CN107221447A - A kind of graphene flexible compound electrode, its preparation method and flexible super capacitor - Google Patents
A kind of graphene flexible compound electrode, its preparation method and flexible super capacitor Download PDFInfo
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- CN107221447A CN107221447A CN201710533489.2A CN201710533489A CN107221447A CN 107221447 A CN107221447 A CN 107221447A CN 201710533489 A CN201710533489 A CN 201710533489A CN 107221447 A CN107221447 A CN 107221447A
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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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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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
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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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 provides a kind of graphene flexible compound electrode, its preparation method and flexible super capacitor.The graphene flexible compound electrode that the present invention is provided includes：Dimethyl silicone polymer substrate, three-dimensional grapheme collector and electrode active material；A part for the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part loads the electrode active material.The flexible compound electrode that the present invention is provided can make the specific capacity of flexible super capacitor and flexible miniature ultracapacitor respectively up to 0.5~1F/cm2With 30~50mF/cm2, and capability retention is higher than 80% after alternating bending is folded 5000 and 2000 times respectively.
Description
Technical field
The present invention relates to supercapacitor technologies field, more particularly to a kind of graphene flexible compound electrode, its preparation side
Method and flexible super capacitor.
Background technology
With developing rapidly for scientific and technical progress, industrialization and informationization, the electronic product such as computer, mobile phone
Turn into the necessity in life, and these electronic products progressively stride forward to portability, transformation from such as desktop computer to notebook；And
For the electronic equipment of portability, its energy-storage system needs just make electronic equipment depart from fixed electricity with good power supply performance
The constraint in source, as the movable fixture for being capable of convenient use.Up to now, ultracapacitor is due to high power capacity, Gao Gong
The advantages of rate density, high charge-discharge speed and as the energy storage device being most widely used in mobile electronic device.
Traditional ultracapacitor mainly includes both positive and negative polarity, barrier film and electrolyte, and its planform is relatively simple.In recent years
Come, with portable and wearable electronic development, the research of flexible super capacitor becomes focus.Flexible capacitor
Mainly it is made up of substrate, electrode and electrolyte；Different from conventional Super capacitor, in flexible super capacitor, substrate, electricity
Pole and electrolyte are flexible, can assign capacitor miscellaneous shape, can provide the form more enriched and work(
Can, it more disclosure satisfy that the growth requirement of electronic equipment.
Flexible electrode directly determines the performance of capacitor as the core component of flexible super capacitor, in case of bending
Under, the positive and negative electrode of capacitor is in compression and tensile stress state, and bends repeatedly and easily cause electrode structure destruction, such as electricity
The disengaging etc. even from flexible substrates of pole material cracks, causes the hydraulic performance decline of energy storage device.At present, three-dimensional grapheme is due to excellent
The features such as different electric conductivity, big specific surface area and be widely used as flexible current-collecting body applied in flexible electrode, on the one hand, three
Dimension graphene pore structure can improve the contact area of collector and electrode active material, on the other hand, its continuous three dimensional network
Network structure can also reduce stress suffered during electrode material is bent, and reduce above-mentioned electrode material and ftracture and the wind that comes off
Danger.But, using the electrode of three-dimensional grapheme, the defects such as Resisting fractre ability are there is, the stability of capacitor is influenceed.
Therefore, how to obtain while the flexible electrode with excellent chemical property and mechanical property still suffers from no small choose
War.
The content of the invention
In view of this, it is an object of the invention to provide a kind of graphene flexible compound electrode, its preparation method and flexibility
Ultracapacitor.Graphene flexible compound electrode that the present invention is provided is while have excellent chemical property and mechanical property.
The invention provides a kind of graphene flexible compound electrode, including：Dimethyl silicone polymer substrate, three-dimensional grapheme
Collector and electrode active material；
A part for the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part is born
Carry the electrode active material.
It is preferred that, the electrode active material is polyaniline.
It is preferred that, load capacity of the electrode active material on three-dimensional grapheme collector is 1~3mg/cm2；
The thickness filled in the dimethyl silicone polymer substrate by three-dimensional grapheme collector is less than polydimethylsiloxanes
The gross thickness at alkyl bottom.
It is preferred that, the three-dimensional grapheme collector includes interdigitated collector.
