CN108269695B - A kind of supercapacitor graphene/carbon nano-tube electrode material and preparation method thereof - Google Patents
A kind of supercapacitor graphene/carbon nano-tube electrode material and preparation method thereof Download PDFInfo
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- CN108269695B CN108269695B CN201810102707.1A CN201810102707A CN108269695B CN 108269695 B CN108269695 B CN 108269695B CN 201810102707 A CN201810102707 A CN 201810102707A CN 108269695 B CN108269695 B CN 108269695B
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- 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
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of supercapacitor graphene/carbon nano-tube electrode materials and preparation method thereof.Three-dimensional porous material made of the electrode material is unmodified graphene and carbon nanotube is interweaved, composition is: 100 mass parts of graphene, 10~100 mass parts of carbon nanotube.Preparation method is: first with carboxylate dispersed graphite alkene and carbon nanotube containing condensed-nuclei aromatics, then regulate and control to realize graphene/carbon nano-tube dispersion liquid in the sol-gel transition of collection liquid surface, finally by freeze-drying in collection liquid surface in-situ preparation graphene/carbon nano-tube electrode material by pH.It is with high conductivity and bigger serface；And can be realized the seamless connection of electrode material and collector by the preparation method of the electrode material, greatly reduce the interface resistance between the two；The final high specific capacitance and excellent cyclical stability for realizing supercapacitor, the quality specific capacitance of double layer capacitor is up to 100~290F/g.
Description
Technical field
The invention belongs to supercapacitor fields, and in particular to a kind of supercapacitor graphene/carbon nano-tube electrode
Material and preparation method thereof.
Background technique
Supercapacitor is as a kind of new type of energy storage device, because of its high power density (500~10000W/kg), good
Good cycle life (> 500,000 times) and the charge-discharge velocity being exceedingly fast become most promising electrochemical energy storage technology
One of [J.Power Sources, 2000,91,37].However, the pole the lower energy density of supercapacitor (5~10Wh/kg)
The earth limits its application.The energy density of supercapacitor and the conductivity and specific surface area of its electrode material itself cease manner of breathing
Close [Nano.Lett., 2015,15,3198；Adv.Mater.,2014,26,2440.].Therefore, high-specific surface area, high electricity are developed
The electrode material of conductance is the research hotspot in supercapacitor field.
Graphene is by single layer of carbon atom with sp2The two-dimensional slice crystal structure that hybridized orbit rearranges, possesses excellent
Different conductivity (106) and huge specific surface area (2630m S/cm2/ g), mechanical property and chemical stability [Science,
2004,306,666].Compared to traditional supercapacitor carbon-based electrode material, such as: active carbon, carbon fiber, graphene because
Its high conductivity and huge specific surface area and show the application potential as new electrode materials.In theory,
If the conductivity and specific surface area of graphene can be efficiently used, the theoretical specific capacitance of graphene supercapacitor be can achieve
~550F/g.
The preparation method of supercapacitor Graphene electrodes material has following several at present: 1) bonding agent method: will restore
Graphene oxide or the graphene of liquid phase stripping method preparation are sticked to collection liquid surface as electrode material by bonding agent
[CN201210407636.9,CN101167204A,CN201610012476.6].Although this method is simple, in electrode system
During standby, it is easy to happen aggregation and stacking between graphene sheet layer, causes the specific surface area of Graphene electrodes and conductivity big
Width declines [Science, 2015,347,1246501].In addition, the use of a large amount of conductive agents, bonding agent increases electrode quality,
So that the specific capacitance of the Graphene electrodes material of this method preparation declines to a great extent.2) redox graphene gel method: with oxidation
Graphene is raw material, prepares redox graphene hydrogel by the methods of hydrothermal reduction, electronation, is then freeze-dried
Redox graphene aeroge is made, in this, as electrode material.Although this method maintains graphene to a certain extent
Specific surface area, but there are a large amount of defects in redox graphene structure, cause its conductivity well below graphene.This
Outside, in graphene oxide production and reduction process, a large amount of strong acid, strong oxidizing property reagent and toxic go back original reagent etc. are used,
Not only preparation process is complicated, and molding time is longer, structure it is uncontrollable [Phys.Chem.Chem.Phys., 2015,17,
30946].3) chemical vapour deposition technique: using carbonaceous gas as raw material, stone is prepared in metallic catalyst surfaces growth in situ graphene
Black alkene electrode material [CN201210051348.4, CN201410583167.5, CN201410061924.2].For example, QiJun Lei
Deng using chemical vapour deposition technique with metallic film catalyst silicon wafer on, first deposit one layer of carbon nanotube, redeposition one
Layer graphene, using this carbon nano tube/graphene film as electrode material [CN201410061924.2].Carbon nanotube/the graphite
Alkene thin-film electrode material causes its specific surface area lower due to a lack of porous structure, and carbon nanotube and graphene stepped depositions
The split-phase aggregated structure of formation causes its conductivity lower.It is prepared compared to metallic film catalyst, metallic foam catalyst
Grapheme foam electrode has three-dimensional porous structure, and the conductivity and specific surface area of grapheme foam electrode material are higher, surpasses
Grade capacitor shows higher specific capacitance and excellent cycle characteristics.But chemical vapour deposition technique production equipment is expensive, raw
Production. art is complicated, preparation cost is high, is unfavorable for industrialized production.So far, directly with unmodified graphene and carbon nanometer
Pipe is raw material, prepares the research of high conductivity and bigger serface Graphene electrodes material still by simple sol-gel method
Without report.
