CN115360024B - Super capacitor and preparation method and application thereof - Google Patents

Super capacitor and preparation method and application thereof Download PDF

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CN115360024B
CN115360024B CN202210955689.8A CN202210955689A CN115360024B CN 115360024 B CN115360024 B CN 115360024B CN 202210955689 A CN202210955689 A CN 202210955689A CN 115360024 B CN115360024 B CN 115360024B
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electrode layer
polyvinyl alcohol
electrode
film
supercapacitor
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CN115360024A (en
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张扬帆
孙晓伟
李林松
马春平
吴彦城
易宁波
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Wuyi University
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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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

The invention discloses a super capacitor, a preparation method and application thereof, wherein the super capacitor comprises a first electrode layer, an electrolyte layer and a second electrode layer which are sequentially arranged; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials; the electrolyte layer is prepared from polyvinyl alcohol; the polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked at the interface of the first electrode layer, the electrolyte layer and the second electrode layer and at the inside of the first electrode layer, the electrolyte layer and the second electrode layer under the action of the crosslinking agent. The super capacitor not only can effectively fuse between the electrode electrolyte electrode of the super capacitor the interface contact resistance is reduced so as to improve the area specific capacity of the flexible supercapacitor, the electrode/electrolyte/electrode interface reinforced interface interaction of the chemical cross-linking can be constructed, so that the bending and torsion deformation resistance of the flexible supercapacitor is improved.

Description

Super capacitor and preparation method and application thereof
Technical Field
The invention relates to the technical field of energy storage, in particular to a super capacitor and a preparation method and application thereof.
Background
The advent of new flexible and wearable electronic devices (flexible displays, wearable sensors, electronic skin, etc.) has greatly facilitated the rapid development of flexible supercapacitors that can be powered. The development of high performance flexible supercapacitors is a hotspot problem. The flexible supercapacitor should have the ability to stably output electric energy under various deformation states including long-time bending, twisting, or folding. At present, a classical flexible supercapacitor generally comprises a flexible electrode material, an electrolyte and other main components which can serve as a positive electrode and a negative electrode at the same time, and is prepared by stacking the flexible electrode material, the electrolyte and the flexible electrode material layer by layer to form an electrode/electrolyte/electrode sandwich structure. However, the sandwich structure flexible super capacitor depends on weaker secondary bond force due to the obvious interface of the electrode/electrolyte/electrode, there are problems of large interface contact resistance and weak interface interaction force, the energy density of the actual output of the flexible supercapacitor is low, the electrode sandwich structure inevitably generates relative displacement and interfacial delamination under repeated deformation to cause the failure of the flexible supercapacitor, the power supply requirement of novel flexible and wearable electronic equipment is difficult to meet, and the industrialized development of the flexible supercapacitor is limited.
Therefore, it is necessary to provide a new supercapacitor having excellent mechanical properties and deformation resistance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides the super capacitor which can effectively improve the mechanical property, the deformation resistance and the excellent area specific capacitance.
The invention also provides a preparation method of the super capacitor.
The invention also provides an application of the super capacitor.
The supercapacitor according to the embodiment of the first aspect of the invention comprises a first electrode layer, an electrolyte layer and a second electrode layer which are sequentially arranged; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials;
The preparation raw materials of the electrolyte layer comprise polyvinyl alcohol;
The polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked at the interface of the first electrode layer, the electrolyte layer and the second electrode layer and at the inside of the first electrode layer, the electrolyte layer and the second electrode layer under the action of the crosslinking agent.
The super capacitor provided by the embodiment of the invention has at least the following beneficial effects:
The invention uses polyvinyl alcohol and cross-linking agent to cross-link, which not only occurs at the interface of the first electrode layer, the electrolyte layer and the second electrode layer, but also occurs inside the first electrode layer, the electrolyte layer and the second electrode layer. Thus, the first and second substrates are bonded together, not only can effectively fuse the interface between the electrode|electrolyte|electrodes of the super capacitor to reduce the interface contact resistance so as to improve the area specific capacity of the flexible super capacitor, the electrode/electrolyte/electrode interface reinforced interface interaction of the chemical cross-linking can be constructed, so that the bending and torsion deformation resistance of the flexible supercapacitor is improved.