Present invention also offers a kind of preparation method of the graphene flexible compound electrode described in above-mentioned technical proposal, including
Following steps：
A) using foam metal piece as template, deposition three-dimensional graphite is grown in the template using chemical vapour deposition technique
Alkene, three-dimensional grapheme collector is obtained after removing the foam metal piece through chemical etching；
B) dimethyl silicone polymer glue body is coated with polydimethylsiloxanefilm film surface, by three-dimensional grapheme collector
A part is placed in the colloid, is heating and curing, and forms integral type substrate-collector；
C) electrochemical deposition method is utilized to deposit electricity on the three-dimensional grapheme collector in the integral type substrate-collector
Pole active material, obtains graphene flexible compound electrode.
It is preferred that, the three-dimensional grapheme collector includes interdigitated collector；
The interdigitated collector is obtained in the following manner：
A1) using foam metal piece as template, deposition three-dimensional graphite is grown in the template using chemical vapour deposition technique
Alkene, three-dimensional grapheme collector is obtained after removing the foam metal piece through chemical etching；
A2 photoetching) is carried out to the three-dimensional grapheme collector using laser beam, interdigitated collector is obtained.
It is preferred that, the foam metal piece is foam nickel sheet, foam copper sheet or foam iron plate；
The chemical vapour deposition technique is using hydrogen and methane as reacting gas.
It is preferred that, the polydimethylsiloxanefilm film is obtained in the following manner：
Dimethyl silicone polymer is mixed with curing agent and substrate surface is coated on, heated solidification, in the substrate table
Face forms polydimethylsiloxanefilm film；
The mass ratio of the dimethyl silicone polymer and curing agent is 10: 1；
The step c) includes：
Using the integral type substrate-collector as working electrode, platinized platinum be to electrode, Ag-AgCl is reference electrode, with containing
The aqueous solution for having aniline and sulfuric acid is electrolyte, carries out electrochemical deposition, the three-dimensional grapheme in integral type substrate-collector
Deposition forms polyaniline electrode active material on collector, obtains graphene flexible compound electrode.
Present invention also offers a kind of flexible super capacitor, including the graphene flexible compound described in above-mentioned technical proposal
Graphene flexible compound electrode made from preparation method described in electrode or above-mentioned technical proposal.
It is preferred that, the flexible super capacitor includes flexible miniature ultracapacitor and flexible non-miniature ultracapacitor
Device；
The flexible non-micro super capacitor is sandwich structure；The flexible miniature ultracapacitor includes the fork
Finger-like collector；
Electrolyte in the flexible super capacitor is PVA-H2SO4Gel electrolyte.
The invention provides a kind of graphene flexible compound electrode, including：Dimethyl silicone polymer substrate, three-dimensional grapheme
Collector and electrode active material；A part for the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate
In, another part loads the electrode active material.The flexible compound electrode that the present invention is provided not only has good electrochemistry
Performance, also with good mechanical property, is conducive to improving the stability of energy storage device.Present invention also offers above-mentioned stone
The preparation method of black alkene flexible compound electrode, its preparation process is simple and easy to apply, can carry out large-scale production.The present invention is also provided
A kind of to include the flexible super capacitor of above-mentioned graphene flexible compound electrode, the performance of the supercapacitor is stable.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
The structural representation for the graphene flexible compound electrode that Fig. 1 provides for one embodiment of the present of invention；
The structural representation for the graphene flexible compound electrode that Fig. 2 provides for an alternative embodiment of the invention；
Fig. 3 is the SEM test charts for the graphene flexible compound electrode that the embodiment of the present invention 1 is provided；
Fig. 4 bends operation chart in being tested for flexible compound electrode bending in the embodiment of the present invention.
Embodiment
The invention provides a kind of graphene flexible compound electrode, including：Dimethyl silicone polymer substrate, three-dimensional grapheme
Collector and electrode active material；
A part for the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part is born
Carry the electrode active material.
Referring to Fig. 1, the structural representation for the graphene flexible compound electrode that Fig. 1 provides for one embodiment of the present of invention,
Wherein, 1 is dimethyl silicone polymer (i.e. PDMS) substrate；2 and 3 be three-dimensional grapheme collector, and 2 are coated by PDMS substrates
Three-dimensional grapheme, 3 be uncoated three-dimensional grapheme；4 be the electrode active material for being carried on three-dimensional grapheme.
