CN107919233B - A kind of high voltage flexible solid-state supercapacitor and preparation method thereof - Google Patents
A kind of high voltage flexible solid-state supercapacitor and preparation method thereof Download PDFInfo
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- CN107919233B CN107919233B CN201710969308.0A CN201710969308A CN107919233B CN 107919233 B CN107919233 B CN 107919233B CN 201710969308 A CN201710969308 A CN 201710969308A CN 107919233 B CN107919233 B CN 107919233B
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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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
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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
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- H—ELECTRICITY
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- 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
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Abstract
A kind of high voltage flexible solid-state supercapacitor and preparation method thereof, including gel electrolyte film, flexible current-collecting body, electrode and encapsulated layer；The electrode is coated on flexible current-collecting body surface, constitutes flexible electrical pole piece；It is stacked according to encapsulated layer-flexible electrical pole piece-gel electrolyte membrane-flexible electrical pole piece-encapsulated layer sequence, encapsulated layer wraps up flexible electrical pole piece-gel electrolyte membrane-flexible electrical pole piece.Electrode active material and flexible electrical pole piece are prepared first, then it prepares ionic gel and is cast into film, two flexible electrical pole pieces and gel electrolyte are stacked according to the sequence of flexible electrical pole piece-gel film-flexible electrical pole piece, high voltage flexible solid-state supercapacitor is made after being encapsulated with thermoplastic high molecular film.
Description
Technical field
The present invention relates to a kind of supercapacitors and preparation method thereof.
Background technique
With continuing to bring out for wearable flexible intelligent equipment, the rollable energy storage of small in size, light weight, flexible section is developed
Device becomes the current research field that everybody pays close attention to.Supercapacitor is a kind of with high power, high security, wide temperature
The electrochemical energy storing device of the advantages that use scope and long circulation life.Flexible super capacitor refers in bending, distorts even
The flexible energy storage device that still can be worked in the state of stretching, is particularly suitable for application to wearable device.Currently, super capacitor
The energy density of device is still not ideal enough, generally 5-10Wh/Kg, limits its further engineering application.
According to the density energy formula E=1/2CU of supercapacitor2, it can be seen that its energy density depends primarily on electricity
Hold C and voltage U.Currently, raising of the researcher for flexible super capacitor energy density is mostly conceived to and prepares high property
Energy flexible electrode is to improve capacitor C.The voltage window of supercapacitor depends on used electrolyte system.Current flexible electrical
The electrolyte that container uses is generally aqueous solution or aquogel system, and voltage window is up to 1.23V.But widen its electricity
Press U, it is clear that can more significantly improve energy density.Ionic liquid is that a kind of had by what organic cation and anion formed
Machine fused salt, voltage window is up to 5V or so.Much higher than the voltage range of aqueous electrolyte, because of referred to herein as high voltage electrolytes.
Currently, in the research of typical ultracapacitor, has the related report that voltage range is improved using ionic liquid.But In
Flexible super capacitor field, there has been no correlations to report.Further, since viscosity of il is big, diffusional resistance is big, needle
Targeted design is carried out to carbon-based electrode material to ionic liquid, the novel high-performance electrode for obtaining suitable ion liquid system is
Develop the important link of high voltage flexible capacitor.
In addition, the multiple bending of device use process will cause the leakage of liquid electrolyte for flexible bendable device.
Therefore in order to overcome leakage hidden danger, and easily prepared encapsulation, solid electrolyte is widely used that in flexible device.Therefore,
It needs ionic liquid and macromolecule matrix material will be mixed, is prepared into the ionic gel of high voltage.Wherein, macromolecule matrix is in
Space net structure is filled with ionic liquid electrolyte in gap, collectively forms ionic gel；Develop high performance carbon base electrode
It is the important channel for obtaining next-generation high-performance flexible supercapacitor with high-voltage ion gel.But there has been no bases at present
It is reported in the flexible super capacitor of high-voltage ion liquid gel.
Summary of the invention
Energy density in order to overcome the problems, such as current flexible solid-state supercapacitor is lower, and the present invention proposes a kind of high voltage
Flexible solid-state supercapacitor and preparation method thereof, it is quasi- to improve device energy density by promoting the voltage of device.
High voltage flexible solid-state supercapacitor of the present invention includes gel electrolyte film, flexible current-collecting body and electrode
And encapsulated layer.The electrode includes active material, conductive agent and binder.The electrode is coated on flexible current-collecting body surface
Face constitutes flexible electrical pole piece.Gel electrolyte film, flexible current-collecting body, electrode and encapsulated layer are according to encapsulated layer-flexible electrode
Piece-gel electrolyte membrane-flexible electrical pole piece-encapsulated layer sequence arrangement stacks.Encapsulated layer wraps up flexible electrical pole piece-gel electrolyte
Plasma membrane-flexible electrical pole piece.
The active material of the electrode be one of graphene, carbon nanotube, porous charcoal or by it is several form it is compound
Object；Preferably, the active material is graphene-based porous carbon composite nano-material.
The gel electrolyte is high-voltage ion gel；High-voltage ion gel include macromolecule matrix material and from
Sub- liquid electrolyte.Macromolecule matrix is in space net structure, is full of ionic liquid electrolyte in gap, it is thin to form gel
Film.
The macromolecule matrix material is Kynoar (PVdF), (Kynoar-hexafluoropropene) copolymer
(PVDF-HFP), polyoxyethylene (PEO)；Preferably, the macromolecule matrix material is (Kynoar-hexafluoropropene) copolymerization
Object (PVDF-HFP).
