CN107919233A - 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 PDF

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CN107919233A
CN107919233A CN201710969308.0A CN201710969308A CN107919233A CN 107919233 A CN107919233 A CN 107919233A CN 201710969308 A CN201710969308 A CN 201710969308A CN 107919233 A CN107919233 A CN 107919233A
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flexible
electrode
pole piece
electrical pole
flexible electrical
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CN107919233B (en
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王凯
马衍伟
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Institute of Electrical Engineering of CAS
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    • 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
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • 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
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, 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
    • 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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  • Electric Double-Layer Capacitors Or The Like (AREA)

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, forms flexible electrical pole piece；Order according to encapsulated layer flexible electrical pole piece gel electrolyte membrane flexible electrical pole piece encapsulated layer stacks, encapsulated layer parcel flexible electrical pole piece gel electrolyte membrane flexible electrical pole piece.Electrode active material and flexible electrical pole piece are prepared first, then prepare ionic gel and be cast into film, two flexible electrical pole pieces and gel electrolyte are stacked according to the order 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

A kind of high voltage flexible solid-state supercapacitor and preparation method thereof
Technical field
The present invention relates to a kind of ultracapacitor and preparation method thereof.
Background technology
With continuing to bring out for wearable flexible intelligent equipment, exploitation is small, light weight, flexible section are rollable energy storage Device becomes the current research field that everybody pays close attention to.Ultracapacitor 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, distortion 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 ultracapacitor2, it can be seen that its energy density depends primarily upon 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 Can flexible electrode to improve capacitance C.The voltage window of ultracapacitor depends on used electrolyte system.Current flexible electrical The electrolyte that container uses is generally aqueous solution or aquogel system, its 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, its voltage window is up to 5V or so.Far above the voltage range of aqueous electrolyte, because of referred to herein as high voltage electrolytes. Currently, in the research of typical ultracapacitor, the related of voltage range has been improved using ionic liquid and has been reported.But Flexible super capacitor field, there has been no correlation to report.Further, since viscosity of il is big, diffusional resistance is big, pin Targeted design is carried out to carbon-based electrode material to ionic liquid, obtaining the novel high-performance electrode of suitable ion liquid system is Develop the important step of high voltage flexible capacitor.
In addition, for flexible bendable device, device can cause the leakage of liquid electrolyte using the multiple bending of process. Therefore in order to overcome leakage hidden danger, and easily prepared encapsulation, solid electrolyte is widely used that in flexible device.Therefore, Need ionic liquid and macromolecule matrix material will be mixed, be prepared into high-tension ionic gel.Wherein, macromolecule matrix is in Space net structure, is filled with ionic liquid electrolyte in its gap, collectively forms ionic gel；Develop high performance carbon base electrode It is the important channel for obtaining high-performance flexible ultracapacitor of future generation with high-voltage ion gel.But there has been no base at present Reported in the flexible super capacitor of high-voltage ion liquid gel.
The content of the invention
In order to overcome the relatively low problem of the energy density of current flexible solid-state supercapacitor, the present invention proposes a kind of high voltage Flexible solid-state supercapacitor and preparation method thereof, intends improving device energy density by lifting 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 binding agent.The electrode is coated on flexible current-collecting body surface Face, forms flexible electrical pole piece.Gel electrolyte film, flexible current-collecting body, electrode and encapsulated layer are according to encapsulated layer-flexible electrode The order arrangement of piece-gel electrolyte membrane-flexible electrical pole piece-encapsulated layer stacks.Encapsulated layer parcel flexible electrical pole piece-gel electrolyte Plasma membrane-flexible electrical pole piece.