Substrate 1 is dimethyl silicone polymer substrate, and it can provide good deformation stability.
A part for three-dimensional grapheme collector is filled in substrate 1, i.e., the three-dimensional grapheme 2 coated by substrate, will
PDMS substrates are combined with three-dimensional grapheme part, are conducive to improving the stretching, bending and crimp property of overall combination electrode.This hair
In bright, preferably, the thickness filled in dimethyl silicone polymer substrate by three-dimensional grapheme collector is less than poly dimethyl silicon
The gross thickness at oxyalkyl bottom.
Another part of three-dimensional grapheme collector be the uncoated load electrode active material of three-dimensional grapheme 3 there is provided
Good chemical property.
In some embodiments of the invention, three-dimensional grapheme collector is interdigitated collector, i.e., by three-dimensional grapheme
Film is processed into interdigitated morphosis；Referring to Fig. 2, Fig. 2 is multiple for the graphene flexibility that an alternative embodiment of the invention is provided
The structural representation of composite electrode, wherein, 1 is dimethyl silicone polymer (i.e. PDMS) substrate；2 and 3 be the three-dimensional graphite of interdigitated
Alkene collector, 2 three-dimensional grapheme to be coated by PDMS substrates, 3 be uncoated three-dimensional grapheme；Electrode active is loaded with 3
Property material.
Interdigited electrode material refers to the class electrode material for having periodic patterns in the face such as finger-like or pectination.At present,
Interdigited electrode is often using the metal collector such as gold, mainly by means such as metal evaporation, wet method photoetching by metal collector
Substrate surface is plated in, however, its preparation process is complicated, cost high, electrochemistry and mechanical property be not good enough, and easily comes off.This hair
Bright use interdigitated three-dimensional grapheme collector inlays combination with substrate, using the teaching of the invention it is possible to provide good electric conductivity and mechanical property,
And cost is low.
In the present invention, the electrode active material 4 is preferably polyaniline.
In the present invention, load capacity of the electrode active material on three-dimensional grapheme collector is preferably 1~3mg/
cm2, more preferably 1~2mg/cm2。
The flexible compound electrode that the present invention is provided includes dimethyl silicone polymer substrate, three-dimensional grapheme collector and electrode
Active material, wherein, dimethyl silicone polymer substrate covered section three-dimensional grapheme collector, in three-dimensional grapheme collector not
The fractional load electrode active material coated by substrate；Gained flexible compound electrode not only has good chemical property, also
With good mechanical property, be conducive to improving the stability of energy storage device.Test result indicates that, it is soft that the present invention is provided
Property combination electrode can make the specific capacity of flexible super capacitor and flexible miniature ultracapacitor respectively up to 0.5~1F/cm2
With 30~50mF/cm2, and capability retention is higher than 80% after alternating bending is folded 5000 and 2000 times respectively.
Present invention also offers the preparation method of graphene flexible compound electrode described in above-mentioned technical proposal, including following step
Suddenly：
A) using foam metal piece as template, deposition three-dimensional graphite is grown in the template using chemical vapour deposition technique
Alkene, three-dimensional grapheme collector is obtained after removing the foam metal piece through chemical etching；
B) dimethyl silicone polymer glue body is coated with polydimethylsiloxanefilm film surface, by three-dimensional grapheme collector
A part is placed in the colloid, is heating and curing, and forms integral type substrate-collector；
C) electrochemical deposition method is utilized to deposit electricity on the three-dimensional grapheme collector in the integral type substrate-collector
Pole active material, obtains graphene flexible compound electrode.
According to the present invention, using foam metal piece as template, deposition is grown in the template using chemical vapour deposition technique
Three-dimensional grapheme, three-dimensional grapheme collector is obtained after removing the foam metal piece through chemical etching.