To sum up, using a kind of low cost, convenient and fast production method, the high conductivity and Large ratio surface of graphene are given full play to
Long-pending advantage is the key that prepare low cost, high specific capacitance graphene supercapacitor.With unmodified graphene and carbon nanometer
Pipe is raw material, and the Graphene electrodes material of high conductivity and bigger serface, Neng Goushi are prepared by simple sol-gel method
The preparation of existing low cost, high specific capacitance graphene supercapacitor.
Summary of the invention
In view of the foregoing, the purpose of the present invention is to provide a kind of graphene/carbon nano-tubes for supercapacitor
Electrode material and preparation method thereof.The electrode material is three-dimensional made of being interweaved as unmodified graphene and carbon nanotube
Porous material, composition is: 100 mass parts of graphene, 10~100 mass parts of carbon nanotube.The graphene/carbon nano-tube electrode
The preparation method of material is: first with carboxylate dispersed graphite alkene and carbon nanotube containing condensed-nuclei aromatics, then being regulated and controled by pH
Graphene/carbon nano-tube dispersion liquid is realized in the sol-gel transition of collection liquid surface, finally by freeze-drying in collector
Surface in situ generates three-dimensional porous graphene/carbon nano-tube electrode material.It solves conventional graphite alkene electrode material conductivity
With specific surface area is lower, preparation process is complicated and the problems such as production cost is high, will greatly push graphene super capacitor
The application and development of device.
In order to achieve the above objectives, graphene/carbon nano-tube electrode material of the invention, is received with unmodified graphene and carbon
Mitron is construction unit, using the excellent conductivity of the two and collaboration dispersing characteristic, regulates and controls sol-gel transition and cold by pH
Drying process is lyophilized to be made.
Graphene is the graphene that graphite method or liquid phase removing intercalated graphite method preparation are removed by liquid phase, i.e., organic molten
In agent, natural graphite or intercalated graphite are removed by ultrasonic treatment or high-speed stirred, take upper layer graphene point after centrifugation or standing
Dispersion liquid.Organic solvent is N,N-dimethylformamide, N-Methyl pyrrolidone or pyridine；The concentration of graphite is 5~100mg/ml；
Ultrasonic treatment condition is 40~500W/25~500kHz/20~60min；High-speed stirred condition be 3000~12000rpm/30~
120min；Centrifugal condition is 500~10000rpm/10~60min；Time of repose is 24~48h.
Carbon nanotube is that single-walled carbon nanotube, double-walled carbon nano-tube, multi-walled carbon nanotube or above two or three kinds of carbon are received
The mixture of mitron.
Graphene/carbon nano-tube electrode material is prepared using following steps:
1) graphene dispersing solution is added in carbon nanotube, graphene/carbon nano-tube is made in sonicated or high-speed stirred
Dispersion liquid obtains graphene/carbon nano-tube hybrid particle after suction filtration.The concentration of graphene is 1~10mg/ml, carbon nanotube
Concentration is 0.1~5mg/ml；Ultrasonic treatment condition is 40~500W/25~500kHz/1~60min；High-speed stirred condition is
500~10000rpm/1~60min.