The active material of the electrode for graphene, carbon nanotubes, one kind in porous charcoal or by it is several form it is compound Thing；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, and ionic liquid electrolyte is full of in its gap, and 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 copolymerized for (Kynoar-hexafluoropropene) Thing (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 tetrafluoroborates (EMIBF4), 1- ethyl-3-methylimidazoles hexafluorophosphate (EMIPF6) and double (the trifluoromethyl sulphurs of 1- ethyl-3-methylimidazoles Acyl) Asia peace salt (EMITFSI)；Preferably, ionic liquid electrolyte is 1- ethyl-3-methylimidazole tetrafluoroborates (EMIBF4)。
High voltage flexible solid-state supercapacitor of the present invention can as gel electrolyte, voltage using high-voltage ion gel Up to 3~4.5V, this is different from the voltage class of traditional 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 ultracapacitor of the present invention is as follows：
Electrode active material and flexible electrical pole piece are prepared first, ionic gel is then prepared and is cast into film, by two Flexible electrical pole piece and gel electrolyte are stacked together according to the order 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.
Comprise the following steps that：
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：Native graphite is oxidized to by oxygen using Hummers methods Graphite, and stripping is disperseed by probe sonication and is prepared into graphene oxide water solution.Then in graphene oxide water solution Conducting polymer monomer, dopant and oxidant ammonium persulfate are added, at a temperature of -10 DEG C to 25 DEG C, stirring reaction 1-48 Hour, graphene oxide-conducting polymer composite material is obtained, and wash drying.By above-mentioned graphene oxide-conducting polymer Composite material is put into tube furnace calcining and activating under an argon atmosphere after being ground with potassium hydroxide, then uses dilute hydrochloric acid at room temperature Washing, dry, the graphene-based porous carbon nanomaterial of acquisition.
Wherein, 0.005-1mol L are 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.
When the reaction time for preparing graphene-conducting polymer composite material is preferably 24 small.
The conducting polymer monomer is the one or more in aniline, pyrroles, thiophene and ethylenedioxy thiophene；It is preferred that , the conducting polymer monomer is aniline monomer.
The dopant is the one or more in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid, 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 calcining heat 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 binding agent according to (60-95) %：(0-20) %：The ratio mixed grinding of (5-20) %, is dissolved in solvent, is prepared into slurry；Solid content is in slurry 30%-60%.By slurry coated on flexible current-collecting body, coating thickness is 20-500 microns, baking oven is then placed into, 120 Dry 24h obtains electrode slice at DEG C.
The conductive agent for conductive black, electrically conductive graphite, carbon nanotubes, nano carbon fiber, one kind in graphene or It is a variety of；It is preferred that conductive black.
The binding agent is Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber；It is preferred that Kynoar.
Solvent is 1-methyl-2-pyrrolidinone, deionized water or ethanol；Preferably, solvent is 1-methyl-2-pyrrolidinone.Activity The ratio of material, conductive agent and binding agent 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
By polymer-based bottom material and ionic liquid electrolyte according to 1:4~4:1 ratio mixing, adds acetone as molten Agent.Overall solution volume is 10-50mL so that solid content is 5%~60%.50 DEG C, when holding 24 is small are heated under closed state, Until polymer-based bottom material is completely dissolved.Solution is poured into glass culture dish, gel electrolyte is obtained after solvent volatilization Film.
The macromolecule matrix material and the ratio of ionic liquid electrolyte are preferably 1:1.
The thickness of the gel electrolyte film obtained is 100 microns -1 millimeter, and preferable thickness is 500 microns.
Solid content is preferably 20% in the step 3).
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Then polydimethylsiloxane thin-film package is used, obtains flexible super capacitor.
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 following advantages：
1), compared to traditional water system electrolyte, greatly improved as electrolyte using high-tension ion liquid system 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 beneficial to the biography of electric charge and ion It is defeated, and Jie's micropore is used to store more charge, this structure is adapted to ionic liquid electrolyte system, effectively lifts 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 of flexible bendable device is avoided, simplifies packaging technology.
4) high voltage flexible solid-state supercapacitor specific capacitance, cyclical stability and the energy density prepared, also with good Good bending resistance.
