CN107221447B - A kind of graphene flexible compound electrode, preparation method and flexible super capacitor - Google Patents
A kind of graphene flexible compound electrode, preparation method and flexible super capacitor Download PDFInfo
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- CN107221447B CN107221447B CN201710533489.2A CN201710533489A CN107221447B CN 107221447 B CN107221447 B CN 107221447B CN 201710533489 A CN201710533489 A CN 201710533489A CN 107221447 B CN107221447 B CN 107221447B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 239000003990 capacitor Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000007772 electrode material Substances 0.000 claims abstract description 34
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 31
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 31
- 239000006260 foam Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 238000005229 chemical vapour deposition Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000000084 colloidal system Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 238000001259 photo etching Methods 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003292 glue Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003486 chemical etching Methods 0.000 claims description 6
- 239000011245 gel electrolyte Substances 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 150000001412 amines Chemical class 0.000 claims 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 9
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 18
- 239000004205 dimethyl polysiloxane Substances 0.000 description 17
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 17
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- -1 polydimethylsiloxanes Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of graphene flexible compound electrode, preparation method and flexible super capacitors.Graphene flexible compound electrode provided by the invention includes: dimethyl silicone polymer substrate, three-dimensional grapheme collector and electrode active material；A part of the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part loads the electrode active material.Flexible compound electrode provided by the invention can make the specific capacity of flexible super capacitor and flexible miniature supercapacitor respectively up to 0.5~1F/cm2With 30~50mF/cm2, and capacity retention ratio is higher than 80% after alternating bending folds 5000 and 2000 times respectively.
Description
Technical field
The present invention relates to supercapacitor technologies field, in particular to a kind of graphene flexible compound electrode, its preparation side
Method and flexible super capacitor.
Background technique
With the rapid development of progress, industrialization and the informationization of science and technology, the electronic products such as computer, mobile phone
The necessity in life is had become, and these electronic products are gradually strided forward to portability, the transformation such as desktop computer to notebook；And
For the electronic equipment of portability, energy-storage system, which needs to have good power supply performance just, can make electronic equipment be detached from fixed electricity
The constraint in source becomes the movable fixture that can be easy to use.Up to now, supercapacitor is due to high capacity, Gao Gong
The advantages that rate density, high charge-discharge speed and become the energy storage device that is most widely used in mobile electronic device.
Traditional supercapacitor mainly includes positive and negative anodes, diaphragm and electrolyte, and planform is relatively simple.In recent years
Come, with portable and wearable electronic development, the research of flexible super capacitor becomes hot spot.Flexible capacitor
Mainly it is made of substrate, electrode and electrolyte；Different from conventional Super capacitor, in flexible super capacitor, substrate, electricity
Pole and electrolyte are flexible, and can be assigned capacitor miscellaneous shape, can be provided form more abundant and function
Can, it more can satisfy the growth requirement of electronic equipment.
Flexible electrode directly determines the performance of capacitor as the core component of flexible super capacitor, in bending state
Under, the positive and negative electrode of capacitor is in compression and tensile stress state, and bends repeatedly and electrode structure is be easy to cause to destroy, such as electricity
The disengaging etc. even from flexible substrates of pole material cracks, causes the performance of energy storage device to decline.Currently, 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
The contact area of collector and electrode active material, on the other hand, continuous three dimensional network can be improved in dimension graphene pore structure
Network structure can also reduce stress suffered in electrode material bending process, reduce above-mentioned electrode material cracking and the wind that falls off
Danger.But using the electrode of three-dimensional grapheme, it is poor there is Resisting fractre ability the defects of, influence the stability of capacitor.
Therefore, how to obtain while there is the flexible electrode of excellent chemical property and mechanical property to still suffer from no small choose
War.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of graphene flexible compound electrode, preparation method and flexibilities
Supercapacitor.Graphene flexible compound electrode provided by the invention has excellent chemical property and mechanical property simultaneously.
The present invention provides a kind of graphene flexible compound electrodes, comprising: dimethyl silicone polymer substrate, three-dimensional grapheme
Collector and electrode active material；
A part of the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part is negative
Carry the electrode active material.
Preferably, the electrode active material is polyaniline.