According to some embodiments of the invention, the cross-linking agent is a dialdehyde compound.
According to some embodiments of the invention, the dialdehyde comprises at least one of glutaraldehyde, glyoxal, succinaldehyde.
According to some embodiments of the invention, the conductive material comprises at least one of carbon nanotubes, graphene, porous carbon, carbon black, or carbon fibers.
According to some embodiments of the invention, in the first electrode layer and the second electrode layer, the mass ratio of the polyvinyl alcohol to the conductive material is 1: (0.25-4).
According to some embodiments of the invention, the energy storage material comprises a conductive polymer or a metal oxide.
According to some embodiments of the invention, the conductive polymer comprises at least one of polyaniline, polypyrrole, or polythiophene.
According to some embodiments of the invention, the metal oxide comprises manganese dioxide or ruthenium dioxide.
An embodiment of the second aspect of the present invention provides a method for manufacturing a supercapacitor, including the steps of:
S1, mixing and stirring polyvinyl alcohol, a conductive material, a surfactant and a first solvent to obtain a mixed solution, and removing the first solvent through heat treatment to obtain a first conductive film and a second conductive film respectively; mixing and stirring polyvinyl alcohol and a second solvent to obtain a polyvinyl alcohol solution, and removing the second solvent through heat treatment to obtain a polyvinyl alcohol film;
S2, swelling the first conductive film, the second conductive film and the polyvinyl alcohol film by a third solvent, assembling the first conductive film, the polyvinyl alcohol film and the second conductive film in sequence, and removing the third solvent by a hot pressing method to obtain a first structure film;
S3, carrying out a crosslinking reaction on the first structural film and a crosslinking agent to obtain a second structural film;
and S4, performing electrodeposition energy storage materials on the two surfaces of the second structural film, and soaking the second structural film in a water-based electrolyte to obtain the supercapacitor.
According to some embodiments of the invention, in step S3, the temperature of the crosslinking reaction is 25 to 60 ℃; the time is 1-36 h.
According to some embodiments of the invention, the mass ratio of the surfactant to the conductive material is 1: (50-1000).
According to some embodiments of the invention, the surfactant comprises at least one of sodium dodecylbenzenesulfonate, sodium octadecylsulfate, sodium stearate, dodecyltrimethylammonium bromide, or octoxynol.
According to some embodiments of the invention, in step S1, the stirring speed is 300-1000 r/min.
According to some embodiments of the invention, in step S1, the stirring time is 60-300 min.
According to some embodiments of the invention, in step S1, the temperature of the heat treatment is 30-100 ℃.
According to some embodiments of the invention, in step S2, the hot pressing method satisfies one of the following conditions:
The temperature is 30-100 ℃, the hot pressing pressure is 0.1-10 MPa, and the hot pressing time is 5-120 min.
According to some embodiments of the invention, in step S4, the electrodeposition method comprises at least one of galvanostatic deposition, potentiostatic deposition, or cyclic voltammetry deposition.
According to some embodiments of the invention, in step S4, the concentration of the aqueous electrolyte is 1 to 3M.
According to some embodiments of the invention, the aqueous electrolyte comprises sulfuric acid.