The room temperature liquid dissolved salt that the ionic liquid electrolyte is made of organic cation and anion, organic cation
There are quaternary ammonium salt ion, quaternary phosphine salt ion, imidazolium ion etc., anion has halide ion, tetrafluoroborate ion, hexafluorophosphoric acid
Radical ion, two (trimethyl fluoride sulfonyl) imines ions.Common ion liquid includes 1- ethyl-3-methylimidazole tetrafluoroborate
(EMIBF4), 1- ethyl-3-methylimidazole hexafluorophosphate (EMIPF6) and bis- (the trifluoromethyl sulphurs of 1- ethyl-3-methylimidazole
Acyl) Asia peace salt (EMITFSI)；Preferably, ionic liquid electrolyte is 1- ethyl-3-methylimidazole tetrafluoroborate
(EMIBF4)。
For high voltage flexible solid-state supercapacitor of the present invention using high-voltage ion gel as gel electrolyte, voltage can
Up to 3~4.5V, this is different from traditional voltage class of 0.7~2.7V of flexible super capacitor.According to formula E=1/2CU2,
The energy density of flexible capacitor can be substantially improved in high voltage capacitor.
The method for preparing supercapacitor of the present invention is as follows:
Electrode active material and flexible electrical pole piece are prepared first, then prepare ionic gel and is cast into film, by two
Flexible electrical pole piece and gel electrolyte are stacked together according to the sequence of flexible electrical pole piece-gel film-flexible electrical pole piece, with heat
High voltage flexible solid-state supercapacitor is formed after plastic macromolecule thin-film package.
Specific step is as follows:
1) electrode active material is prepared
Using business carbon nano tube or synthesizing graphite alkene Quito hole carbon nanomaterial as active material.
Synthesizing graphite alkene Quito hole carbon nanomaterial technique is as follows: natural graphite being oxidized to oxygen using Hummers method
Graphite, and graphene oxide water solution is prepared by probe sonication dispersion removing.Then in graphene oxide water solution
Conducting polymer monomer, dopant and oxidant ammonium persulfate is added, -10 DEG C to 25 DEG C at a temperature of, be stirred to react 1-48
Hour, graphene oxide-conducting polymer composite material is obtained, and wash drying.By above-mentioned graphene oxide-conducting polymer
Composite material and potassium hydroxide are put into tube furnace calcining and activating under an argon atmosphere after being ground, and then use dilute hydrochloric acid at room temperature
Washing, dry, the graphene-based porous carbon nanomaterial of acquisition.
Wherein, 0.005-1mol L is contained in the graphene oxide water solution-1Conducting polymer monomer, 0.01-
2mol L-1Dopant and 0.005-1mol L-1Ammonium persulfate；Preferably, contain in the graphene oxide water solution
0.05mol L-1Conducting polymer monomer, 1mol L-1Dopant, 0.05mol L-1Ammonium persulfate.
Preparing graphene-conducting polymer composite material reaction time is preferably 24 hours.
The conducting polymer monomer is one of aniline, pyrroles, thiophene and ethylenedioxy thiophene or a variety of；It is preferred that
, the conducting polymer monomer is aniline monomer.
The dopant is one of sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid or a variety of, excellent
Select perchloric acid.
The ratio of graphene oxide-conducting polymer composite material and potassium hydroxide is 2:1 to 1:8；Preferably 1:4.
The calcination temperature of synthesizing graphite alkene Quito hole carbon nanomaterial is 500 DEG C -900 DEG C；It is preferred that 700 DEG C.
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous carbon nanomaterial as active material, by active material, conductive agent and binder according to
(60-95) %:(0-20) %:(5-20) % ratio mixed grinding, be dissolved in solvent, be prepared into slurry；Solid content is in slurry
30%-60%.Slurry is coated on flexible current-collecting body, coating thickness is 20-500 microns, baking oven is then placed into, 120
Drying obtains electrode slice for 24 hours at DEG C.
The conductive agent be one of conductive black, electrically conductive graphite, carbon nanotubes, nano carbon fiber, graphene or
It is a variety of；It is preferred that conductive black.
The binder is Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber；It is preferred that Kynoar.
Solvent is N-Methyl pyrrolidone, deionized water or ethyl alcohol；Preferably, solvent is N-Methyl pyrrolidone.Activity
The ratio of material, conductive agent and binder is preferably 80%:10%:10%.
The preferred carbon nano-tube film of collector.
The thickness of electrode of flexible electrode on piece is 10 microns to 200 microns, and carbon electrode active material is negative in single electrode
Load content is 0.1-5mg/cm2.Preferably, the loading content of carbon electrode active material is 0.5-2mg/cm in single electrode2。
3) high-voltage ion gel film is prepared
Polymer-based bottom material and ionic liquid electrolyte are mixed according to the ratio of 1:4~4:1, acetone is added as molten
Agent.Overall solution volume is 10-50mL, so that solid content is 5%~60%.It is heated to 50 DEG C under closed state, is kept for 24 hours,
Until polymer-based bottom material is completely dissolved.Solution is poured into glass culture dish, obtains gel electrolyte after solvent volatilization
Film.
The ratio of the macromolecule matrix material and ionic liquid electrolyte is preferably 1:1.
Gel electrolyte film obtained with a thickness of 100 microns -1 millimeter, preferably with a thickness of 500 microns.
Solid content is preferably 20% in the step 3).
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Then polydimethylsiloxane thin-film package is used, flexible super capacitor is obtained.
The voltage of the flexible super capacitor is 3.5-4V, capacitance 100-250F/g；Energy density is 50-
106Wh/Kg；Capacity retention after charge and discharge cycles 10000 times is 80-98%.