Preferably, 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 overall thickness at alkyl bottom.
Preferably, the three-dimensional grapheme collector includes interdigitated collector.
The present invention also provides a kind of preparation methods of 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 obtains three-dimensional grapheme collector after chemical etching removes the foam metal piece；
B) it is coated with dimethyl silicone polymer glue body on polydimethylsiloxanefilm film surface, by three-dimensional grapheme collector
A part is placed in the colloid, is heating and curing, and integral type substrate-collector is formed；
C) electricity is deposited on the three-dimensional grapheme collector in the integral type substrate-collector using electrochemical deposition method
Pole active material obtains graphene flexible compound electrode.
Preferably, the three-dimensional grapheme collector includes interdigitated collector；
The interdigitated collector obtains 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 obtains three-dimensional grapheme collector after chemical etching removes the foam metal piece；
A2 photoetching) is carried out to the three-dimensional grapheme collector using laser beam, obtains interdigitated collector.
Preferably, 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 reaction gas.
Preferably, the polydimethylsiloxanefilm film obtains in the following manner:
Dimethyl silicone polymer is mixed to curing agent and is coated on substrate surface, 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 is to electrode, and Ag-AgCl is reference electrode, to contain
Having the aqueous solution of 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.
The present invention also provides a kind of flexible super capacitors, including 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.
Preferably, the flexible super capacitor includes flexible miniature supercapacitor and flexible non-miniature ultracapacitor
Device；
The non-micro super capacitor of flexibility is sandwich structure；The flexible miniature supercapacitor includes the fork
Finger-like collector；
Electrolyte in the flexible super capacitor is PVA-H2SO4Gel electrolyte.
The present invention provides a kind of graphene flexible compound electrodes, comprising: dimethyl silicone polymer substrate, three-dimensional grapheme
Collector and electrode active material；A part of the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate
In, another part loads the electrode active material.Flexible compound electrode provided by the invention not only has good electrochemistry
Performance also has good mechanical property, is conducive to the stability for improving energy storage device.The present invention also provides above-mentioned stones
The preparation method of black alkene flexible compound electrode, preparation process is simple and easy, is able to carry out large-scale production.The present invention also provides
A kind of flexible super capacitor including above-mentioned graphene flexible compound electrode, the performance of the supercapacitor are stablized.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the structural schematic diagram for the graphene flexible compound electrode that one embodiment of the present of invention provides；
Fig. 2 be another embodiment of the present invention provides graphene flexible compound electrode structural schematic diagram；
Fig. 3 is the SEM test chart for the graphene flexible compound electrode that the embodiment of the present invention 1 provides；
Fig. 4 is to bend operation chart in flexible compound electrode bending experiment in the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of graphene flexible compound electrodes, comprising: dimethyl silicone polymer substrate, three-dimensional grapheme
Collector and electrode active material；
A part of the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part is negative
Carry the electrode active material.
Referring to Fig. 1, Fig. 1 is the structural schematic diagram for the graphene flexible compound electrode that one embodiment of the present of invention provides,
Wherein, 1 is dimethyl silicone polymer (i.e. PDMS) substrate；2 and 3 be three-dimensional grapheme collector, and 2 are coated by PDMS substrate
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, is capable of providing good deformation stability.
A part of three-dimensional grapheme collector is filled in substrate 1, i.e., the three-dimensional grapheme 2 coated by substrate, will
PDMS substrate is conducive to the stretching, bending and crimp property that improve whole combination electrode in conjunction with three-dimensional grapheme part.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 overall thickness at oxyalkyl bottom.
The 3 load electrode active material of three-dimensional grapheme of another part of three-dimensional grapheme collector, that is, uncoated, provides
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 be another embodiment of the present invention provides graphene flexibility it is multiple
The structural schematic diagram 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 be the three-dimensional grapheme coated by PDMS substrate, and 3 be uncoated three-dimensional grapheme；Load has electrode active in 3
Property material.