Embodiments of a third aspect of the present invention provide for the use of a supercapacitor in a flexible electronic device or a wearable electronic device.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a three-dimensional microscopic view of super depth of field of super capacitors prepared in examples 1,2,3 and 4 of the present invention, wherein a is example 1, b is example 2, c is example 3, and d is example 4;
FIG. 2 is a scanning electron microscope image of the super capacitor prepared in examples 1,2,3 and 4 of the present invention, wherein a is example 1, b is example 2, c is example 3, and d is example 4;
FIG. 3 is a graph showing stress-strain curves and elastic modulus, tensile strength versus elongation at break for supercapacitors prepared in examples 1,2,3 and 4 of the present invention;
FIG. 4 is a graph showing the area ratio capacitance comparison of the super capacitors prepared in examples 1,2,3 and 4 of the present invention;
FIG. 5 is a graph showing the impedance comparison of supercapacitors prepared in examples 1, 2, 3 and 4 of the present invention;
FIG. 6 is a graph showing the bending resistance of the supercapacitor prepared in example 1 of the present invention, wherein a is the change in specific capacitance from 0℃to 90℃and 180℃and the corresponding cyclic voltammogram, and b is the change in capacitance and the corresponding cyclic voltammogram repeatedly bent 50000 times between 0℃and 180℃;
FIG. 7 shows the twist resistance of the supercapacitor prepared in example 1 of the present invention, wherein a is the change in specific capacitance from 0℃to 20℃and 40℃and 60℃and the corresponding cyclic voltammogram, and b is the change in capacitance and the corresponding cyclic voltammogram repeatedly twisted 50000 times between 0℃and 60℃respectively;
FIG. 8 is a three-dimensional microscopic view of super depth of field of the super capacitor prepared in comparative example 1 of the present invention;
FIG. 9 is a graph showing the area ratio capacitance of the supercapacitor prepared in example 1 according to the present invention and the supercapacitor prepared in comparative example 1;
Fig. 10 is a graph of the super capacitor series 3-section of the present invention prepared in example 1, which lights up the LED lamp in the flat, bent, twisted and folded state.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
Embodiment 1 provides a supercapacitor comprising a first electrode layer, an electrolyte layer, and a second electrode layer disposed in that order; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials; the electrolyte layer is prepared from polyvinyl alcohol; the polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked with a crosslinking agent.
The preparation method comprises the following steps:
S1, mixing 0.4g of polyvinyl alcohol, 0.6g of multi-wall carbon nano tube, 0.01g of surfactant octoxynol and 100mL of deionized water, mixing for 120min at 500r/min by using mechanical stirring, performing ultrasonic dispersion for 30min to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mould, and performing heat treatment at 50 ℃ to remove the solvent to obtain a first conductive film and a second conductive film; mixing 4g of polyvinyl alcohol and 100ml of deionized water, then mixing for 120min at 500r/min by mechanical stirring to obtain a polyvinyl alcohol solution, pouring the polyvinyl alcohol solution into a mold, and performing heat treatment at 50 ℃ to remove water to obtain a polyvinyl alcohol film;
S2, swelling the first conductive film, the second conductive film and the polyvinyl alcohol film by using deionized water, assembling the first conductive film, the polyvinyl alcohol film and the second conductive film in sequence, and hot-pressing at 50 ℃ to remove the solvent to prepare a first structural film;
s3, placing the first structural film in a vacuum dryer filled with saturated glutaraldehyde and hydrochloric acid steam, and crosslinking the glutaraldehyde and the polyvinyl alcohol for 18 hours at 25 ℃ under the catalysis of hydrochloric acid to obtain a second structural film;
S4, using two surfaces in the second structural film as working electrodes, using a platinum sheet electrode as an auxiliary electrode, using a saturated calomel electrode as a reference electrode, using a 0.1M aniline/0.1M sulfuric acid aqueous solution as an electrolyte, adopting a three-electrode system to accumulate aniline through electrodeposition by a constant current method, and finally saturating and absorbing the 1M sulfuric acid aqueous solution to prepare the supercapacitor.
Example 2
Embodiment 2 provides a supercapacitor comprising a first electrode layer, an electrolyte layer, and a second electrode layer disposed in that order; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials; the electrolyte layer is prepared from polyvinyl alcohol; the polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked with a crosslinking agent.