Flexible super capacitor prepared by the present invention has the advantage that
1) it greatly improved as electrolyte compared to traditional water system electrolyte using the ion liquid system of high voltage
The voltage U of flexible super capacitor, therefore effectively improve the energy density of flexible super capacitor.
2) graphene-based porous carbon electrodes active material has Hierarchical porosity structure, and macropore is conducive to the biography of charge and ion
It is defeated, and Jie's micropore is used to store more charge, this structure is suitble to ionic liquid electrolyte system, effectively promotes electrode specific capacitance
C, and then improve the energy density of storage.
3) ionic liquid electrolyte is mixed with macromolecule matrix, being prepared into not only has high-strength mechanical properties, but also has
The gel solid state electrolyte of high ion conductivity.The leakage hidden danger for avoiding flexible bendable device, simplifies packaging technology.
4) high voltage flexible solid-state supercapacitor specific capacitance, cyclical stability and the energy density prepared also has good
Good bending resistance.
Detailed description of the invention
The schematic diagram of the section structure of Fig. 1 high voltage flexible solid-state supercapacitor；
The photo in kind of Fig. 2 high voltage flexible solid-state supercapacitor；
Graphene oxide-conducting polymer composite precursor scanning electron microscopic picture prepared by Fig. 3 embodiment 1；
The scanning electron microscopic picture of graphene-based carbon composite nano structure electrode material prepared by Fig. 4 embodiment 1；
The charging and discharging curve figure of flexible solid-state supercapacitor prepared by Fig. 5 embodiment 1；
The cycle charge-discharge stability curve figure of flexible solid-state supercapacitor prepared by Fig. 6 embodiment 1；
The capacitance curve graph of flexible solid-state supercapacitor prepared by Fig. 7 embodiment 2；
The capacitance curve graph of flexible solid-state supercapacitor prepared by Fig. 8 embodiment 5；
The electron microscopic picture of graphene oxide prepared by Fig. 9 comparative example 1；
The flexible solid-state supercapacitor of Figure 10 application examples preparation lights the photo in kind of 30 LED light.
Specific embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Steps are as follows for preparation method of the present invention:
1) it prepares electrode active material: being made using business carbon nano tube or synthesizing graphite alkene Quito hole carbon nanomaterial
For electrode active material.
Synthesizing graphite alkene Quito hole carbon nanomaterial technique is as follows: natural graphite being oxidized to oxygen using Hummers method
Graphite, and graphene oxide water solution is prepared by probe sonication dispersion removing.Then in graphene oxide water solution
Conducting polymer monomer, dopant and oxidant ammonium persulfate is added, -10 DEG C to 25 DEG C at a temperature of, be stirred to react 1-48
Hour, it obtains graphene oxide-conducting polymer composite material and washs drying.By above-mentioned graphene oxide-conducting polymer
Composite material and potassium hydroxide are put into tube furnace calcining and activating under an argon atmosphere after being ground in the ratio of 2:1 to 1:8, so
It is washed at room temperature with dilute hydrochloric acid afterwards, is dry, obtaining graphene-based porous carbon composite nano-material.
Wherein, 0.005-1mol L is contained in the graphene oxide water solution-1Conducting polymer monomer, 0.01-
2mol L-1Dopant and 0.005-1mol L-1Ammonium persulfate；Preferred graphene oxide-conducting polymer composite material
Contain 0.05molL-1Conducting polymer monomer, 1molL-1Dopant, 0.05mol L-1Ammonium persulfate；
Preparing graphene oxide-conducting polymer composite material reaction time is preferably 24 hours；
The conducting polymer monomer is one of aniline, pyrroles, thiophene and ethylenedioxy thiophene or a variety of, preferably
For aniline monomer；
The dopant is one of sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid or a variety of, excellent
It is selected as perchloric acid.
The ratio of graphene oxide-conducting polymer composite material and potassium hydroxide is 2:1 to 1:8；Preferably 1:4.
The calcination temperature of synthesizing graphite alkene Quito hole carbon nanomaterial be 500 DEG C -900 DEG C at any temperature, preferably 700
℃。
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous carbon nanomaterial as active material, by active material, conductive agent and binder according to
(60-95) %:(0-20) %:(5-20) % ratio mixed grinding, be dissolved in solvent and be prepared into slurry；Solid content is in slurry
30%-60%.Then slurry being coated on flexible current-collecting body, coating thickness is 20 microns to 500 microns, it is placed in baking oven,
Drying obtains electrode for 24 hours at 120 DEG C.
Wherein the conductive agent is one of conductive black, electrically conductive graphite, carbon nanotubes, conductive Carbon fibe or more
Kind, preferably conductive black.
The binder is Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber, preferably Kynoar.
The solvent is N-Methyl pyrrolidone, deionized water or ethyl alcohol, preferably N-Methyl pyrrolidone.
The ratio of active material, conductive agent and binder is preferably 80%:10%:10%.
The preferred carbon nano-tube film of the collector.
The thickness of electrode of flexible electrode on piece is 10 microns to 200 microns, and carbon electrode active material is negative in single electrode
Load content is 0.1-5mg/cm2.Preferably, the loading content of carbon electrode active material is 0.5-2mg/cm in single electrode2。
3) high-voltage ion gel film is prepared
Polymer-based bottom material and ionic liquid electrolyte are mixed according to the ratio of 1:4~4:1, acetone is added as molten
Agent.Overall solution volume is 10-50mL, and solid content is 5%~80%.It is heated to 50 DEG C in the closed state, is kept for 24 hours, directly
To being completely dissolved.Solution is poured into glass culture dish, obtains gel electrolyte film after solvent volatilization.