Interdigited electrode material refers to a kind of electrode material as there is periodic patterns in the face of finger-like or pectination.Currently,
Interdigited electrode often uses the metal collectors such as gold, mainly passes through the means such as metal evaporation, wet process photoetching for metal collector
It is plated in substrate surface, however, its preparation process is complicated, at high cost, electrochemistry and mechanical property be not good enough, and is easy to fall off.This hair
It is bright that combination is inlayed using interdigitated three-dimensional grapheme collector and substrate, it is capable of providing good electric conductivity and mechanical property,
And it is at low cost.
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。
Flexible compound electrode provided by the invention 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 the stability for improving energy storage device.The experimental results showed that provided by the invention soft
Property combination electrode can make the specific capacity of flexible super capacitor and flexible miniature supercapacitor respectively up to 0.5~1F/cm2
With 30~50mF/cm2, and capacity retention ratio is higher than 80% after alternating bending folds 5000 and 2000 times respectively.
The present invention also provides the preparation methods of graphene flexible compound electrode described in above-mentioned technical proposal, including following step
It is rapid:
A) using foam metal piece as template, deposition three-dimensional graphite is grown in the template using chemical vapour deposition technique
Alkene obtains three-dimensional grapheme collector after chemical etching removes the foam metal piece；
B) it is coated with dimethyl silicone polymer glue body on polydimethylsiloxanefilm film surface, by three-dimensional grapheme collector
A part is placed in the colloid, is heating and curing, and integral type substrate-collector is formed；
C) electricity is deposited on the three-dimensional grapheme collector in the integral type substrate-collector using electrochemical deposition method
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 obtains three-dimensional grapheme collector after chemical etching removes the foam metal piece.
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, chemical vapor deposition preferably is carried out using hydrogen and methane as reaction 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 having carried out chemical vapor deposition, preferably pass through chemistry
The sheet metal template that defoams is etched, then is cleaned and is dried, to obtain three-dimensional grapheme collector.
In certain embodiments, three-dimensional grapheme collector can be prepared as follows: foam nickel sheet is set
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
Sliding rail cools down furnace body removal at room temperature.The foam nickel sheet that grown three-dimensional grapheme is placed in FeCl3With the mixed liquor of HCl
In, the nickel sheet that defoams is etched at 80 DEG C, then it is thin successively to obtain three-dimensional grapheme through ultrapure water, ethyl alcohol cleaning and drying
Film collector.
In some embodiments of the invention, three-dimensional grapheme collector is interdigitated morphosis, as interdigitated collection
Fluid；The interdigitated collector can obtain in the following manner: using foam metal piece as template, utilize chemical vapor deposition
Method grows deposition three-dimensional graphene in the template, obtains three-dimensional grapheme film current collector；Using laser beam to described three
It ties up graphene film collector and carries 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 obtaining three-dimensional grapheme film current collector, using swash
Light beam carries out photoetching to gained three-dimensional grapheme collector, forms interdigitated morphosis, obtains interdigitated collector.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, after obtaining collector, dimethyl silicone polymer glue is coated on polydimethylsiloxanefilm film surface
A part of three-dimensional grapheme collector is placed in the colloid, is heating and curing by body, forms integral type substrate-collector.
In the present invention, the polydimethylsiloxanefilm film preferably obtains in the following manner: by dimethyl silicone polymer
Substrate surface is mixed and is coated on curing agent, and heated solidification forms polydimethylsiloxanefilm film in the substrate surface.
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 field.In the present invention, the heating temperature being heating and curing is preferably
25~125 DEG C.In some embodiments of the invention, the polydimethylsiloxanefilm film is by 184 silicon of DOW CORNING SYLGARD
Rubber is prepared comprising the basic pre-polymerization component and curing agent of mass ratio 10: 1, it 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
It can be 184 silicon rubber of DOW CORNING SYLGARD.
In the present invention, a part of three-dimensional grapheme collector is placed in the colloid, is heating and curing later；This
In invention, the thickness of colloid is less than the overall thickness of three-dimensional grapheme collector.In the present invention, the temperature being heating and curing is preferred
It is 25~125 DEG C.After described be heating and curing, integral type substrate-collector is formd.
According to the present invention, after obtaining integral type substrate-collector, 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 are to electrode, and Ag-AgCl is reference electrode, using the aqueous solution containing aniline and sulfuric acid as electrolyte, carry out electrification
Deposition is learned, so that deposition forms polyaniline electrode activity material on the three-dimensional grapheme collector in integral type substrate-collector
Material, and then obtain graphene flexible compound electrode.