Brief description of the drawings
The cross-sectional view of Fig. 1 high voltage flexible solid-state supercapacitors；
The photo in kind of Fig. 2 high voltage flexible solid-state supercapacitors；
The scanning electron microscopic picture of graphene oxide-conducting polymer composite precursor prepared by Fig. 3 embodiments 1；
The scanning electron microscopic picture of graphene-based carbon composite nano structure electrode material prepared by Fig. 4 embodiments 1；
The charging and discharging curve figure of flexible solid-state supercapacitor prepared by Fig. 5 embodiments 1；
The cycle charge-discharge stability curve figure of flexible solid-state supercapacitor prepared by Fig. 6 embodiments 1；
The capacitance curve map of flexible solid-state supercapacitor prepared by Fig. 7 embodiments 2；
The capacitance curve map of flexible solid-state supercapacitor prepared by Fig. 8 embodiments 5；
The electron microscopic picture of graphene oxide prepared by Fig. 9 comparative examples 1；
Flexible solid-state supercapacitor prepared by Figure 10 application examples lights the photo in kind of 30 LED light.
Embodiment
The present invention is further illustrated below in conjunction with the drawings and specific embodiments.
Preparation method step of the present invention is as follows：
1) electrode active material is prepared：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：Native graphite is oxidized to by oxygen using Hummers methods Graphite, and stripping is disperseed by probe sonication and is prepared into graphene oxide water solution.Then in graphene oxide water solution Conducting polymer monomer, dopant and oxidant ammonium persulfate are added, at a temperature of -10 DEG C to 25 DEG C, stirring reaction 1-48 Hour, obtain graphene oxide-conducting polymer composite material and wash drying.By above-mentioned graphene oxide-conducting polymer Composite material presses 2 with potassium hydroxide:1 to 1:8 ratio is put into tube furnace calcining and activating under an argon atmosphere after being ground, so Washed at room temperature with dilute hydrochloric acid afterwards, is dry, obtaining graphene-based porous carbon composite nano-material.
Wherein, 0.005-1mol L are contained in the graphene oxide water solution-1Conducting polymer monomer, 0.01- 2mol L-1Dopant and 0.005-1mol L-1Ammonium persulfate；Preferable graphene oxide-conducting polymer composite material Contain 0.05molL-1Conducting polymer monomer, 1molL-1Dopant, 0.05mol L-1Ammonium persulfate；
When the reaction time for preparing graphene oxide-conducting polymer composite material is preferably 24 small；
The conducting polymer monomer is the one or more in aniline, pyrroles, thiophene and ethylenedioxy thiophene, preferably For aniline monomer；
The dopant is the one or more in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid, excellent Elect perchloric acid as.
The ratio of graphene oxide-conducting polymer composite material and potassium hydroxide is 2:1 to 1:8；Preferably 1:4.
The calcining heat 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 binding agent according to (60-95) %：(0-20) %：The ratio mixed grinding of (5-20) %, is dissolved in solvent and is prepared into slurry；Solid content is in slurry 30%-60%.Then by slurry coated on flexible current-collecting body, coating thickness is 20 microns to 500 microns, is positioned over baking oven, Dry 24h obtains electrode at 120 DEG C.
The wherein described conductive agent is one kind or more in conductive black, electrically conductive graphite, carbon nanotubes, conductive Carbon fibe Kind, preferably conductive black.
The binding agent is Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber, preferably Kynoar.
The solvent is 1-methyl-2-pyrrolidinone, deionized water or ethanol, preferably 1-methyl-2-pyrrolidinone.
The ratio of active material, conductive agent and binding agent 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
By polymer-based bottom material and ionic liquid electrolyte according to 1:4~4:1 ratio mixing, adds acetone as molten Agent.Overall solution volume is 10-50mL, and solid content is 5%~80%.50 DEG C are heated in the closed state, when holding 24 is small, directly To being completely dissolved.Solution is poured into glass culture dish, gel electrolyte film is obtained after solvent volatilization.
The ratio of polymer-based bottom material and ionic liquid electrolyte is preferably 1:1.
The thickness of the gel electrolyte film is 100 microns -1 millimeter, and preferred thickness is 500 microns.