The ratio of polymer-based bottom material and ionic liquid electrolyte is preferably 1:1.
The gel electrolyte film with a thickness of 100 microns -1 millimeter, preferred thickness is 500 microns.
Solid content is preferably 20%.
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte membrane electrode-flexible electrical pole piece sequence stacks, and guarantees to coat in flexible electrical pole piece
There is the one side of electrode material to contact with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained,
As depicted in figs. 1 and 2.The flexible super capacitor of preparation is connected to the electrochemical workstation of French BioLogic, passes through perseverance
Charge-discharge test is flowed, the voltage for obtaining the flexible super capacitor is 3.5-4V, capacitance 100-250F/g；Energy density
For 50-106Wh/Kg；Capacity retention after charge and discharge cycles 10000 times is 80-98%.
Embodiment 1
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 0.05molL is added in graphene oxide water solution-1Aniline, 1mol L-1Perchloric acid
And 0.05molL-1Ammonium persulfate, -10 DEG C at a temperature of, be stirred to react 24 hours, it is multiple to obtain graphene oxide-polyaniline
Condensation material simultaneously washs drying, as shown in Figure 3.
Tube furnace is put into after above-mentioned compound and potassium hydroxide are ground in 1:4 ratio to be fired under an argon atmosphere
Then 700 DEG C of activation are washed at room temperature with dilute hydrochloric acid, are dry, obtaining graphene-based porous carbon nanomaterial, as shown in Figure 4.
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous carbon nanomaterial as active material.By active material, conductive black and polyvinylidene fluoride
Alkene is dissolved in N-Methyl pyrrolidone according to the ratio mixed grinding of 80%:10%:10% and is prepared into slurry；Contain admittedly in slurry
Amount is 50%.Then slurry being coated on carbon nano-tube film, coating thickness is 100 microns, and is placed in baking oven, 120 DEG C
Lower drying for 24 hours, obtains flexible electrical pole piece.Thickness of electrode is 50 microns；The loading content of carbon electrode active material in single electrode
For 2mg/cm2；
3) high-voltage ion gel film is prepared
By (Kynoar-hexafluoropropene) copolymer (PVDF-HFP) and ionic liquid electrolyte EMIBF4 according to 1:1
Ratio mixing, be added acetone as solvent.So that total volume is 20mL, solid content 20%.50 are heated under closed state
DEG C, it is kept for 24 hours, until being completely dissolved.Solution is poured into φ 90mm glass culture dish, obtains thickness after solvent volatilization
For 500 microns of gel electrolyte film.
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, as shown in figure 5, capacitance be 250F/g；Energy density is 106Wh/Kg；Charge and discharge
Capacity retention after circulation 10000 times is 90%, as shown in Figure 6.
Embodiment 2
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 0.005molL is added in graphene oxide water solution-1Ethylenedioxy thiophene, 0.02mol
L-1Camphorsulfonic acid and 0.005molL-1Ammonium persulfate, 0 DEG C at a temperature of, be stirred to react 48 hours, obtain graphite oxide
Alkene-Polyglycolic acid fibre composite material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, it is ground in 1:8 ratio
After be put into tube furnace and be fired to 700 DEG C of activation under an argon atmosphere, then washed at room temperature with dilute hydrochloric acid, be dry, obtaining graphite
The porous carbon composite nano-material of alkenyl；
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous material as active material, by active material, electrically conductive graphite and butadiene-styrene rubber according to
The ratio mixed grinding of 70%:20%:10%, is dissolved in ethyl alcohol and is prepared into slurry；Solid content is 50% in slurry.It then will slurry
Material is coated on carbon nano-tube film, and coating thickness is 20 microns, is then placed into baking oven, and dry acquisition for 24 hours is flexible at 120 DEG C
Electrode plate electrode, with a thickness of 10 microns, the load capacity of carbon electrode active material is 0.1mg/cm in single electrode2；
3) high-voltage ion gel film is prepared
By (Kynoar-hexafluoropropene) copolymer (PVDF-HFP) and ionic liquid electrolyte EMIBF4 according to 4:1
Ratio mixing, be added acetone as solvent.Overall solution volume 10mL, so that solid content is 5%.50 are heated under closed state
DEG C, it is kept for 24 hours, until being completely dissolved.Solution is poured into the glass culture dish of φ 90mm, is obtained after solvent volatilization thick
The gel electrolyte film that degree is 100 microns；
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, capacitance 147F/g, as shown in Figure 7；Energy density is 62Wh/Kg；Charge and discharge
Capacity retention after circulation 10000 times is 80%.
Embodiment 3
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 1molL is added in graphene oxide water solution-1Pyrroles, 2mol L-1To toluene sulphur
Acid and 1molL-1Ammonium persulfate, 25 DEG C at a temperature of, be stirred to react 12 hours, obtain graphene oxide-polypyrrole it is compound
Material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, tube furnace is put into after being ground in 1:8 ratio in argon atmosphere
Under be fired to 800 DEG C of activation, then washed at room temperature with dilute hydrochloric acid, be dry, obtaining graphene-based porous carbon composite nano-material；
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous material as active material, by active material, carbon nanotube and Kynoar according to
The ratio mixed grinding of 70%:20%:10%, is dissolved in N-Methyl pyrrolidone and is prepared into slurry；Solid content is in slurry
30%.Then slurry is coated on carbon nano-tube film, coating thickness is 500 microns, and is placed in baking oven, is done at 120 DEG C
It is dry to obtain flexible electrode plate electrode for 24 hours, with a thickness of 150 microns.The load capacity of carbon electrode active material is in single electrode
1.5mg/cm2。
3) high-voltage ion gel film is prepared
By (Kynoar-hexafluoropropene) copolymer (PVDF-HFP) and ionic liquid electrolyte EMIBF4 according to 2:1
Ratio mixing, be added acetone as solvent.Overall solution volume 50mL, solid content 50%.50 DEG C are heated under closed state
It is kept for 24 hours, until being completely dissolved.Solution is poured into φ 90mm glass culture dish, obtains gel electrolyte after solvent volatilization
Matter film, film thickness are 1 millimeter.