Above-mentioned preparation process provided by the invention is simple and easy, at low cost, is able to carry out large-scale production.
The present invention also provides a kind of flexible super capacitors, including 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 supercapacitor and flexible non-miniature ultracapacitor
Device.
Flexible miniature supercapacitor is the miniature energy storage device of a kind of miniaturization or micromation developed in recent years.
In the present invention, the flexible miniature supercapacitor 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 a kind of micro super capacitor for using interdigited electrode；In the present invention, in the interdigital flexible miniature supercapacitor,
Three-dimensional grapheme collector employed in its graphene flexible compound electrode is interdigitated collector.
In the present invention, the non-micro super capacitor of flexibility refers to its in addition to above-mentioned flexible miniature supercapacitor
Its typical ultracapacitor；In the present invention, the non-micro super capacitor of flexibility is preferably sandwich structure；Sandwich structure
Supercapacitor be a kind of common capacitor in supercapacitor field, specifically refer to for electrolyte to be clipped in two plate electrodes
The supercapacitor of sandwich sandwich structure is formed between piece.In the present invention, the flexibility of the sandwich structure is non-miniature super
In grade capacitor, at least one of two electrode slices are above-mentioned graphene flexible compound electrode；The graphene flexible compound
Three-dimensional grapheme collector employed in electrode preferably directly grows formation through above-mentioned chemical vapour deposition technique 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 H2SO4It is dissolved in the gel formed after water jointly.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation 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 furnace body removal is cooled down at room temperature by sliding rail.The foam nickel sheet that grown three-dimensional grapheme is set
In FeCl3In the mixed liquor of HCl, the nickel sheet that defoams is etched at 80 DEG C, then is successively cleaned and done through ultrapure water, ethyl alcohol
It is dry, obtain three-dimensional grapheme film current collector.
By mixture (184 silicon rubber of the DOW CORNING SYLGARD) painting of PDMS performed polymer and curing agent that mass ratio is 10: 1
It is distributed in glass pane surface, is heating and curing at 90 DEG C, transparent PDMS film is formed.PDMS glue is coated on gained PDMS film surface
Body (184 silicon rubber of DOW CORNING SYLGARD), colloid thickness is lower 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, so that the filling of PDMS colloid has been coated partial 3-D graphene, is formed one
Formula substrate-collector.
Using gained integral type substrate-collector as working electrode, platinized platinum is to electrode, and Ag-AgCl is reference electrode, to contain
There are 0.1M aniline and 1M H2SO4Aqueous solution be electrolyte, electrochemical deposition is carried out under the operating voltage of 0.8V, 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 characterization 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 substrate；2 be the three-dimensional grapheme coated by PDMS substrate, and 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 tests:
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 water and obtains), after drying at room temperature removes excessive moisture, 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, the results show that
Its specific capacity is up to 0.5~1F/cm2, there is good chemical property.
By (referring to fig. 4), capacity retention ratio still reaches after the folding bending of gained flexible super capacitor 5000 times
80% or more.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 furnace body removal is cooled down at room temperature by sliding rail.The foam nickel sheet that grown three-dimensional grapheme is set
In FeCl3In the mixed liquor of HCl, the nickel sheet that defoams is etched at 80 DEG C, then is successively cleaned and done through ultrapure water, ethyl alcohol
It is dry, obtain three-dimensional grapheme film current collector.
Photoetching is carried out to gained three-dimensional grapheme film current collector using the laser beam of 532nm, spot size is 10 μm, is swashed
The photoetching power of light beam is 0.5W, obtains interdigitated collector.
By mixture (184 silicon rubber of the DOW CORNING SYLGARD) painting of PDMS performed polymer and curing agent that mass ratio is 10: 1
It is distributed in glass pane surface, is heating and curing at 90 DEG C, transparent PDMS film is formed.PDMS glue is coated on gained PDMS film surface
Body (184 silicon rubber of DOW CORNING SYLGARD), colloid thickness is lower 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, so that the filling of PDMS colloid 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 is to electrode, and Ag-AgCl is reference electrode, to contain
There are 0.1M aniline and 1M H2SO4Aqueous solution be electrolyte, electrochemical deposition is carried out under the operating voltage of 0.8V, 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 schematic diagram such as Fig. 2 institute of gained graphene flexible compound electrode
Show.