Solid content is preferably 20%.
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte membrane electrode-flexible electrical pole piece stacks, and ensures to coat in flexible electrical pole piece The one side for having electrode material is contacted 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
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into Graphene oxide water solution.Then 0.05molL is added in graphene oxide water solution-1Aniline, 1mol L-1Perchloric acid And 0.05molL-1Ammonium persulfate, at a temperature of -10 DEG C, stirring reaction 24 it is small when, obtain graphene oxide-polyaniline answer Condensation material simultaneously washs drying, as shown in Figure 3.
Above-mentioned compound and potassium hydroxide are pressed 1:4 ratios are put into tube furnace after being ground and are fired under an argon atmosphere 700 DEG C of activation, are then washed with dilute hydrochloric acid, are dry, obtaining graphene-based porous carbon nanomaterial, as shown in Figure 4 at room temperature.
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 according to 80%：10%：10% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry；Contain admittedly in slurry Measure as 50%.Then by slurry coated on carbon nano-tube film, coating thickness is 100 microns, and is positioned over baking oven, 120 DEG C Lower dry 24h, 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, add acetone as solvent.So that cumulative volume is 20mL, solid content 20%.50 are heated under closed state DEG C, when holding 24 is small, until being completely dissolved.Solution is poured into φ 90mm glass culture dish, thickness is obtained after solvent volatilization For 500 microns of gel electrolyte film.
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 3.5V, as shown in figure 5, capacitance is 250F/g；Energy density is 106Wh/Kg；Discharge and recharge Capacity retention after circulating 10000 times is 90%, as shown in Figure 6.
Embodiment 2
1) electrode active material is prepared
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into 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, at a temperature of 0 DEG C, stirring reaction 48 it is small when, obtain graphite oxide Alkene-Polyglycolic acid fibre composite material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, by 1:8 ratios are ground 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 70%：20%：10% ratio mixed grinding, is dissolved in ethanol and is prepared into slurry；Solid content is 50% in slurry.Then will slurry For material coated on carbon nano-tube film, coating thickness is 20 microns, is then placed into baking oven, and dry 24h acquisitions are flexible at 120 DEG C Electrode plate electrode, thickness are 10 microns, and 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, add acetone as solvent.Overall solution volume 10mL so that solid content 5%.50 are heated under closed state DEG C, when holding 24 is small, until being completely dissolved.Solution is poured into the glass culture dish of φ 90mm, is obtained after solvent volatilization thick Spend the gel electrolyte film for 100 microns；
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 3.5V, capacitance 147F/g, as shown in Figure 7；Energy density is 62Wh/Kg；Discharge and recharge Capacity retention after circulating 10000 times is 80%.
Embodiment 3
1) electrode active material is prepared
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into Graphene oxide water solution.Then 1molL is added in graphene oxide water solution-1Pyrroles, 2mol L-1To toluene sulphur Acid and 1molL-1Ammonium persulfate, at a temperature of 25 DEG C, stirring reaction 12 it is small when, obtain graphene oxide-polypyrrole it is compound Material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, by 1:8 ratios are put into tube furnace in argon gas atmosphere after being ground 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 nanotubes and Kynoar according to 70%：20%：10% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry；Solid content is in slurry 30%.Then by slurry coated on carbon nano-tube film, coating thickness is 500 microns, and is positioned over baking oven, is done at 120 DEG C Dry 24h obtains flexible electrode plate electrode, and thickness is 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, add acetone as solvent.Overall solution volume 50mL, solid content 50%.50 DEG C are heated under closed state Keep 24 it is small when, until be completely dissolved.Solution is poured into φ 90mm glass culture dish, gel electrolyte is obtained after solvent volatilization Matter film, film thickness are 1 millimeter.