The preparation method comprises the following steps:
S1, mixing 0.4g of polyvinyl alcohol, 0.6g of multi-wall carbon nano tube, 0.01g of surfactant octoxynol and 100mL of deionized water, mixing for 120min at 500r/min by using mechanical stirring, performing ultrasonic dispersion for 30min to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mould, and performing heat treatment at 50 ℃ to remove the solvent to obtain a first conductive film and a second conductive film; mixing 4g of polyvinyl alcohol and 100mL of deionized water, and then mixing for 120min at 500r/min by mechanical stirring to obtain a polyvinyl alcohol solution, pouring the polyvinyl alcohol solution into a mold, and performing heat treatment at 50 ℃ to remove water to obtain a polyvinyl alcohol film;
S2, swelling the first conductive film, the second conductive film and the polyvinyl alcohol film by using deionized water, assembling the first conductive film, the polyvinyl alcohol film and the second conductive film in sequence, and hot-pressing at 50 ℃ to remove the solvent to prepare a first structural film;
S3, placing the first structural film in a vacuum dryer filled with saturated glutaraldehyde and hydrochloric acid steam, and crosslinking the glutaraldehyde and the polyvinyl alcohol for 24 hours at 25 ℃ under the catalysis of hydrochloric acid to obtain a second structural film;
S4, using two surfaces in the second structural film as working electrodes, using a platinum sheet electrode as an auxiliary electrode, using a saturated calomel electrode as a reference electrode, using a 0.1M aniline/0.1M sulfuric acid aqueous solution as an electrolyte, adopting a three-electrode system to accumulate aniline through electrodeposition by a constant current method, and finally saturating and absorbing the 1M sulfuric acid aqueous solution to prepare the supercapacitor.
Example 3
Embodiment 3 provides a supercapacitor comprising a first electrode layer, an electrolyte layer, and a second electrode layer disposed in that order; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials; the electrolyte layer comprises polyvinyl alcohol; the polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked with a crosslinking agent. The preparation method comprises the following steps:
S1, mixing 0.4g of polyvinyl alcohol, 0.6g of multi-wall carbon nano tube, 0.01g of surfactant octoxynol and 100mL of deionized water, mixing for 120min at 500r/min by using mechanical stirring, performing ultrasonic dispersion for 30min to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mould, and performing heat treatment at 50 ℃ to remove the solvent to obtain a first conductive film and a second conductive film; mixing 4g of polyvinyl alcohol and 100ml of deionized water, then mixing for 120min at 500r/min by mechanical stirring to obtain a polyvinyl alcohol solution, pouring the polyvinyl alcohol solution into a mold, and performing heat treatment at 50 ℃ to remove water to obtain a polyvinyl alcohol film;
S2, swelling the first conductive film, the second conductive film and the polyvinyl alcohol film by using deionized water, assembling the first conductive film, the polyvinyl alcohol film and the second conductive film in sequence, and hot-pressing at 50 ℃ to remove the solvent to prepare a first structural film;
s3, placing the first structural film in a vacuum dryer filled with saturated glutaraldehyde and hydrochloric acid steam, and crosslinking the glutaraldehyde and the polyvinyl alcohol for 30 hours at 25 ℃ under the catalysis of hydrochloric acid to obtain a second structural film;
S4, using two surfaces in the second structural film as working electrodes, using a platinum sheet electrode as an auxiliary electrode, using a saturated calomel electrode as a reference electrode, using a 0.1M aniline/0.1M sulfuric acid aqueous solution as an electrolyte, adopting a three-electrode system to accumulate aniline through electrodeposition by a constant current method, and finally saturating and absorbing the 1M sulfuric acid aqueous solution to prepare the supercapacitor.
Example 4
Embodiment 4 provides a supercapacitor comprising a first electrode layer, an electrolyte layer, and a second electrode layer disposed in that order; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials; the electrolyte layer is prepared from polyvinyl alcohol; the polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked with a crosslinking agent.