2) graphene/carbon nano-tube hybrid particle is added in the carboxylate alkaline aqueous solution containing condensed-nuclei aromatics, through super
Graphene/carbon nano-tube aqueous dispersions are made in sonication or high-speed stirred.Carboxylate containing condensed-nuclei aromatics is salt containing naphthalene-carboxylic acid, contains
Anthracene carboxylic acid's salt, salt containing phenanthrene carboxylic acid, carboxylate containing pyrene or carboxylate-containing；The concentration of graphene/carbon nano-tube is 2~15mg/ml,
Carboxylate salt concentration containing condensed-nuclei aromatics is 1~5mg/ml；Alkaline aqueous solution be the pH that sodium hydroxide or potassium hydroxide are adjusted be 8~
12 aqueous solution；Ultrasonic treatment condition is 40~500W/25~500kHz/1~60min；High-speed stirred condition be 500~
10000rpm/1~60min.
3) graphene/carbon nano-tube aqueous dispersions are coated in collection liquid surface, hydrochloric acid solution is added and adjusts pH value to acid
Property 2~4, after collection liquid surface in-situ preparation graphene/carbon nano-tube hydrogel, freeze forming, be freeze-dried be made load
In the graphene/carbon nano-tube electrode material of collection liquid surface.Collector is nickel foam, foam copper, stainless (steel) wire, aluminium flake, gold
Piece or silver strip；Freeze forming condition be -196~-5 DEG C/0.5~for 24 hours；Freeze-drying condition be -40~-80 DEG C/1.3~
13Pa/12~48h.
Compared with prior art, the invention has the following advantages: graphene used in (1) and carbon nanotube do not pass through
It crosses and is modified, structural integrity can assign electrode material more excellent conductivity；(2) graphene and carbon nanotube need not be modified,
Technique simplification, environmental pollution reduction, preparation efficiency improves, cost reduces；(3) sol-gel transition and freezing are regulated and controled by pH
Drying process is in the three-dimensional porous graphene/carbon nano-tube electrode material of collection liquid surface in-situ preparation, and not only preparation process is simple,
And seamless connection between graphene/carbon nano-tube electrode material and collector, interface resistance can greatly be reduced；(4) stone
Black alkene and carbon nanotube collaboration dispersion, can be avoided respective aggregation, it is uniform to guarantee that graphene/carbon nano-tube electrode material has
Three-dimensional porous structure and higher specific surface area；(5) electrode material is securely fixed in collection liquid surface, ensure that capacitor
Stability.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of graphene prepared by comparative example 2 and embodiment 1.
Fig. 2 is graphene in embodiment 1/single-walled carbon nanotube electrode material scanning electron microscopic picture.
Fig. 3 is the cyclic voltammetry curve of supercapacitor in embodiment 1.
Fig. 4 is the constant current charge-discharge curve of supercapacitor in embodiment 1.
Specific embodiment
With reference to the accompanying drawing and by specific embodiment come present invention be described in more detail.It should be understood that following embodiments
It is to limit its protection scope for illustrating rather than.
Comparative example 1:
Single-walled carbon nanotube electrode material, the electrode material are prepared using following steps:
1) single-walled carbon nanotube (the organic institute TNSAR in Chengdu) is added in the alkaline aqueous solution of 1- pyrene sodium formate, through super
Single-walled carbon nanotube aqueous dispersions are made in sonication.The concentration of single-walled carbon nanotube is 5mg/ml, and the concentration of 1- pyrene sodium formate is
2mg/ml, alkaline aqueous solution are the aqueous solution for the pH=9 that sodium hydroxide is adjusted, and ultrasonic treatment condition is 200W/250kHz/
30min。
2) single-walled carbon nanotube aqueous dispersions are coated in foam nickel surface, hydrochloric acid solution is added and adjusts pH=3, in foam
Nickel surface in-situ preparation single-walled carbon nanotube hydrogel, after freeze forming, the list for being carried on foam nickel surface is made in freeze-drying
Wall carbon nano tube electrode material.Freeze forming condition is -30 DEG C/12h, and freeze-drying condition is -55 DEG C/7.8Pa/24h.
The conductivity of single-walled carbon nanotube electrode material is 96S/cm, specific surface area 1063m2/g.With single
Pipe electrode material is assembled into double electric layers supercapacitor using 6M KOH aqueous solution as electrolyte for electrode, measures it in 1A/g electricity
Specific capacitance when current density is 70F/g.