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 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
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into 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, at a temperature of 0 DEG C, stirring reaction 48 it is small when, obtain graphene oxide-poly- thiophene Fen composite material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, by 1:2 ratios are put into tube furnace in argon after being ground 700 DEG C of activation are fired under gas atmosphere, is then washed at room temperature with dilute hydrochloric acid, is dry, obtain 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 60%：20%：20% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry；Solid content is in slurry 60%.Then by slurry coated on carbon nano-tube film, coating thickness is 500 microns, and is positioned over baking oven, is done at 120 DEG C Dry to obtain flexible electrode plate electrode overnight, thickness is 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 Ratio mixes, and adds acetone as solvent.Overall solution volume 20mL, solid content 5%.50 DEG C are heated under closed state, is protected Hold 24 it is small when until be completely dissolved.Solution is poured into the glass culture dish of φ 90mm, gel electrolyte is obtained after solvent volatilization Matter film, film thickness are 100 microns；
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures 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 prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 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
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into Graphene oxide water solution.Then 0.2molL is added in graphene oxide water solution-1Aniline, 1mol L-1Sulfuric acid and 0.2molL-1Iron chloride, at a temperature of -10 DEG C, stirring reaction 24 it is small when, obtain graphene oxide-polyaniline composite material And wash drying.By above-mentioned compound and potassium hydroxide, by 2:1 ratio is put into tube furnace after being ground and forges under an argon atmosphere Burn to 700 DEG C of activation, 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 60%：20%：20% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry；Solid content is in slurry 45%.Then by slurry coated on carbon nano-tube film, coating thickness is 200 microns, is then placed into baking oven, 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 Ratio mixes, and adds acetone as solvent.Liquor capacity is 20mL, solid content 20%.50 DEG C of guarantors are heated under closed state Hold 24 it is small when, until be completely dissolved.Solution is poured into φ 90mm glass culture dish, gel electrolyte is obtained after solvent volatilization Film, film thickness are 800 microns；
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 3.5V, capacitance 180F/g, as shown in Figure 8；Energy density is 75Wh/Kg；Discharge and recharge Capacity retention after circulating 10000 times is 82%.
Embodiment 6
1) electrode active material is prepared
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into Graphene oxide water solution.Then 0.1molL is added in graphene oxide water solution-1Pyrroles, 2mol L-1Hydrochloric acid and 0.1molL-1Ammonium persulfate, at a temperature of 25 DEG C, stirring reaction 12 it is small when, obtain graphene oxide-polypyrrole composite wood Expect and wash drying.By above-mentioned compound and potassium hydroxide, by 1:4 ratios are put into tube furnace under an argon atmosphere after being ground 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 90%：0%：10% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry；Solid content is in slurry 60%.Then by slurry coated on carbon nano-tube film, coating thickness is 200 microns, and is positioned over baking oven, is done at 120 DEG C Dry to obtain flexible electrode plate electrode overnight, thickness is 110 microns；The carbon electrode active material loading content of single electrode is 1.0mg/cm2。
3) high-voltage ion gel film is prepared
By polyvinyl alcohol (PEO) and ionic liquid electrolyte EMITFSI according to 1:4 ratio mixing, adds acetone conduct Solvent.Liquor capacity is 20mL, solid content 10%.50 DEG C are heated under closed state, until being completely dissolved when holding 24 is small. Solution is poured into the glass culture dish of φ 90mm, gel electrolyte film is obtained after solvent volatilization, film thickness is micro- for 500 Rice；
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 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
Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into Graphene oxide water solution.Then 1molL is added in graphene oxide water solution-1Pyrroles, 2mol L-1To toluene sulphur Acid and 1molL-1Ammonium persulfate, at a temperature of 25 DEG C, stirring reaction 12 it is small when, obtain graphene oxide-polypyrrole it is compound Material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, by 1:8 ratios are put into tube furnace in argon gas atmosphere after being ground 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 75%：15%：10% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry；Solid content is in slurry 30%.Then by slurry coated on carbon nano-tube film, coating thickness is 500 microns, and is positioned over baking oven, is done at 120 DEG C Dry 24h obtains flexible electrode plate electrode, and thickness is 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, add acetone as solvent.Overall solution volume 50mL, solid content 50%.50 DEG C are heated under closed state Keep 24 it is small when, until be completely dissolved.Solution is poured into φ 90mm glass culture dish, gel electrolyte is obtained after solvent volatilization Matter film, film thickness are 1 millimeter.