The preparation method comprises the following steps:
S1, mixing 0.4g of polyvinyl alcohol, 0.6g of multi-wall carbon nano tube, 0.01g of surfactant octoxynol and 100mL of deionized water, mixing for 120min at 500r/min by using mechanical stirring, performing ultrasonic dispersion for 30min to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mould, and performing heat treatment at 50 ℃ to remove the solvent to obtain a first conductive film and a second conductive film; mixing 4g of polyvinyl alcohol and 100ml of deionized water, then mixing for 120min at 500r/min by mechanical stirring to obtain a polyvinyl alcohol solution, pouring the polyvinyl alcohol solution into a mold, and performing heat treatment at 50 ℃ to remove water to obtain a polyvinyl alcohol film;
S2, swelling the first conductive film, the second conductive film and the polyvinyl alcohol film by using deionized water, assembling the first conductive film, the polyvinyl alcohol film and the second conductive film in sequence, and hot-pressing at 50 ℃ to remove the solvent to prepare a first structural film;
S3, placing the first structural film in a vacuum dryer filled with saturated glutaraldehyde and hydrochloric acid steam, and crosslinking the glutaraldehyde and the polyvinyl alcohol for 36 hours at 25 ℃ under the catalysis of hydrochloric acid to obtain a second structural film;
S4, using two surfaces in the second structural film as working electrodes, using a platinum sheet electrode as an auxiliary electrode, using a saturated calomel electrode as a reference electrode, using a 0.1M aniline/0.1M sulfuric acid aqueous solution as an electrolyte, adopting a three-electrode system to accumulate aniline through electrodeposition by a constant current method, and finally saturating and absorbing the 1M sulfuric acid aqueous solution to prepare the supercapacitor.
Comparative example 1
Comparative example 1 provides a supercapacitor comprising a first electrode layer, an electrolyte layer, and a second electrode layer disposed in that order; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials; the electrolyte layer is prepared from polyvinyl alcohol; the preparation method comprises the following steps:
S1, mixing 0.4g of polyvinyl alcohol, 0.6g of multi-wall carbon nano tube, 0.01g of surfactant octoxynol and 100mL of deionized water, mixing for 120min at 500r/min by using mechanical stirring, performing ultrasonic dispersion for 30min to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mould, performing heat treatment at 50 ℃ to remove the solvent to obtain a conductive film, finally placing the conductive film into a vacuum dryer filled with saturated glutaraldehyde and hydrochloric acid steam, and crosslinking the glutaraldehyde and the polyvinyl alcohol for 18h at 25 ℃ under the catalysis of hydrochloric acid to obtain a crosslinked polyvinyl alcohol/carbon nano tube composite conductive film;
s2, using a conductive film as a working electrode, a platinum sheet electrode as an auxiliary electrode, a saturated calomel electrode as a reference electrode, and 0.1M aniline/0.1M sulfuric acid aqueous solution as electrolyte, and adopting a three-electrode system to electrodeposit polyaniline through a constant current method to prepare a crosslinked polyvinyl alcohol/carbon nano tube/polyaniline flexible electrode material;
S3, mixing 2g of polyvinyl alcohol and 20ml of 1M sulfuric acid aqueous solution, and then mixing for 120min at 500r/min by mechanical stirring to obtain a polyvinyl alcohol/sulfuric acid gel electrolyte;
S4, assembling the polyvinyl alcohol/carbon nano tube/polyaniline flexible electrode material, the polyvinyl alcohol/sulfuric acid gel electrolyte and the polyvinyl alcohol/carbon nano tube/polyaniline flexible electrode material into the supercapacitor.