1.2 performance tests:
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 water and obtains), after drying at room temperature removes excessive moisture, i.e. acquisition interdigitated is miniature
Supercapacitor.
Gained flexible super capacitor is subjected to electrochemical property test between 0~0.8V of operating voltage, the results show that
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 gap), there is good chemical property.
By gained flexible miniature supercapacitor it is folding bending 2000 times after, capacity retention ratio still reach 80% with
On.As can be seen that it is with good flexibility, while keeping good chemical property.
As seen from the above embodiment, flexible compound electrode provided by the invention can make flexible super capacitor and flexibility micro-
The specific capacity of type supercapacitor is respectively up to 0.5~1F/cm2With 30~50mF/cm2, and 5000 are folded in alternating bending respectively
Capacity retention ratio is higher than 80% after with 2000 times, it is seen then that provided flexible compound electrode has good chemical property simultaneously
And mechanical property, be conducive to the stability for improving energy storage device.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.To these embodiments
A variety of modifications will be readily apparent to those skilled in the art, the general principles defined herein can be with
Without departing from the spirit or scope of the present invention, it realizes in other embodiments.Therefore, the present invention will not be limited
In the embodiments shown herein, and it is to fit to widest model consistent with the principles and novel features disclosed in this article
It encloses.
Claims (10)
1. a kind of graphene flexible compound electrode characterized by comprising dimethyl silicone polymer substrate, three-dimensional grapheme collection
Fluid and electrode active material；
A part of the three-dimensional grapheme collector is filled in the dimethyl silicone polymer substrate, and another part loads institute
State electrode active material.
2. graphene flexible compound electrode according to claim 1, which is characterized in that the electrode active material is polyphenyl
Amine.
3. graphene flexible compound electrode according to claim 1 or 2, which is characterized 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 overall thickness at bottom.
4. graphene flexible compound electrode according to claim 1, which is characterized in that the three-dimensional grapheme collector packet
Include interdigitated collector.
5. a kind of preparation method of graphene flexible compound electrode according to any one of claims 1 to 4, which is characterized in that
The following steps are included:
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) it is coated with dimethyl silicone polymer glue body on polydimethylsiloxanefilm film surface, by one of three-dimensional grapheme collector
It is placed in the colloid, is heating and curing, form integral type substrate-collector；
C) using electrochemical deposition method, depositing electrode is living on the three-dimensional grapheme collector in the integral type substrate-collector
Property material, obtains graphene flexible compound electrode.
6. preparation method according to claim 5, which is characterized in that the three-dimensional grapheme collector includes interdigitated collection
Fluid；
The interdigitated collector obtains 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, obtains interdigitated collector.
7. preparation method according to claim 5 or 6, which is characterized 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 reaction gas.
8. preparation method according to claim 5 or 6, which is characterized in that the polydimethylsiloxanefilm film by with
Under type obtains:
Dimethyl silicone polymer is mixed to curing agent and is coated on substrate surface, heated solidification, in the substrate surface shape
At 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 to electrode, and Ag-AgCl is reference electrode, to contain benzene
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, which is characterized in that flexible including graphene according to any one of claims 1 to 4
Graphene flexible compound electrode made from preparation method described in any one of combination electrode or claim 5~8.
10. flexible super capacitor according to claim 9, which is characterized in that the flexible super capacitor includes flexibility
Micro super capacitor and flexible non-micro super capacitor；
The non-micro super capacitor of flexibility is sandwich structure；The flexible miniature supercapacitor includes interdigitated afflux
Body；
Electrolyte in the flexible super capacitor is PVA-H2SO4Gel electrolyte.
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| US11315742B2 (en) * | 2018-07-02 | 2022-04-26 | Korea Institute Of Energy Research | Freely detachable sticker-type electronic device, method of manufacturing the same, and method of forming electrode for the same |
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