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, capacitance 160F/g；Energy density is 68Wh/Kg；Charge and discharge cycles 10000 times
Capacity retention afterwards is 85%.
Embodiment 4
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 0.01molL is added in graphene oxide water solution-1Thiophene, 0.5mol L-1To first
Benzene sulfonic acid and 0.01molL-1Ammonium persulfate, 0 DEG C at a temperature of, be stirred to react 48 hours, obtain the poly- thiophene of graphene oxide-
Pheno composite material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, tube furnace is put into after being ground in 1:2 ratio in argon
It is fired to 700 DEG C of activation under gas atmosphere, is then washed at room temperature with dilute hydrochloric acid, is dry, obtains that graphene-based porous carbon is compound to be received
Rice material.
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous material as active material, by active material, conductive black and Kynoar according to
The ratio mixed grinding of 60%:20%:20%, is dissolved in N-Methyl pyrrolidone and is prepared into slurry；Solid content is in slurry
60%.Then slurry is coated on carbon nano-tube film, coating thickness is 500 microns, and is placed in baking oven, is done at 120 DEG C
It is dry to obtain flexible electrode plate electrode overnight, with a thickness of 300 microns.The carbon electrode active material loading content of single electrode is 5mg/
cm2。
3) high-voltage ion gel film is prepared
By Kynoar-hexafluoropropylene copolymer (PVDF-HFP) and ionic liquid electrolyte EMIBF4 according to 4:1's
Acetone is added as solvent in ratio mixing.Overall solution volume 20mL, solid content 5%.It is heated to 50 DEG C under closed state, protects
It holds 24 hours until being completely dissolved.Solution is poured into the glass culture dish of φ 90mm, obtains gel electrolyte after solvent volatilization
Matter film, film thickness are 100 microns；
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stacks, and guarantees electrode coated material in flexible electrical pole piece
The side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, capacitance 120F/g；Energy density is 51Wh/Kg；Charge and discharge cycles 10000 times
Capacity retention afterwards is 85%.
Embodiment 5
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 0.2molL is added in graphene oxide water solution-1Aniline, 1mol L-1Sulfuric acid and
0.2molL-1Iron chloride, -10 DEG C at a temperature of, be stirred to react 24 hours, obtain graphene oxide-polyaniline composite material
And wash drying.By above-mentioned compound and potassium hydroxide, tube furnace is put into after being ground in 2:1 ratio and is forged under an argon atmosphere
It burns to 700 DEG C and activates, then washed at room temperature with dilute hydrochloric acid, is dry, obtaining graphene-based porous carbon composite nano-material；
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous material as active material, by active material, electrically conductive graphite and Kynoar according to
The ratio mixed grinding of 60%:20%:20%, is dissolved in N-Methyl pyrrolidone and is prepared into slurry；Solid content is in slurry
45%.Then slurry is coated on carbon nano-tube film, coating thickness is 200 microns, baking oven is then placed into, at 120 DEG C
It is dried overnight and obtains flexible electrode plate electrode, thickness of electrode is 90 microns；Carbon electrode active material loading content in single electrode
For 0.6mg/cm2。
3) high-voltage ion gel film is prepared
By Kynoar-hexafluoropropylene copolymer (PVDF-HFP) and ionic liquid electrolyte EMIBF4 according to 1:4's
Acetone is added as solvent in ratio mixing.Liquor capacity is 20mL, solid content 20%.50 DEG C of guarantors are heated under closed state
It holds 24 hours, until being completely dissolved.Solution is poured into φ 90mm glass culture dish, obtains gel electrolyte after solvent volatilization
Film, film thickness are 800 microns；
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, capacitance 180F/g, as shown in Figure 8；Energy density is 75Wh/Kg；Charge and discharge
Capacity retention after circulation 10000 times is 82%.
Embodiment 6
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 0.1molL is added in graphene oxide water solution-1Pyrroles, 2mol L-1Hydrochloric acid and
0.1molL-1Ammonium persulfate, 25 DEG C at a temperature of, be stirred to react 12 hours, obtain graphene oxide-polypyrrole composite wood
Expect and washs drying.By above-mentioned compound and potassium hydroxide, tube furnace is put into after being ground in 1:4 ratio under an argon atmosphere
700 DEG C of activation are fired to, is then washed at room temperature with dilute hydrochloric acid, is dry, obtaining graphene-based porous carbon composite nano-material；
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous material as active material, by active material, conductive black and Kynoar according to
The ratio mixed grinding of 90%:0%:10%, is dissolved in N-Methyl pyrrolidone and is prepared into slurry；Solid content is in slurry
60%.Then slurry is coated on carbon nano-tube film, coating thickness is 200 microns, and is placed in baking oven, is done at 120 DEG C
It is dry to obtain flexible electrode plate electrode overnight, with a thickness of 110 microns；The carbon electrode active material loading content of single electrode is
1.0mg/cm2。
3) high-voltage ion gel film is prepared
Polyvinyl alcohol (PEO) and ionic liquid electrolyte EMITFSI are mixed according to the ratio of 1:4, acetone conduct is added
Solvent.Liquor capacity is 20mL, solid content 10%.It is heated to 50 DEG C under closed state, is kept for 24 hours until being completely dissolved.
