-carbon nano tube-polymer composite described in claim 22.
26. a kind of preparation method of the electrode of super capacitor comprising accordion graphene complex characterized by comprising
Prepare the mixing for mixing the carbon nanotube through acid processing, graphene oxide, electroconductive polymer monomer and solvent Solution (step i)；
The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii)；
It is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction, and prepares accordion graphene complex by being heat-treated (step iii)；And
It mixes above-mentioned complex, graphene oxide and solvent and is heat-treated (step iv) after being coated on collector.
27. the preparation method of the electrode of super capacitor according to claim 26 comprising accordion graphene complex, It is characterized in that, above-mentioned complex: the mixed weight ratio of graphene oxide is 1:0.02 to 1:0.5 in above-mentioned steps iv.
28. the preparation method of the electrode of super capacitor according to claim 26 comprising accordion graphene complex, It is characterized in that, the heat treatment of above-mentioned steps iv be 200 DEG C to 500 DEG C at a temperature of carry out 1 hour to 10 hours.
29. a kind of electrode of super capacitor characterized by comprising
Accordion graphene-carbon nano tube-polymer composite, including accordion graphene film, be included in above-mentioned graphene film Internal carbon nanotube and electroconductive polymer, above-mentioned accordion graphene-carbon nano tube-polymer composite are spherical shape, And average particle size is 1 μm to 10 μm；
Collector is being formed with multiple above-mentioned complexs on one side；And
Graphene film, for making above-mentioned complex be fixed on above-mentioned collector and making to realize between above-mentioned complex and complex solid It is fixed.
30. a kind of supercapacitor, which is characterized in that
Include:
A pair of electrodes, it is mutually opposed；
Electrolyte is set between above-mentioned a pair of electrodes；And
Seperation film is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit,
Above-mentioned electrode is electrode of super capacitor described in claim 29.
Illustrate or states (according to the 19th article of modification of treaty)
According to the 19th (1) article of statement
1, modified claim
Modification right requires 29.
2, content is modified
In order to further clarify the content of claim 29 record, by graphene film, for fixing above-mentioned collector and answering Zoarium, and for fixing above-mentioned complex and complex is revised as graphene film, for making above-mentioned complex be fixed on above-mentioned collection Electric body simultaneously makes to realize fixation between above-mentioned complex and complex.
3, influence of the modification of claim to specification and attached drawing
The modification basis of above-mentioned claim 29 is specification [57], [252], [256] section and attached drawing 15, will not Any influence is brought to the description and the appended drawings.

Claims (30)

1. a kind of preparation method of accordion graphene-carbon nano tube complex characterized by comprising
Prepare the colloid mixed solution (step 1) for mixing carbon nanotube, graphene oxide and solvent through acid processing；With And
It is spray-dried above-mentioned mixed solution, and is heat-treated (step 2).
2. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on Stating carbon nanotube is multi-walled carbon nanotube (MWCNT).
3. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on The cabonic acid processing for stating step 1 is carried out by dispersing carbon nanotube in the acid solution comprising sulfuric acid and nitric acid.
4. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on The mixed weight ratio of the carbon nanotube and graphene oxide of stating step 1 is 0.01:1 to 0.4:1.
5. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on The graphene oxide concentration for stating the mixed solution of step 1 is 0.10 weight percent to 0.50 weight percent.
6. the preparation method of accordion graphene-carbon nano tube complex according to claim 1, which is characterized in that on Stating step 2 includes:
Pass through the mixed solution (step 2a) of second fluid nozzle spraying above-mentioned steps 1 in the form of aerosol droplets；And
Spraying above-mentioned droplet transfer is dried to heating furnace, and forms the accordion stone of self assembly by heat treatment Black alkene-Carbon Nanotube (step 2b).
7. the preparation method of accordion graphene-carbon nano tube complex according to claim 6, which is characterized in that on The diameter for stating the second fluid nozzle of step 2a is 1.0mm to 3.0mm.
8. the preparation method of accordion graphene-carbon nano tube complex according to claim 1 or 6, which is characterized in that The heat treatment of above-mentioned steps 2 or step 2b 200 DEG C to 500 DEG C at a temperature of carry out.
9. the preparation method of accordion graphene-carbon nano tube complex according to claim 1 or 6, which is characterized in that The heat treatment of above-mentioned steps 2 or step 2b carry out 1 hour to 10 hours.
10. a kind of accordion graphene-carbon nano tube complex, which is characterized in that
It is prepared by the preparation method of accordion graphene-carbon nano tube complex described in claim 1,
Above-mentioned accordion graphene-carbon nano tube complex includes:
Accordion graphene film；And
Carbon nanotube is included in inside above-mentioned graphene film,
Above-mentioned accordion graphene-carbon nano tube complex is spherical shape, and average particle size is 1 μm to 10 μm.
11. accordion graphene-carbon nano tube complex according to claim 10, which is characterized in that above-mentioned carbon nanometer Pipe is multi-walled carbon nanotube (MWCNT).
12. a kind of electrode of super capacitor, which is characterized in that include accordion graphene-carbon nanometer described in any one of claim 10 Tube complex.
13. a kind of supercapacitor, which is characterized in that
Include:
A pair of electrodes, it is mutually opposed, and include active material；
Electrolyte is set between above-mentioned a pair of electrodes；And
Seperation film is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit,
Above-mentioned active material includes accordion graphene-carbon nano tube complex described in any one of claim 10.
14. a kind of preparation method of accordion graphene-carbon nano tube-polymer composite characterized by comprising
Prepare the mixing for mixing the carbon nanotube through acid processing, graphene oxide, electroconductive polymer monomer and solvent Solution (step i)；
The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii)；And
It is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction and is heat-treated (step iii).
15. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that the carbon nanotube of above-mentioned steps i and the mixed weight ratio of graphene oxide are 0.01:1 to 0.5:1.
16. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that the monomer concentration of the mixed solution of above-mentioned steps i is 5mM to 50mM.
17. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is, the electroconductive polymer monomer of above-mentioned steps i be selected from by aniline, pyrroles, thiophene, acetylene, furans, phenylene and it Derivative composition one or more of group.
18. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that above-mentioned steps ii passes through the addition polymerization initiator into above-mentioned mixed solution and handles ultrasonic wave to carry out.
19. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 14, special Sign is that above-mentioned steps iii includes:
The above-mentioned mixed solution (step iiia) of polymerization reaction is sprayed through in the form of aerosol droplets by second fluid nozzle；And
Spraying above-mentioned droplet transfer is dried to heating furnace, and forms the accordion stone of self assembly by heat treatment Black alkene-carbon nanotube-polymer composite (step iiib).
20. the preparation method of accordion graphene-carbon nano tube-polymer composite according to claim 19, special Sign is that the diameter of the second fluid nozzle of above-mentioned steps iiia is 1.0mm to 3.0mm.
21. the graphene-carbon nano tube of accordion described in 4 or 19-polymer composite preparation method according to claim 1, It is characterized in that, the heat treatment of above-mentioned steps iii or step iiib are 1 hour to 10 small in 200 DEG C to 500 DEG C of at a temperature of progress When.
22. a kind of accordion graphene-carbon nano tube-polymer composite, which is characterized in that
It is prepared by accordion graphene-carbon nano tube-polymer composite preparation method described in claim 14,
Above-mentioned accordion graphene-carbon nano tube-polymer composite includes:
Accordion graphene film；
Carbon nanotube is included in inside above-mentioned graphene film；And
Electroconductive polymer,
Above-mentioned accordion graphene-carbon nano tube-polymer composite is spherical shape, and average particle size is 1 μm to 10 μm.
23. accordion graphene-carbon nano tube-polymer composite according to claim 22, which is characterized in that above-mentioned Electroconductive polymer is selected from by one in polyaniline, polypyrrole, polythiophene, polyacetylene, poly- furans and the poly- group formed to benzene Kind.
24. a kind of electrode of super capacitor, which is characterized in that include accordion graphene-carbon nanometer described in claim 22 Pipe-polymer composite.
25. a kind of supercapacitor, which is characterized in that
Include:
A pair of electrodes, it is mutually opposed, and include active material；
Electrolyte is set between above-mentioned a pair of electrodes；And
Seperation film is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit,
Above-mentioned active material includes accordion graphene-carbon nano tube-polymer composite described in claim 22.
26. a kind of preparation method of the electrode of super capacitor comprising accordion graphene complex characterized by comprising
Prepare the mixing for mixing the carbon nanotube through acid processing, graphene oxide, electroconductive polymer monomer and solvent Solution (step i)；
The monomer of above-mentioned mixed solution is set to carry out polymerization reaction (step ii)；
It is spray-dried the above-mentioned mixed solution Jing Guo polymerization reaction, and prepares accordion graphene complex by being heat-treated (step iii)；And
It mixes above-mentioned complex, graphene oxide and solvent and is heat-treated (step iv) after being coated on collector.
27. the preparation method of the electrode of super capacitor according to claim 26 comprising accordion graphene complex, It is characterized in that, above-mentioned complex: the mixed weight ratio of graphene oxide is 1:0.02 to 1:0.5 in above-mentioned steps iv.
28. the preparation method of the electrode of super capacitor according to claim 26 comprising accordion graphene complex, It is characterized in that, the heat treatment of above-mentioned steps iv be 200 DEG C to 500 DEG C at a temperature of carry out 1 hour to 10 hours.
29. a kind of electrode of super capacitor characterized by comprising
Accordion graphene-carbon nano tube-polymer composite, including accordion graphene film, be included in above-mentioned graphene film Internal carbon nanotube and electroconductive polymer, above-mentioned accordion graphene-carbon nano tube-polymer composite are spherical shape, And average particle size is 1 μm to 10 μm；
Collector is being formed with multiple above-mentioned complexs on one side；And
Graphene film, for fixing above-mentioned collector and complex, and for fixing above-mentioned complex and complex.
30. a kind of supercapacitor, which is characterized in that
Include:
A pair of electrodes, it is mutually opposed；
Electrolyte is set between above-mentioned a pair of electrodes；And
Seperation film is set between above-mentioned a pair of electrodes, for inhibiting electric short circuit,
Above-mentioned electrode is electrode of super capacitor described in claim 29.
CN201780076905.9A 2016-12-12 2017-03-29 Preparation method of corrugated graphene composite, composite prepared by preparation method and supercapacitor containing composite Active CN110073458B (en)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
KR1020160169022A KR101744122B1 (en) 2016-12-12 2016-12-12 Manufacturing method of crumpled graphene-carbon nanotube composite, crumpled graphene-carbon nanotube composite manufactured thereby and supercapacitor containing the composite
KR10-2016-0169022 2016-12-12
KR1020160174818A KR101742593B1 (en) 2016-12-20 2016-12-20 Manufacturing method of crumpled graphene-carbon nanotube-polymer composite, the composite manufactured thereby and supercapacitor containing the composite
KR10-2016-0174818 2016-12-20
KR1020170001353A KR101753129B1 (en) 2017-01-04 2017-01-04 Manufacturing method of supercapacitor electrode containing crumpled graphene composite, electrode manufactured thereby and supercapacitor containing the same
KR10-2017-0001353 2017-01-04
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