In the present invention, the foam metal piece can be nickel foam piece, foam copper sheet or foam iron plate, preferably nickel foam
Piece.In the present invention, in the chemical vapour deposition technique, preferably chemical vapor deposition is carried out using hydrogen and methane as reacting gas；
Wherein, the volume ratio of hydrogen and methane is preferably 10: 1.In the present invention, the reaction temperature of the chemical vapour deposition technique is preferably
900~1100 DEG C, the reaction time is preferably 30min.In the present invention, after chemical vapor deposition has been carried out, preferably pass through chemistry
The sheet metal template that defoams is etched, then is cleaned and is dried, so as to obtain three-dimensional grapheme collector.
In certain embodiments, three-dimensional grapheme collector can be prepared as follows：Foam nickel sheet is put
In tube furnace, logical hydrogen 180sccm is simultaneously warming up to 1000 DEG C, is then passed through methane 18sccm and continues 30min；Then pass through
Body of heater is removed and cooled down at room temperature by slide rail.The foam nickel sheet that grown three-dimensional grapheme is placed in FeCl3With HCl mixed liquor
In, defoamed nickel sheet in etching at 80 DEG C, then through ultra-pure water, ethanol clean and dry successively, obtain three-dimensional grapheme thin
Film collector.
In some embodiments of the invention, three-dimensional grapheme collector is interdigitated morphosis, as interdigitated collection
Fluid；The interdigitated collector can be obtained in the following manner：Using foam metal piece as template, chemical vapor deposition is utilized
Method grows deposition three-dimensional graphene in the template, obtains three-dimensional grapheme film current collector；Using laser beam to described three
Tie up graphene film collector and carry out photoetching, obtain interdigitated collector.Wherein, chemical vapour deposition technique growth deposition three is utilized
The process for tieing up graphene is consistent with above-mentioned technical proposal, repeats no more.After three-dimensional grapheme film current collector is obtained, using swash
Light beam carries out photoetching to gained three-dimensional grapheme collector, forms interdigitated morphosis, obtains interdigitated collector.At some
In specific embodiment, the wavelength of the laser beam is 532nm, and the spot diameter of the laser beam is 10 μm；The laser beam
Photoetching power is 0.5W.
According to the present invention, obtain after collector, dimethyl silicone polymer glue is coated with polydimethylsiloxanefilm film surface
Body, a part for three-dimensional grapheme collector is placed in the colloid, is heating and curing, and forms integral type substrate-collector.
In the present invention, the polydimethylsiloxanefilm film is preferably obtained in the following manner：By dimethyl silicone polymer
Mixed with curing agent and be coated on substrate surface, heated solidification, in substrate surface formation polydimethylsiloxanefilm film.
In the present invention, the mass ratio of the dimethyl silicone polymer and curing agent is preferably 10: 1.In the present invention, the kind of the curing agent
Class is not particularly limited, and is conventional solidified dose in this area.In the present invention, the heating-up temperature that is heating and curing is preferably
25~125 DEG C.In some embodiments of the invention, the polydimethylsiloxanefilm film is by the silicon of DOW CORNING SYLGARD 184
Rubber is prepared, and it includes the basic pre-polymerization component and curing agent that mass ratio is 10: 1, can be in 25~125 DEG C of temperature range
Interior solidification.
In the present invention, the source of the dimethyl silicone polymer glue body is not particularly limited, and is general commercially available product, such as
Can be the silicon rubber of DOW CORNING SYLGARD 184.
In the present invention, a part for three-dimensional grapheme collector is placed in the colloid, is heating and curing afterwards；This
In invention, the thickness of colloid is less than the gross thickness of three-dimensional grapheme collector.In the present invention, the temperature being heating and curing is preferred
For 25~125 DEG C.After described be heating and curing, integral type substrate-collector is formd.
According to the present invention, after integral type substrate-collector is obtained, using electrochemical deposition method in the integral type base
Settling electrode active material on three-dimensional grapheme collector in bottom-collector, obtains graphene flexible compound electrode.
In the present invention, the electrode active material is preferably polyaniline.
In the present invention, load capacity of the electrode active material on three-dimensional grapheme collector is preferably 1~3mg/
cm2, more preferably 1~2mg/cm2。
In the present invention, the process of the electrochemical deposition method is preferably as follows：Using the integral type substrate-collector as work
Electrode, platinized platinum is that Ag-AgCl is reference electrode, using the aqueous solution containing aniline and sulfuric acid as electrolyte to electrode, carries out electrification
Deposition is learned, so that deposition forms the active material of polyaniline electrode on the three-dimensional grapheme collector in integral type substrate-collector
Material, and then obtain graphene flexible compound electrode.