Comparative example 2:
Graphene electrodes material, the electrode material are prepared using following steps:
1) in n,N-Dimethylformamide, natural graphite is removed by ultrasonic treatment, upper layer graphene point is taken after centrifugation
Dispersion liquid obtains graphene after suction filtration.The concentration of natural graphite is 50mg/ml；Ultrasonic treatment condition is 200W/250kHz/
30min, centrifugal condition 4500rpm/30min.Fig. 1 is the transmission electron microscope photo of graphene.It is from photo as can be seen that made
Standby graphene is relatively thin, and size is at 2~4 μm.
2) graphene is added in 1- pyrene sodium formate alkaline aqueous solution, sonicated obtained graphene aqueous dispersions.
The concentration of graphene is 5mg/ml, and the concentration of 1- pyrene sodium formate is 2mg/ml, and alkaline aqueous solution is the pH=9 that sodium hydroxide is adjusted
Aqueous solution, ultrasonic treatment condition be 200W/250kHz/30min.
3) graphene aqueous dispersions are coated in foam nickel surface, hydrochloric acid solution is added and adjusts pH value to acidity 3, in foam
Nickel surface in-situ preparation graphene hydrogel, after freeze forming, the graphene electricity for being carried on foam nickel surface is made in freeze-drying
Pole material.Freeze forming condition is -30 DEG C/12h, and freeze-drying condition is -55 DEG C/7.8Pa/24h.
The conductivity of Graphene electrodes material is 127S/cm, specific surface area 987m2/g.It is with Graphene electrodes material
Electrode is assembled into double electric layers supercapacitor using 6M KOH aqueous solution as electrolyte, measures its ratio in 1A/g current density
Capacitor is 120F/g.
Embodiment 1:
A kind of supercapacitor graphene/carbon nano-tube electrode material, the electrode material are by graphene and carbon nanometer
Three-dimensional porous material made of pipe is interweaved, composition is 100 mass parts of graphene, single-walled carbon nanotube (the organic institute in Chengdu
TNSAR) 100 mass parts.The nanocomposite is prepared using following steps:
1) in n,N-Dimethylformamide, natural graphite is removed by ultrasonic treatment, upper layer graphene point is taken after centrifugation
Dispersion liquid.The concentration of natural graphite is 50mg/ml, and ultrasonic treatment condition is 200W/250kHz/30min, and centrifugal condition is
4500rpm/30min。
2) graphene dispersing solution, sonicated obtained graphene/single-walled carbon nanotube point is added in single-walled carbon nanotube
Dispersion liquid obtains graphene/single-walled carbon nanotube hybrid particle after suction filtration.The concentration of graphene is 2.5mg/ml, carbon nanotube
Concentration is 2.5mg/ml, and ultrasonic treatment condition is 200W/250kHz/30min.
3) graphene/single-walled carbon nanotube hybrid particle is added in 1- pyrene sodium formate alkaline aqueous solution, at ultrasound
It manages and graphene/single-walled carbon nanotube aqueous dispersions is made.Graphene/single-walled carbon nanotube concentration is 5mg/ml, 1- pyrene formic acid
The concentration of sodium is 2mg/ml, and alkaline aqueous solution is the aqueous solution for the pH=9 that sodium hydroxide is adjusted, and ultrasonic treatment condition is 200W/
250kHz/30min。
4) graphene/single-walled carbon nanotube aqueous dispersions are coated in foam nickel surface, hydrochloric acid solution is added and adjusts pH=
3, after nickel foam surface in situ generation graphene/single-walled carbon nanotube hydrogel, freeze forming, freeze-drying is made and is carried on
The graphene of foam nickel surface/single-walled carbon nanotube electrode material.Freeze forming condition is -30 DEG C/12h, is freeze-dried condition
For -55 DEG C/7.8Pa/24h.Fig. 2 is graphene/single-walled carbon nanotube electrode material stereoscan photograph.It can be with from photo
Find out, graphene/single-walled carbon nanotube electrode material is in three-dimensional porous structure, phase interconnection between graphene and single-walled carbon nanotube
It connects to form dual network.