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 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 nanotubes as active material, by active material and Kynoar according to 90%：10% ratio is mixed Grinding is closed, is dissolved in 1-methyl-2-pyrrolidinone 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
By (Kynoar-hexafluoropropene) copolymer (PVDF) and ionic liquid EMIPF6 according to 1:4 ratio mixing, Acetone is added as solvent.Liquor capacity is 20mL, solid content 20%.Be heated under closed state 50 DEG C keep 24 it is small when, Until being completely dissolved.Solution is poured into φ 90mm glass culture dish, gel electrolyte film, thickness are obtained after solvent volatilization For 800 microns；
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte film-flexible electrical pole piece stacks, and ensures to be coated with electrode in flexible electrical pole piece The one side of material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained.It will prepare Flexible super capacitor be connected to by French BioLogic electrochemical workstations, it is soft that this is obtained by constant current charge-discharge test The voltage of property ultracapacitor is 4V, capacitance 155F/g, as shown in Figure 8；Energy density is 86Wh/Kg；Discharge and recharge follows Capacity retention after ring 10000 times is 79%.
Comparative example 1
1) electrode active material prepares graphene：Native graphite is oxidized to by graphite oxide using Hummers methods, and is led to Cross probe sonication and disperse stripping and be prepared into graphene oxide water solution.Then graphene oxide water solution washing and vacuum are done It is dry.By the above-mentioned graphene oxide and potassium hydroxide shown in Fig. 9, by 1:4 ratios are put into tube furnace in argon gas gas after being ground 700 DEG C of activation are fired 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 80%：10%：10% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry； Solid content is 50% in slurry.Then by slurry coated on carbon nano-tube film, coating thickness is 100 microns, and is positioned over 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 1:1 ratio Example mixing, adds acetone as solvent.So that cumulative volume is 20mL, solid content 20%.50 DEG C of guarantors are heated under closed state Hold 24 it is small when until be completely dissolved.Solution is poured into φ 90mm glass culture dish, it is micro- for 500 to obtain thickness after solvent volatilization The gel electrolyte film of rice.
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte membrane electrode-flexible electrical pole piece stacks, and ensures to coat in flexible electrical pole piece The one side for having electrode material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained. The flexible super capacitor of preparation is connected to by French BioLogic electrochemical workstations, 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) electrode active material is prepared：Native graphite is oxidized to by graphite oxide using Hummers methods, and passes through probe Ultrasonic disperse is peeled off and 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, at a temperature of -10 DEG C, stirring reaction 24 it is small when, obtain Graphene oxide-polyaniline composite material simultaneously washs drying.By above-mentioned compound and potassium hydroxide, by 1:4 ratios are ground 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 80%：10%：10% ratio mixed grinding, is dissolved in 1-methyl-2-pyrrolidinone and is prepared into slurry； Solid content is 50% in slurry.Then by slurry coated on carbon nano-tube film, coating thickness is 100 microns, and is positioned over 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) normal pressure hydrogel thin film is prepared：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 that thickness is 100 microns.
4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to soft The order of property electrode slice-ionic gel electrolyte membrane electrode-flexible electrical pole piece stacks, and ensures to coat in flexible electrical pole piece The one side for having electrode material is contacted with electrolytic thin-membrane.Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained. The flexible super capacitor of preparation is connected to by French BioLogic electrochemical workstations, 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, can be driven after charging according to the high voltage flexible super capacitor prepared by the method for embodiment 1 Move 30 LED operations.In addition, capacitor bending does not influence the working status of capacitor.

Claims (10)

  1. A kind of 1. 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 electrode is coated on flexible current-collecting body surface, forms Flexible electrical pole piece；Order according to encapsulated layer-flexible electrical pole piece-gel electrolyte membrane-flexible electrical pole piece-encapsulated layer stacks, envelope Fill layer parcel flexible electrical pole piece-gel electrolyte membrane-flexible electrical pole piece.