Above-mentioned preparation process that the present invention is provided is simple and easy to apply, cost is low, can carry out large-scale production.
Present invention also offers a kind of flexible super capacitor, including the graphene flexible compound described in above-mentioned technical proposal
Graphene flexible compound electrode made from electrode or above-mentioned preparation method.
In the present invention, the flexible super capacitor includes flexible miniature ultracapacitor and flexible non-miniature ultracapacitor
Device.
Flexible miniature ultracapacitor is the miniature energy storage device of class miniaturization developed in recent years or miniaturization.
In the present invention, the flexible miniature ultracapacitor preferably comprises above-mentioned interdigitated collector, i.e. the gained super electricity of flexible miniature
Container is interdigital micro super capacitor；Interdigital micro super capacitor is a kind of common type in micro super capacitor,
It is the micro super capacitor that a class uses interdigited electrode；In the present invention, in the interdigital flexible miniature ultracapacitor,
Three-dimensional grapheme collector employed in its graphene flexible compound electrode is interdigitated collector.
In the present invention, the flexible non-micro super capacitor refers to its in addition to above-mentioned flexible miniature ultracapacitor
Its typical ultracapacitor；In the present invention, the flexible non-micro super capacitor is preferably sandwich structure；Sandwich structure
Ultracapacitor be the common capacitor of a class in ultracapacitor field, it specifically refers to electrolyte being clipped in two plate electrodes
The ultracapacitor of sandwich sandwich structure is formed between piece.In the present invention, the sandwich structure it is flexible non-miniature super
In level capacitor, at least one in two electrode slices is above-mentioned graphene flexible compound electrode；The graphene flexible compound
Three-dimensional grapheme collector employed in electrode is preferably through the formation of above-mentioned chemical vapour deposition technique direct growth and without shape
The three-dimensional grapheme film of shape engraving.
In the present invention, the electrolyte in the flexible super capacitor is preferably PVA-H2SO4Gel electrolyte.The present invention
In, the PVA-H2SO4Gel electrolyte refers to PVA (i.e. polyvinyl alcohol) and H2SO4The gel formed after water is dissolved in jointly.
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
The preparation of 1.1 graphene flexible compound electrodes：
Foam nickel sheet is placed in tube furnace, logical hydrogen 180sccm is simultaneously warming up to 1000 DEG C, is then passed through methane 18sccm
And continue 30min；Then body of heater is removed by slide rail and cooled down at room temperature.The foam nickel sheet that grown three-dimensional grapheme is put
In FeCl3Cleaned and dry through ultra-pure water, ethanol with HCl mixed liquor, being defoamed nickel sheet in etching at 80 DEG C, then successively
It is dry, obtain three-dimensional grapheme film current collector.
It is that 10: 1 PDMS performed polymers and the mixture (silicon rubber of DOW CORNING SYLGARD 184) of curing agent are applied by mass ratio
Glass pane surface is distributed in, is heating and curing at 90 DEG C, transparent PDMS film is formed.PDMS glue is coated with gained PDMS film surface
Body (silicon rubber of DOW CORNING SYLGARD 184), colloid thickness is less than above-mentioned three-dimensional grapheme afflux body thickness, by three-dimensional grapheme
Collector is placed in colloid, is heating and curing at 90 DEG C, the filling of PDMS colloids has been coated partial 3-D graphene, is formed one
Formula substrate-collector.
Using gained integral type substrate-collector as working electrode, platinized platinum be to electrode, Ag-AgCl is reference electrode, with containing
There are 0.1M aniline and 1M H2SO4The aqueous solution be electrolyte, in carrying out electrochemical deposition under 0.8V operating voltage, in integral type
Deposition forms polyaniline electrode active material on three-dimensional grapheme collector in substrate-collector, and Polyaniline-Supported amount is
2mg/cm2, and then obtain graphene flexible compound electrode.