Solution is poured into the glass culture dish of φ 90mm, gel electrolyte film is obtained after solvent volatilization, film thickness is 500 micro-
Rice；
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, capacitance 119F/g；Energy density is 50Wh/Kg；Charge and discharge cycles 10000 times
Capacity retention afterwards is 98%.
Embodiment 7
1) electrode active material is prepared
Natural graphite is oxidized to by graphite oxide using Hummers method, and is prepared by probe sonication dispersion removing
Graphene oxide water solution.Then 1molL is added in graphene oxide water solution-1Pyrroles, 2mol L-1To toluene sulphur
Acid and 1molL-1Ammonium persulfate, 25 DEG C at a temperature of, be stirred to react 12 hours, obtain graphene oxide-polypyrrole it is compound
Material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, tube furnace is put into after being ground in 1:8 ratio in argon atmosphere
Under be fired to 800 DEG C of activation, then washed at room temperature with dilute hydrochloric acid, be dry, obtaining graphene-based porous carbon composite nano-material；
2) flexible electrical pole piece is prepared
Using above-mentioned graphene-based porous material as active material, active material, conductive carbon fibres peacekeeping Kynoar are pressed
According to the ratio mixed grinding of 75%:15%:10%, it is dissolved in N-Methyl pyrrolidone and is prepared into slurry；Solid content is in slurry
30%.Then slurry is coated on carbon nano-tube film, coating thickness is 500 microns, and is placed in baking oven, is done at 120 DEG C
It is dry to obtain flexible electrode plate electrode for 24 hours, with a thickness of 150 microns.The carbon electrode active material loading content of single electrode is
1.6mg/cm2。
3) high-voltage ion gel film is prepared
By (Kynoar-hexafluoropropene) copolymer (PVDF-HFP) and ionic liquid electrolyte EMIPF6 according to 2:1
Ratio mixing, be added acetone as solvent.Overall solution volume 50mL, solid content 50%.50 DEG C are heated under closed state
It is kept for 24 hours, until being completely dissolved.Solution is poured into φ 90mm glass culture dish, obtains gel electrolyte after solvent volatilization
Matter film, film thickness are 1 millimeter.
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 3.5V, capacitance 150F/g；Energy density is 64Wh/Kg；Charge and discharge cycles 10000 times
Capacity retention afterwards is 88%.
Embodiment 8
1) electrode active material is prepared
Using Chengdu organic chemical reagent Products carbon nanometer single-wall carbon tube.
2) flexible electrical pole piece is prepared
Using above-mentioned carbon nanotube as active material, active material and Kynoar are mixed according to the ratio of 90%:10%
Grinding is closed, is dissolved in N-Methyl pyrrolidone and is prepared into slurry；Solid content is 45% in slurry.Then slurry is received coated on carbon
On mitron film, coating thickness is 200 microns, is then placed into baking oven, is dried overnight at 120 DEG C and obtains flexible electrical pole piece electricity
Pole, thickness of electrode are 90 microns；The carbon electrode active material loading content of single electrode is 0.9mg/cm2。
3) high-voltage ion gel film is prepared
(Kynoar-hexafluoropropene) copolymer (PVDF) and ionic liquid EMIPF6 are mixed according to the ratio of 1:4,
Acetone is added as solvent.Liquor capacity is 20mL, solid content 20%.50 DEG C are heated under closed state to be kept for 24 hours,
Until being completely dissolved.Solution is poured into φ 90mm glass culture dish, obtains gel electrolyte film, thickness after solvent volatilization
It is 800 microns；
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte film-flexible electrical pole piece sequence stack, and guarantee in flexible electrical pole piece be coated with electrode
The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will preparation
Flexible super capacitor be connected to through French BioLogic electrochemical workstation, it is soft that this is obtained by constant current charge-discharge test
Property supercapacitor voltage be 4V, capacitance 155F/g, as shown in Figure 8；Energy density is 86Wh/Kg；Charge and discharge follow
Capacity retention after ring 10000 times is 79%.
Comparative example 1
1) electrode active material prepares graphene: natural graphite being oxidized to graphite oxide using Hummers method, and is led to
It crosses probe sonication dispersion removing and is prepared into graphene oxide water solution.Then by graphene oxide water solution washing, simultaneously vacuum is done
It is dry.By above-mentioned graphene oxide shown in Fig. 9 and potassium hydroxide, tube furnace is put into after being ground in 1:4 ratio in argon gas gas
It is fired to 700 DEG C of activation under atmosphere, is then washed at room temperature with dilute hydrochloric acid, is dry, obtaining pure grapheme material.
2) prepared by flexible electrical pole piece: using above-mentioned graphene-based porous material as active material, by active material, conductive black
With Kynoar according to the ratio mixed grinding of 80%:10%:10%, it is dissolved in N-Methyl pyrrolidone and is prepared into slurry；
Solid content is 50% in slurry.Then slurry is coated on carbon nano-tube film, coating thickness is 100 microns, and is placed in
Baking oven is dried overnight at 120 DEG C and obtains flexible electrode plate electrode.Thickness of electrode is 50 microns；Carbon electrode activity in single electrode
The loading content of material is 2mg/cm2。
3) prepared by high-voltage ion gel film: by macromolecule PVDF-HFP and ionic liquid EMIBF4 according to the ratio of 1:1
Acetone is added as solvent in example mixing.So that total volume is 20mL, solid content 20%.50 DEG C of guarantors are heated under closed state
It holds 24 hours until being completely dissolved.Solution is poured into φ 90mm glass culture dish, is obtained after solvent volatilization micro- with a thickness of 500
The gel electrolyte film of rice.