  2. 2. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that：The active material of the electrode Expect for one kind in graphene, carbon nanotubes, porous charcoal or by several compounds formed.
  3. 3. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that：The active material of the electrode Material preferably graphene-based porous carbon composite nano-material.
  4. 4. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that：The gel electrolyte For high-voltage ion gel；High-voltage ion gel includes macromolecule matrix material and ionic liquid electrolyte, macromolecule matrix In space net structure, ionic liquid electrolyte is full of in its gap, forms gel film；The macromolecule matrix material has poly- Vinylidene (PVdF), (Kynoar-hexafluoropropene) copolymer (PVDF-HFP), polyoxyethylene (PEO)；The ionic liquid The room temperature liquid dissolved salt that body electrolyte is made of organic cation and anion；The ionic liquid electrolyte includes 1- second Base -3- methyl imidazolium tetrafluoroborates (EMIBF4), 1- ethyl-3-methylimidazoles hexafluorophosphate (EMIPF6) and 1- ethyls - 3- methylimidazoles double (trimethyl fluoride sulfonyls), sub- peace salt (EMITFSI)；The thickness of gel film is 10 microns -5 millimeters.
  5. 5. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that：The macromolecule matrix material Material preferably (Kynoar-hexafluoropropene) copolymer (PVDF-HFP)；The preferred 1- ethyls -3- methyl miaows of ionic liquid electrolyte Azoles tetrafluoroborate (EMIBF4).
  6. 6. high voltage flexible solid-state supercapacitor described in accordance with the claim 1, it is characterised in that：The thickness of the electrode is 5 microns to 500 microns；The loading content of carbon electrode active material is 0.1-5mg/cm in single electrode2。
  7. 7. prepare the method for high voltage flexible solid-state supercapacitor described in claim 1, it is characterised in that：The preparation side Method comprises the following steps：
    1) electrode active material is prepared
    Native graphite is oxidized to by graphite oxide using Hummers methods, and stripping is disperseed by probe sonication and is prepared into oxidation stone Black aqueous solution；Then conducting polymer monomer, dopant and oxidant ammonium persulfate are added in graphene oxide water solution, At a temperature of -10 DEG C to 25 DEG C, when stirring reaction 1-48 is small, graphene oxide-conducting polymer composite material is obtained, and wash Wash drying；Tube furnace is put into argon gas gas after graphene oxide-conducting polymer composite material and potassium hydroxide are ground Calcining and activating under atmosphere, is then washed with dilute hydrochloric acid, is dry, obtaining graphene-based porous carbon composite nano-material at room temperature；
    2) flexible electrical pole piece is prepared
    Using the graphene-based porous carbon composite nano-material as active material, by active material, conductive agent and binding agent according to (60-95) %：(0-20) %：The ratio mixed grinding of (5-20) %, is dissolved in solvent, is prepared into slurry；Solid content is in slurry 30%-60%；Then by slurry coated on flexible current-collecting body, coating thickness is 20 microns to 500 microns, is coated with slurry Flexible current-collecting body be positioned in baking oven, dry 24h obtains electrode slice at 120 DEG C；
    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 Measure as 0.1-5mg/cm2；
    3) high-voltage ion gel film is prepared
    By polymer-based bottom material and ionic liquid electrolyte according to 1:4-4:1 ratio mixing, adds acetone as solvent；It is molten Liquid cumulative volume arrives 50mL for 10 so that solid content 5%-60%；50 DEG C, when holding 24 is small are heated under closed state, until Polymer-based bottom material is completely dissolved；Solution is poured into glass culture dish, gel electrolyte film is obtained after solvent volatilization；
    The thickness of the gel electrolyte film obtained is 100 microns -1 millimeter；