The sign of 1.2 graphene flexible compound electrodes：
Electron scanning Electronic Speculum (SEM) test is carried out to gained graphene flexible compound electrode, as a result as shown in Figure 3；Wherein,
1 is PDMS substrates；2 three-dimensional grapheme to be coated by PDMS substrates, 3 be uncoated three-dimensional grapheme；4 be to be carried on three-dimensional
The electrode active material of graphene.As can be seen that in gained graphene flexible compound electrode, one of three-dimensional grapheme collector
Filling is divided to be coated in the dimethyl silicone polymer substrate, another part loads the electrode active material.Its structural representation
Figure is as shown in Figure 1.
1.3 performance test：
Using 1.1 gained graphene flexible compound electrodes as basal electrode piece, PVA-H is added dropwise2SO4Gel electrolyte (by
6gPVA and 6g H2SO4It is dissolved in 60mL deionized waters and obtains), drying at room temperature is removed after excessive moisture, and two panels electrode slice is suppressed
The symmetric form flexible super capacitor of sandwich structure is obtained together.
Gained flexible super capacitor is subjected to electrochemical property test between 0~0.8V of operating voltage, as a result shown,
Its specific capacity is up to 0.5~1F/cm2, with good chemical property.
By gained flexible super capacitor it is folding bending 5000 times after (referring to Fig. 4), its capability retention still reaches
More than 80%.As can be seen that gained flexible compound electrode has good flexibility, while keeping good chemical property.
Embodiment 2
The preparation of 1.1 graphene flexible compound electrodes：
Foam nickel sheet is placed in tube furnace, logical hydrogen 180sccm is simultaneously warming up to 1000 DEG C, is then passed through methane 18sccm
And continue 30min；Then body of heater is removed by slide rail and cooled down at room temperature.The foam nickel sheet that grown three-dimensional grapheme is put
In FeCl3Cleaned and dry through ultra-pure water, ethanol with HCl mixed liquor, being defoamed nickel sheet in etching at 80 DEG C, then successively
It is dry, obtain three-dimensional grapheme film current collector.
Photoetching is carried out to gained three-dimensional grapheme film current collector using 532nm laser beam, spot size is 10 μm, is swashed
The photoetching power of light beam is 0.5W, obtains interdigitated collector.
It is that 10: 1 PDMS performed polymers and the mixture (silicon rubber of DOW CORNING SYLGARD 184) of curing agent are applied by mass ratio
Glass pane surface is distributed in, is heating and curing at 90 DEG C, transparent PDMS film is formed.PDMS glue is coated with gained PDMS film surface
Body (silicon rubber of DOW CORNING SYLGARD 184), colloid thickness is less than above-mentioned interdigitated afflux body thickness, by interdigitated three-dimensional graphite
Alkene collector is placed in colloid, is heating and curing at 90 DEG C, the filling of PDMS colloids has been coated partial 3-D graphene, is formed one
Body formula substrate-collector.
Using gained integral type substrate-collector as working electrode, platinized platinum be to electrode, Ag-AgCl is reference electrode, with containing
There are 0.1M aniline and 1M H2SO4The aqueous solution be electrolyte, in carrying out electrochemical deposition under 0.8V operating voltage, in integral type
Deposition forms polyaniline electrode active material on three-dimensional grapheme collector in substrate-collector, and Polyaniline-Supported amount is
2mg/cm2, and then obtain graphene flexible compound electrode.Structural representation such as Fig. 2 institutes of gained graphene flexible compound electrode
Show.
1.2 performance test：
Using 1.1 gained graphene flexible compound electrodes as basal electrode piece, PVA-H is added dropwise2SO4Gel electrolyte (by
6gPVA and 6g H2SO4It is dissolved in 60mL deionized waters and obtains), drying at room temperature is removed after excessive moisture, that is, obtains interdigitated miniature
Ultracapacitor.
Gained flexible super capacitor is subjected to electrochemical property test between 0~0.8V of operating voltage, as a result shown,
Its specific capacity is up to 30~50mF/cm2(CA=Cdevice/ A, wherein CAFor device area specific capacity, CdeviceFor device capacitance, A
For device area, including interdigital electrode area and it is interdigital between space), with good chemical property.
By gained flexible miniature ultracapacitor it is folding bending 2000 times after, its capability retention still reach 80% with
On.As can be seen that it has good flexibility, while keeping good chemical property.