Performance testing
The cross sections of the supercapacitors prepared in examples 1,2, 3 and 4 were subjected to morphology observation of electrode/electrolyte/electrode interface by using a super-depth three-dimensional microscope and a cold field emission scanning electron microscope, and the results are shown in fig. 1 (a is example 1, b is example 2, c is example 3, d is example 4) and fig. 2 (a is example 1, b is example 2, c is example 3, d is example 4), respectively. It is known that the electrode|electrolyte|electrode of the integrated flexible supercapacitor prepared by different crosslinking time has no obvious interface, and is crosslinked and fused into an integrated structure.
The supercapacitors prepared in examples 1,2,3 and 4 were tested for tensile properties according to GBT 528 standard, and the stress-strain curves and the calculated elastic modulus, tensile strength and elongation at break are shown in fig. 3. As can be seen, the mechanical properties of the integrated flexible supercapacitor are relatively similar along with the extension of the crosslinking time, the elastic modulus is 100.8-138.2 MPa, the tensile strength is 4.8-7.4 MPa, and the elongation at break is 6.5-8.2%, so that the supercapacitor prepared by the invention has good mechanical properties.
The supercapacitors prepared in examples 1, 2, 3 and 4 were tested for electrochemical performance and impedance using an electrochemical workstation, and the results are shown in fig. 4 and 5, respectively. As can be seen from fig. 4, the area specific capacities of the integrated flexible supercapacitors were gradually decreased with the increase of the crosslinking time, and the area specific capacities of the integrated flexible supercapacitors prepared in examples 1, 2, 3 and 4 were 268.8, 172.7, 157.6 and 142.6mF/cm 2, respectively. As can be seen from fig. 5, as the crosslinking time is prolonged, the interfacial transfer resistance of the area specific capacitance of the integrated flexible supercapacitor is gradually increased, and the area specific capacitances of the integrated flexible supercapacitors prepared in examples 1, 2, 3 and 4 are 8.0, 26.9, 51.5 and 133.9 Ω, respectively, which indicates that the supercapacitors prepared in the present invention can exhibit low interfacial transfer resistance and excellent area specific capacitance through optimization of the crosslinking time.
The integrated flexible supercapacitor prepared in example 1 was subjected to bending and torsion deformation tests using a flexible electronic tester in combination with an electrochemical workstation, and the results are shown in fig. 6 and 7, respectively. As can be seen from fig. 6 (a is a specific capacitance change from 0 ° to 90 ° and 180 ° and a corresponding cyclic voltammogram, and b is a capacitance change and a corresponding cyclic voltammogram repeatedly bent 50000 times between 0 ° and 180 °), the integrated flexible supercapacitor prepared in example 1 has substantially no change in specific capacitance from 0 ° to 90 ° and 180 °, and the capacitance remains up to 103% after repeatedly bent 50000 times between 0 ° and 180 °. As can be seen from fig. 7 (a is a change of specific capacitance from 0 ° to 20 °, 40 ° and 60 ° and corresponding cyclic voltammogram, and b is a change of capacitance and corresponding cyclic voltammogram repeatedly twisted for 50000 times between 0 ° and 60 °), the integrated flexible supercapacitor prepared in example 1 has substantially no change of specific capacitance from 0 ° to 20 °, 40 ° and 60 °, and the capacitance remains up to 101% after repeatedly twisted for 50000 times between 0 ° and 60 °. The result shows that the integrated flexible supercapacitor prepared by the invention has excellent bending and twisting deformation resistance.
To highlight the integrated structure of the supercapacitor prepared in example 1, the morphology observation of the electrode/electrolyte/electrode interface was performed on the sandwich-structured flexible supercapacitor prepared in comparative example 1 by using a super-depth three-dimensional microscope, and the result is shown in fig. 8. It can be known that the sandwich structure flexible supercapacitor prepared in the comparative example 1 has an obvious electrode/electrolyte/electrode interface, and the comparative illustration shows that the polyvinyl alcohol crosslinking method of the invention can effectively fuse the electrode/electrolyte/electrode interface into an integrated structure.