    4) gel electrolyte film made from flexible electrical pole piece and a piece of step 3) prepared by two panels step 2) is taken, according to flexible electrical The order of pole piece-ionic gel electrolyte film-flexible electrical pole piece stacks, and the one side of electrode material is coated with flexible electrical pole piece Contacted with electrolytic thin-membrane；Using polydimethylsiloxane thin-film package, flexible super capacitor is obtained；
    In the step 1), 0.005-1mol L are contained in the graphene oxide water solution-1Conducting polymer monomer, 0.01-2molL-1Dopant and 0.005-1molL-1Ammonium persulfate；
    In the step 1), when the reaction time for preparing graphene-conducting polymer composite material is preferably 24 small；
    Conducting polymer monomer in the step 1) is the one or more in aniline, pyrroles, thiophene and ethylenedioxy thiophene；
    In the step 1), the dopant is one kind in sulfuric acid, perchloric acid, hydrochloric acid, p-methyl benzenesulfonic acid and camphorsulfonic acid It is or a variety of；
    In the step 1), the ratio of graphene oxide-conducting polymer composite material and potassium hydroxide is 2:1 to 1:8；
    In the step 1), the calcining heat of synthesizing graphite alkene Quito hole carbon nanomaterial is 500 DEG C -900 DEG C；
    Conductive agent is one kind in conductive black, electrically conductive graphite, carbon nanotubes, nano carbon fiber, graphene in the step 2) It is or a variety of；
    Binding agent is Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber in the step 2)；
    Solvent is 1-methyl-2-pyrrolidinone or ethanol in the step 2)；
    Preferably, the loading content of carbon electrode active material is 0.5-2mg/cm in single electrode2。
  8. 8. according to the method for preparing high voltage flexible solid-state supercapacitor described in claim 7, it is characterised in that：Described In step 1), 0.05molL is preferably comprised in the graphene oxide water solution-1Conducting polymer monomer, 1molL-1's Dopant, 0.05molL-1Ammonium persulfate；The preferred aniline monomer of conducting polymer monomer；The dopant is preferably high Chloric acid；The ratio of graphene oxide-conducting polymer composite material and potassium hydroxide preferably 1:4；Synthesizing graphite alkene base porous carbon Preferably 700 DEG C of the calcining heat of nano material.
  9. 9. according to the method for preparing high voltage flexible solid-state supercapacitor described in claim 7, it is characterised in that：Described In step 2), the preferred conductive black of conductive agent；The preferred Kynoar of binding agent；The preferred 1-methyl-2-pyrrolidinone of solvent； The preferred carbon nanotubes self-supporting film of collector；The ratio of active material, conductive agent and binding agent is preferably 80%：10%： 10%；
    Preferably, the loading content of carbon electrode active material is 0.5-2mg/cm in single electrode2。
  10. 10. according to the method for preparing high voltage flexible solid-state supercapacitor described in claim 7, it is characterised in that：It is described Step 3) in, the ratio of polymer-based bottom material and ionic liquid is preferably 1:1；Polymer-based bottom material, ionic liquid electricity The content for solving polymer-based bottom material and ionic liquid electrolyte in the mixed solution of matter and acetone is preferably 20%.
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CN110970233A (en) * 2019-12-26 2020-04-07 上海交通大学 Preparation method of micro super capacitor based on conjugated organic framework material
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CN111504520A (en) * 2020-04-20 2020-08-07 河北工业大学 Integrated flexible stretchable touch sensor based on super-capacitor sensing principle
CN111504520B (en) * 2020-04-20 2022-05-24 河北工业大学 Integrated flexible stretchable touch sensor based on super-capacitor sensing principle
CN112834086A (en) * 2020-12-31 2021-05-25 华中科技大学 Ultra-sensitive capacitive flexible pressure sensor and preparation method thereof
CN113203504A (en) * 2021-04-01 2021-08-03 上海交通大学 Flexible wearable pressure sensor with ultrahigh capacitance and pressure sensor array
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
CN115360024A (en) * 2022-08-10 2022-11-18 五邑大学 Super capacitor and preparation method and application thereof

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