Graphene/single-walled carbon nanotube electrode material conductivity is 153S/cm, specific surface area 1517m2/g.With stone
Black alkene/single-walled carbon nanotube electrode material is assembled into electric double layer super capacitor using 6M KOH aqueous solution as electrolyte for electrode
Device.Fig. 3 is the cyclic voltammetry curve of supercapacitor.It can be seen from the figure that being followed under the scanning speed of 10~1000mv/s
Ring volt-ampere curve shows good rectangular shape, illustrates that supercapacitor possesses excellent double layer characteristic.Fig. 4 is super electricity
The constant current charge-discharge curve of container, calculate specific capacitance of the supercapacitor in 1A/g current density be 290F/g, present
Biggish quality specific capacitance.Compared with comparative example 1 and comparative example 2, the collaboration of graphene and carbon nanotube is used, and can be increased
The conductivity and specific surface area of electrode material, to obtain higher specific capacitance.
Embodiment 2:
A kind of supercapacitor graphene/carbon nano-tube electrode material, the electrode material are by graphene and carbon nanometer
Three-dimensional porous material made of pipe is interweaved, composition is 100 mass parts of graphene, single-walled carbon nanotube (the organic institute in Chengdu
TNSAR) 25 mass parts, multi-walled carbon nanotube (the organic institute TNGM2 in Chengdu) 25 mass parts.The nanocomposite uses and implementation
The similar step preparation of example 1, difference is:
Using pyridine as solvent in step 1, using intercalated graphite as raw material, ultrasonic removing prepares graphene dispersing solution.Intercalation stone
The concentration of ink is 5mg/ml, and ultrasonic treatment condition is 40W/25kHz/60min, centrifugal condition 10000rpm/10min.
The concentration of graphene is 10mg/ml in step 2, and the concentration of single-walled carbon nanotube is 2.5mg/ml, multi-wall carbon nano-tube
The concentration of pipe is 2.5mg/ml, and ultrasonic treatment condition is 40W/25kHz/60min.
Using 2- naphthoxy acetic acid sodium as dispersing aid in step 3.The concentration of graphene/carbon nano-tube is 15mg/ml, 2- naphthalene
The concentration of ethoxyacetic acid sodium is 5mg/ml, and alkaline aqueous solution is the aqueous solution for the pH=12 that sodium hydroxide is adjusted, and is ultrasonically treated item
Part is 40W/25kHz/60min.
Using foam copper as collector in step 4, hydrochloric acid solution is added and adjusts pH=2.Freeze forming condition is -196 DEG C of (liquid
Nitrogen)/0.5h, freeze-drying condition is -80 DEG C/13Pa/12h.
The conductivity of graphene/carbon nano-tube electrode material is 135S/cm, specific surface area 1275m2/g.With graphene/
Carbon nanotube electrode material is that electrode using 6M KOH aqueous solution as electrolyte is assembled into double electric layers supercapacitor, measure its
Specific capacitance when 1A/g current density is 270F/g, and has excellent double layer characteristic and cycle characteristics.
Embodiment 3:
A kind of supercapacitor graphene/carbon nano-tube electrode material, the electrode material are by graphene and carbon nanometer
Three-dimensional porous material made of pipe is interweaved, composition is 100 mass parts of graphene, double-walled carbon nano-tube (the organic institute in Chengdu
TND) 10 mass parts.The nanocomposite is prepared using step similar to Example 1, and difference is:
Using N-Methyl pyrrolidone as solvent in step 1, ultrasound removing preparing graphite alkene dispersion liquid.The concentration of graphite
For 100mg/ml, ultrasonic treatment condition is 500W/500kHz/20min, centrifugal condition 500rpm/60min.
The concentration of graphene is 1mg/ml in step 2, and the concentration of double-walled carbon nano-tube is 0.1mg/ml, is ultrasonically treated condition
For 500W/500kHz/1min.
Using 1- pyrene sodium butyrate as dispersing aid in step 3.Graphene/double-walled carbon nano-tube concentration is 2mg/ml, 1- pyrene
The concentration of sodium butyrate is 1mg/ml, and alkaline aqueous solution is the aqueous solution for the pH=8 that potassium hydroxide is adjusted, and ultrasonic treatment condition is
500W/500kHz/1min。
Using aluminium flake as collector in step 4, hydrochloric acid solution is added and adjusts pH=4.Freeze forming condition be -5 DEG C/for 24 hours, it is cold
Jelly drying condition is -40 DEG C/1.3Pa/48h.