For the electrochemical performance of the integrated flexible supercapacitor prepared in comparative example 1, the electrochemical performance test was performed on the sandwich-structured flexible supercapacitor prepared in comparative example 1 using an electrochemical workstation, and the results are shown in fig. 9. Compared with the prior art, the area specific capacitance of the integrated flexible supercapacitor prepared in the embodiment 1 is larger than that of the sandwich structure flexible supercapacitor prepared in the comparative embodiment 1 under different scanning rates, and when the scanning rate is 5mV/s, the area specific capacitance of the integrated flexible supercapacitor prepared in the embodiment 1 can reach 268.8mF/cm 2, while the area specific capacitance of the sandwich structure flexible supercapacitor prepared in the comparative embodiment 1 is only 59.5mF/cm 2, which indicates that the integrated flexible supercapacitor prepared in the invention has excellent area specific capacitance.
As shown in fig. 10, the three-section series integrated flexible supercapacitor prepared in the embodiment 1 can light up the LED lamp in the flat, bent, twisted and folded states, which indicates that the integrated flexible supercapacitor prepared in the invention has a wide application prospect in novel flexible electronic devices.
The present invention has been described in detail with reference to the above embodiments, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (8)

1. The preparation method of the supercapacitor is characterized in that the supercapacitor comprises a first electrode layer, an electrolyte layer and a second electrode layer which are sequentially arranged; the preparation raw materials of the first electrode layer and the second electrode layer comprise polyvinyl alcohol, conductive materials and energy storage materials;
The preparation raw materials of the electrolyte layer comprise polyvinyl alcohol;
The polyvinyl alcohol in the first electrode layer, the electrolyte layer and the second electrode layer is crosslinked on the interfaces of the first electrode layer, the electrolyte layer and the second electrode layer and inside the first electrode layer, the electrolyte layer and the second electrode layer under the action of the crosslinking agent; the cross-linking agent is a dialdehyde compound;
the preparation method comprises the following steps:
S1, mixing and stirring polyvinyl alcohol, a conductive material, a surfactant and a first solvent to obtain a mixed solution, and removing the first solvent through heat treatment to obtain a first conductive film and a second conductive film respectively; mixing and stirring polyvinyl alcohol and a second solvent to obtain a polyvinyl alcohol solution, and removing the second solvent through heat treatment to obtain a polyvinyl alcohol film;
S2, swelling the first conductive film, the second conductive film and the polyvinyl alcohol film by a third solvent, assembling the first conductive film, the polyvinyl alcohol film and the second conductive film in sequence, and removing the third solvent by a hot pressing method to obtain a first structure film;
S3, carrying out a crosslinking reaction on the first structural film and a crosslinking agent to obtain a second structural film;
and S4, performing electrodeposition energy storage materials on the two surfaces of the second structural film, and soaking the second structural film in a water-based electrolyte to obtain the supercapacitor.
2. The method of claim 1, wherein the conductive material comprises at least one of carbon nanotubes, graphene, porous carbon, carbon black, or carbon fibers.
3. The method for manufacturing a supercapacitor according to claim 1, wherein in the first electrode layer and the second electrode layer, the mass ratio of the polyvinyl alcohol to the conductive material is 1: (0.25-4).
4. The method of claim 1, wherein the energy storage material comprises a conductive polymer or a metal oxide.
5. The method for manufacturing a supercapacitor according to claim 1, wherein in step S3, the temperature of the crosslinking reaction is 25 to 60 ℃; the time is 1-36 h.
6. The method for manufacturing a supercapacitor according to claim 1, wherein the mass ratio of the surfactant to the conductive material is 1: (50-1000).
7. The method for manufacturing a supercapacitor according to claim 1, wherein in step S1, the stirring speed is 300-1000 r/min.
8. The application of the supercapacitor prepared by the preparation method of the supercapacitor in any one of claims 1-7 in flexible electronic devices or wearable electronic equipment.
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