As seen from the above embodiment, the flexible compound electrode that the present invention is provided can make flexible super capacitor and flexibility micro-
The specific capacity of type ultracapacitor is respectively up to 0.5~1F/cm2With 30~50mF/cm2, and fold 5000 in alternating bending respectively
With 2000 times after capability retention be higher than 80%, it is seen then that provide flexible compound electrode while having good chemical property
And mechanical property, be conducive to improving the stability of energy storage device.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.To these embodiments
A variety of modifications will be apparent for those skilled in the art, generic principles defined herein can be with
Without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to the most wide model consistent with features of novelty with principles disclosed herein
Enclose.
Claims (10)
1. a kind of graphene flexible compound electrode, it is characterised in that including：Dimethyl silicone polymer substrate, three-dimensional grapheme collection
Fluid and electrode active material；
A part for the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, another part load institute
State electrode active material.
2. graphene flexible compound electrode according to claim 1, it is characterised in that the electrode active material is polyphenyl
Amine.
3. graphene flexible compound electrode according to claim 1 or 2, it is characterised in that the electrode active material exists
Load capacity on three-dimensional grapheme collector is 1~3mg/cm2；
The thickness filled in the dimethyl silicone polymer substrate by three-dimensional grapheme collector is less than dimethyl silicone polymer base
The gross thickness at bottom.
4. graphene flexible compound electrode according to claim 1, it is characterised in that the three-dimensional grapheme collector bag
Include interdigitated collector.
5. a kind of preparation method of graphene flexible compound electrode according to any one of claims 1 to 4, it is characterised in that
Comprise the following steps：
A) using foam metal piece as template, deposition three-dimensional graphene is grown in the template using chemical vapour deposition technique, is passed through
Chemical etching obtains three-dimensional grapheme collector after removing the foam metal piece；
B) dimethyl silicone polymer glue body is coated with polydimethylsiloxanefilm film surface, by one of three-dimensional grapheme collector
It is placed in the colloid, is heating and curing, forms integral type substrate-collector；
C) electrochemical deposition method depositing electrode work on the three-dimensional grapheme collector in the integral type substrate-collector is utilized
Property material, obtains graphene flexible compound electrode.
6. preparation method according to claim 5, it is characterised in that the three-dimensional grapheme collector includes interdigitated collection
Fluid；
The interdigitated collector is obtained in the following manner：
A1) using foam metal piece as template, deposition three-dimensional graphene is grown in the template using chemical vapour deposition technique, is passed through
Chemical etching obtains three-dimensional grapheme collector after removing the foam metal piece；
A2 photoetching) is carried out to the three-dimensional grapheme collector using laser beam, interdigitated collector is obtained.
7. the preparation method according to claim 5 or 6, it is characterised in that the foam metal piece is foam nickel sheet, foam
Copper sheet or foam iron plate；
The chemical vapour deposition technique is using hydrogen and methane as reacting gas.
8. the preparation method according to claim 5 or 6, it is characterised in that the polydimethylsiloxanefilm film by with
Under type is obtained：
Dimethyl silicone polymer is mixed with curing agent and substrate surface is coated on, heated solidification, in the substrate surface shape
Into polydimethylsiloxanefilm film；
The mass ratio of the dimethyl silicone polymer and curing agent is 10: 1；
The step c) includes：
Using the integral type substrate-collector as working electrode, platinized platinum is that Ag-AgCl is reference electrode, to contain benzene to electrode
The aqueous solution of amine and sulfuric acid is electrolyte, carries out electrochemical deposition, the three-dimensional grapheme afflux in integral type substrate-collector
Deposition forms polyaniline electrode active material on body, obtains graphene flexible compound electrode.
9. a kind of flexible super capacitor, it is characterised in that flexible including graphene according to any one of claims 1 to 4
Graphene flexible compound electrode made from preparation method any one of combination electrode or claim 5~8.
10. flexible super capacitor according to claim 9, it is characterised in that the flexible super capacitor includes flexibility
Micro super capacitor and flexible non-micro super capacitor；
The flexible non-micro super capacitor is sandwich structure；The flexible miniature ultracapacitor includes the interdigitated
Collector；
Electrolyte in the flexible super capacitor is PVA-H2SO4Gel electrolyte.
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