Graphene/double-walled carbon nano-tube electrode material conductivity is 82S/cm, specific surface area 1093m2/g.With graphite
Alkene/carbon nanotube electrode material is assembled into double electric layers supercapacitor using 6M KOH aqueous solution as electrolyte for electrode, measures
Its specific capacitance in 1A/g current density is 107F/g, and has excellent double layer characteristic and cycle characteristics.
Embodiment 4:
A kind of supercapacitor graphene/carbon nano-tube electrode material, the electrode material are by graphene and carbon nanometer
Three-dimensional porous material made of pipe is interweaved, composition is 100 mass parts of graphene, single-walled carbon nanotube (the organic institute in Chengdu
TNSAR) 25 mass parts.The nanocomposite is prepared using step similar to Example 1, and difference is:
Graphene dispersing solution is prepared using high-speed stirred intercalated graphite in step 1.The concentration of intercalated graphite is 80mg/ml,
High-speed stirred condition is 4500rpm/60min, time of repose 36h.
High-speed stirred admixed graphite alkene and single-walled carbon nanotube are used in step 2.The concentration of graphene is 4mg/ml, single wall
The concentration of carbon nanotube is 1mg/ml, and high-speed stirred condition is 3000rpm/30min.
Using 9- anthroic acid sodium as dispersing aid in step 3, graphene/single-walled carbon nanotube moisture is prepared using high-speed stirred
Dispersion liquid.Graphene/single-walled carbon nanotube concentration is 2mg/ml, and the concentration of 9- anthroic acid sodium is 2mg/ml, high-speed stirred condition
For 10000rpm/1min.
Using gold plaque as collector in step 4.
Graphene/single-walled carbon nanotube electrode material conductivity is 129S/cm, specific surface area 1367m2/g.With stone
Black alkene/single carbon nanotube electrode material is assembled into double electric layers supercapacitor using 6M KOH aqueous solution as electrolyte for electrode,
Measuring its specific capacitance in 1A/g current density is 263F/g, and has excellent double layer characteristic and cycle characteristics.
Embodiment 5:
A kind of supercapacitor graphene/carbon nano-tube electrode material, the electrode material are by graphene and carbon nanometer
Three-dimensional porous material made of pipe is interweaved, composition is 100 mass parts of graphene, single-walled carbon nanotube (the organic institute in Chengdu
TNSAR) 20 mass parts, double-walled carbon nano-tube (the organic institute TND in Chengdu) 20 mass parts.The nanocomposite uses and embodiment
1 similar step preparation, difference is:
Graphene dispersing solution is prepared using high-speed stirred natural graphite in step 1.High-speed stirred condition is 3000rpm/
120min, time of repose are for 24 hours.
High-speed stirred admixed graphite alkene, single-walled carbon nanotube and double-walled carbon nano-tube are used in step 2.The concentration of graphene
For 4mg/ml, the concentration of single-walled carbon nanotube is 0.8mg/ml, and the concentration of double-walled carbon nano-tube is 0.8mg/ml, high-speed stirred item
Part is 500rpm/60min.
Using 4- phenanthrene carboxylic acid sodium as dispersing aid in step 3, graphene/single-walled carbon nanotube/bis- is prepared using high-speed stirred
Wall carbon nano tube aqueous dispersions.The concentration of graphene/carbon nano-tube is 10mg/ml, and the concentration of 4- phenanthrene carboxylic acid sodium is 3mg/ml, high
Fast stirring condition is 500rpm/60min.
Using stainless (steel) wire as collector in step 4.
The conductivity of graphene/carbon nano-tube electrode material is 117S/cm, specific surface area 1120m2/g.With graphene/
Single carbon nanotube electrode material is assembled into double electric layers supercapacitor using 6M KOH aqueous solution as electrolyte for electrode, measures it
Specific capacitance in 1A/g current density is 195F/g, and has excellent double layer characteristic and cycle characteristics.
Embodiment 6:
A kind of supercapacitor graphene/carbon nano-tube electrode material, the electrode material are by graphene and carbon nanometer
Three-dimensional porous material made of pipe is interweaved, composition is 100 mass parts of graphene, multi-walled carbon nanotube (the organic institute in Chengdu
TNGM2) 80 mass parts.The nanocomposite is prepared using step similar to Example 1, and difference is:
Graphene dispersing solution is prepared using high-speed stirred natural graphite in step 1.High-speed stirred condition is 12000rpm/
30min, time of repose 48h.