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte membrane electrode-flexible electrical pole piece sequence stacks, and guarantees to coat in flexible electrical pole piece
There is the one side of electrode material to contact with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.
The flexible super capacitor of preparation is connected to through French BioLogic electrochemical workstation, is obtained by constant current charge-discharge test
The voltage for obtaining the flexible super capacitor is 3.5V, capacitance 80F/g；Energy density is 34Wh/Kg；Charge and discharge cycles
Capacity retention after 10000 times is 98%.
2 hydrogel electrolyte of comparative example
1) it prepares electrode active material: natural graphite being oxidized to by graphite oxide using Hummers method, and passes through probe
Ultrasonic disperse removing is prepared into graphene oxide water solution.Then 0.05molL is added in graphene oxide water solution-1Benzene
Amine, 1mol L-1Perchloric acid and 0.05molL-1Ammonium persulfate, -10 DEG C at a temperature of, be stirred to react 24 hours, obtain
Graphene oxide-polyaniline composite material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, it is ground in 1:4 ratio
After be put into tube furnace and be fired to 700 DEG C of activation under an argon atmosphere, then washed at room temperature with dilute hydrochloric acid, be dry, obtaining graphite
The porous carbon composite nano-material of alkenyl.
2) flexible electrical pole piece is prepared: using above-mentioned graphene-based porous material as active material, by active material, conductive black
With Kynoar according to the ratio mixed grinding of 80%:10%:10%, it is dissolved in N-Methyl pyrrolidone and is prepared into slurry；
Solid content is 50% in slurry.Then slurry is coated on carbon nano-tube film, coating thickness is 100 microns, and is placed in
Baking oven is dried overnight at 120 DEG C and obtains flexible electrode plate electrode.Thickness of electrode is 50 microns；Carbon electrode activity in single electrode
The loading content of material is 2mg/cm2。
3) it prepares normal pressure hydrogel thin film: 1g polyethylene PVP is added to 10mL 1mol L-1Aqueous sulfuric acid, electromagnetism
95 DEG C are heated under stirring until solution becomes to clarify.Solution is poured into φ 90mm plastic culture dish, after solvent volatilization, is obtained
Obtain the gel electrolyte film with a thickness of 100 microns.
4) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 2) to prepare and a piece of step 3), according to soft
Property electrode slice-ionic gel electrolyte membrane electrode-flexible electrical pole piece sequence stacks, and guarantees to coat in flexible electrical pole piece
There is the one side of electrode material to contact with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.
The flexible super capacitor of preparation is connected to through French BioLogic electrochemical workstation, is obtained by constant current charge-discharge test
The voltage for obtaining the flexible super capacitor is 1V, capacitance 300F/g；Energy density is 10Wh/Kg；Charge and discharge cycles
Capacity retention after 10000 times is 92%.
Application examples
As shown in Figure 10, it will can be driven after high voltage flexible super capacitor charging prepared according to the method for embodiment 1
Move 30 LED operations.In addition, capacitor bending does not influence the working condition of capacitor.
Claims (10)
1. a kind of high voltage flexible solid-state supercapacitor, it is characterised in that: the high voltage flexible solid-state supercapacitor
Including gel electrolyte film, flexible current-collecting body, electrode and encapsulated layer；
The gel electrolyte film is high-voltage ion gel；High-voltage ion gel include macromolecule matrix material and from
Sub- liquid electrolyte, the macromolecule matrix of macromolecule matrix material are in space net structure, and ionic liquid electricity is full of in gap
Xie Zhi forms high-voltage ion gel film；The macromolecule matrix material is Kynoar (PVdF) or (polyvinylidene fluoride
Alkene-hexafluoropropene) copolymer (PVDF-HFP) or polyoxyethylene (PEO)；The ionic liquid electrolyte is by organic cation
With the room temperature liquid dissolved salt of anion composition；The ionic liquid electrolyte is 1- ethyl-3-methylimidazole tetrafluoroborate
(EMIBF4) or 1- ethyl-3-methylimidazole hexafluorophosphate (EMIPF6) or bis- (the trifluoromethyl sulphurs of 1- ethyl-3-methylimidazole
Acyl) or sub- peace salt (EMITFSI)；Gel film with a thickness of 10 microns -5 millimeters；
The electrode is coated on flexible current-collecting body surface, constitutes flexible electrical pole piece；According to encapsulated layer-flexible electrical pole piece-gel electricity
Solution plasma membrane-flexible electrical pole piece-encapsulated layer sequence stacks, and encapsulated layer wraps up flexible electrical pole piece-gel electrolyte membrane-flexible electrode
Piece；
The active material of the electrode is the graphene-based porous carbon nanometer that graphene oxide-conducting polymer calcining and activating is formed
Material, preparation method are as follows；
Natural graphite is oxidized to by graphite oxide using Hummers method, and oxidation stone is prepared by probe sonication dispersion removing
Black aqueous solution；Then conducting polymer monomer, dopant and oxidant ammonium persulfate are added in graphene oxide water solution,
- 10 DEG C to 25 DEG C at a temperature of, be stirred to react 1-48 hours, obtain graphene oxide-conducting polymer composite material, and wash
Wash drying；Tube furnace is put into argon gas gas after graphene oxide-conducting polymer composite material and potassium hydroxide are ground
Then calcining and activating under atmosphere is washed at room temperature with dilute hydrochloric acid, is dry, obtaining graphene-based porous carbon composite nano-material；
The voltage of the flexible super capacitor is 3.5-4V, capacitance 100-250F/g；Energy density is 50-106Wh/
Kg；Capacity retention after charge and discharge cycles 10000 times is 80-98%.
2. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that: the graphene oxide
Contain 0.005-1mol L in aqueous solution-1Conducting polymer monomer, 0.01-2molL-1Dopant and 0.005-1molL-1
Ammonium persulfate；
Preparing graphene-conducting polymer composite material reaction time is 24 hours；
The conducting polymer monomer is one of aniline, pyrroles, thiophene and ethylenedioxy thiophene or a variety of；
The dopant is one of sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid or a variety of；
The ratio of the graphene oxide-conducting polymer composite material and potassium hydroxide is 2:1 to 1:8；
The calcination temperature of described synthesizing graphite alkene Quito hole carbon nanomaterial is 500 DEG C -900.
3. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that the graphene oxide
Aqueous solution contains 0.05molL-1Conducting polymer monomer, 1molL-1Dopant and 0.05molL-1Ammonium persulfate；It is described
Conducting polymer monomer is aniline monomer；The dopant is perchloric acid；Graphene oxide-conducting polymer composite material with
The ratio of potassium hydroxide is 1:4；The calcination temperature of synthesizing graphite alkene Quito hole carbon nanomaterial is 700 DEG C.
4. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that: the macromolecule matrix material
Material is (Kynoar-hexafluoropropene) copolymer (PVDF-HFP).
5. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that: the ionic liquid electricity
Xie Zhiwei 1- ethyl-3-methylimidazole tetrafluoroborate (EMIBF4).
6. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that: the electrode with a thickness of
5 microns to 500 microns；The loading content of carbon electrode active material is 0.1-5mg/cm in single electrode2。
7. the method for preparing high voltage flexible solid-state supercapacitor described in claim 1, it is characterised in that: the preparation side
Method the following steps are included:
1) flexible electrical pole piece is prepared
Using the graphene-based porous carbon composite nano-material as active material, by active material, conductive agent and binder according to
(60-95) %:(0-20) %:(5-20) % ratio mixed grinding, be dissolved in solvent, be prepared into slurry；Solid content is in slurry
30%-60%；Then slurry is coated on flexible current-collecting body, coating thickness is 20 microns to 500 microns, is coated with slurry
Flexible current-collecting body be placed in baking oven, at 120 DEG C drying obtain electrode slice for 24 hours；
The thickness of electrode of flexible electrode on piece is 10 microns to 200 microns；The load of carbon electrode active material contains in single electrode
Amount is 0.1-5mg/cm2；
2) high-voltage ion gel film is prepared
Polymer-based bottom material and ionic liquid electrolyte are mixed according to the ratio of 1:4-4:1, acetone is added as solvent；It is molten
Liquid total volume is 10 to 50mL, so that solid content is 5%-60%；It is heated to 50 DEG C under closed state, is kept for 24 hours, until
Polymer-based bottom material is completely dissolved；Solution is poured into glass culture dish, obtains gel electrolyte film after solvent volatilization；
Gel electrolyte film obtained with a thickness of 100 microns -1 millimeter；
3) gel electrolyte film made from the flexible electrical pole piece for taking two panels step 1) to prepare and a piece of step 2), according to flexible electrical
Pole piece-ionic gel electrolyte film-flexible electrical pole piece sequence stacks, and the one side of electrode material is coated in flexible electrical pole piece
It is contacted with electrolytic thin-membrane；Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained；
Conductive agent is one of conductive black, electrically conductive graphite, carbon nanotubes, nano carbon fiber, graphene in the step 1)
Or it is a variety of；
Binder is Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber in the step 1)；
Solvent is N-Methyl pyrrolidone or ethyl alcohol in the step 1).
8. preparing the method for high voltage flexible solid-state supercapacitor according to claim 6, it is characterised in that: described
In step 1), the conductive agent is conductive black；Binder is Kynoar；Solvent is N-Methyl pyrrolidone；Collector
For carbon nanotube self-supporting film；The ratio of active material, conductive agent and binder is 80%:10%:10%.
9. preparing the method for high voltage flexible solid-state supercapacitor according to claim 6, it is characterised in that: described
In step 1), the loading content of carbon electrode active material is 0.5-2mg/cm in single electrode2。
10. preparing the method for high voltage flexible solid-state supercapacitor according to claim 6, it is characterised in that: described
Step 2) in, the ratio of polymer-based bottom material and ionic liquid is 1:1；Polymer-based bottom material, ionic liquid electrolyte
It is 20% with the total content of bottom material polymer-based in the mixed solution of acetone and ionic liquid electrolyte.
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| FR3098003B1 (en) * | 2019-06-26 | 2022-07-15 | Solvionic | Method and device for manufacturing electrodes for an ionic liquid-based supercapacitor and method for manufacturing such a supercapacitor |
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| CN110970233B (en) * | 2019-12-26 | 2021-09-24 | 上海交通大学 | Preparation method of micro super capacitor based on conjugated organic framework material |
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| CN111504519B (en) * | 2020-04-20 | 2022-03-01 | 河北工业大学 | Flexible cable type touch sensor |
| CN112834086B (en) * | 2020-12-31 | 2022-02-15 | 华中科技大学 | Ultra-sensitive capacitive flexible pressure sensor and preparation method thereof |
| CN113203504B (en) * | 2021-04-01 | 2022-05-06 | 上海交通大学 | Flexible wearable pressure sensor with ultrahigh capacitance and pressure sensor array |
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