High-speed stirred admixed graphite alkene and multi-walled carbon nanotube are used in step 2.The concentration of graphene is 5mg/ml, multi wall
The concentration of carbon nanotube is 4mg/ml, and high-speed stirred condition is 10000rpm/1min.
Using 4- tetrabasic carboxylic acid sodium as dispersing aid in step 3, graphene/multi-walled carbon nanotube water is prepared using high-speed stirred
Dispersion liquid.Graphene/multi-walled carbon nanotube concentration is 9mg/ml, and the concentration of 4- tetrabasic carboxylic acid sodium is 3mg/ml, high-speed stirred
Condition is 3000rpm/30min.
Using silver strip as collector in step 4.
The conductivity of graphene/carbon nano-tube electrode material is 125S/cm, specific surface area 1350m2/g.With graphene/
Single carbon nanotube electrode material is assembled into double electric layers supercapacitor using 6M KOH aqueous solution as electrolyte for electrode, measures it
Specific capacitance in 1A/g current density is 236F/g, and has excellent double layer characteristic and cycle characteristics.
The above embodiments merely illustrate the technical concept and features of the present invention, and protection model of the invention can not be limited with this
It encloses.It is all any equivalent transformation or modification made according to the spirit of the present invention, should be covered by the scope of protection of the present invention.
Claims (1)
1. a kind of preparation method of graphene/carbon nano-tube electrode material, which is characterized in that including following preparation step:
(1) graphene dispersing solution: in organic solvent, natural graphite or intercalation stone are removed by ultrasonic treatment or high-speed stirred
Upper layer graphene dispersing solution is taken after ink, centrifugation or standing, organic solvent used is n,N-Dimethylformamide, N- crassitude
Ketone or pyridine；The concentration of graphite is 5~100mg/ml；Ultrasonic treatment condition is 40~500W/25~500kHz/20~60min；
High-speed stirred condition is 3000~12000rpm/30~120min；Centrifugal condition is 500~10000rpm/10~60min；It is quiet
Setting the time is 24~48h；
(2) graphene dispersing solution, sonicated or high-speed stirring graphene/carbon nano-tube hybrid particle: is added in carbon nanotube
Mixing obtains graphene/carbon nano-tube dispersion liquid, and graphene/carbon nano-tube hybrid particle is obtained after suction filtration, graphene used
Concentration is 1~10mg/ml, and the concentration of carbon nanotube is 0.1~5mg/ml；Ultrasonic treatment condition be 40~500W/25~
500kHz/1~60min；High-speed stirred condition is 500~10000rpm/1~60min；
(3) graphene/carbon nano-tube hybrid particle graphene/carbon nano-tube aqueous dispersions: is added to the carboxylic containing condensed-nuclei aromatics
In hydrochlorate alkaline aqueous solution, graphene/carbon nano-tube aqueous dispersions are made in sonicated or high-speed stirred, and used contains condensed ring
The carboxylate of aromatic hydrocarbons is salt containing naphthalene-carboxylic acid, salt containing anthracene carboxylic acid, salt containing phenanthrene carboxylic acid, carboxylate containing pyrene or carboxylate-containing；Used
The concentration of graphene/carbon nano-tube hybrid particle is 2~15mg/ml, and the carboxylate salt concentration containing condensed-nuclei aromatics is 1~5mg/ml；
Alkaline aqueous solution is the aqueous solution that the pH that sodium hydroxide or potassium hydroxide are adjusted is 8~12；Ultrasonic treatment condition is 40~500W/
25~500kHz/1~60min；High-speed stirred condition is 500~10000rpm/1~60min；
(4) graphene/carbon nano-tube electrode material: graphene/carbon nano-tube aqueous dispersions are coated in collection liquid surface, are added
Hydrochloric acid solution adjusts pH value to acidity 2~4, in collection liquid surface in-situ preparation graphene/carbon nano-tube hydrogel, freeze forming
Afterwards, the graphene/carbon nano-tube electrode material for being carried on collection liquid surface is made in freeze-drying, and collector used is foam
Nickel, foam copper, stainless (steel) wire, aluminium flake, gold plaque or silver strip；Freeze forming condition be -196~-5 DEG C/0.5~for 24 hours；Freeze-drying
Condition is -40~-80 DEG C/1.3~13Pa/12~48h；
The electrode material is three-dimensional porous material made of being interweaved as unmodified graphene and carbon nanotube, composition
It is: 100 mass parts of graphene, 10~100 mass parts of carbon nanotube.
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