CN111029162B - Graphene/polypyrrole composite electrode material, preparation and application thereof in super capacitor - Google Patents

Graphene/polypyrrole composite electrode material, preparation and application thereof in super capacitor Download PDF

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CN111029162B
CN111029162B CN201911392165.7A CN201911392165A CN111029162B CN 111029162 B CN111029162 B CN 111029162B CN 201911392165 A CN201911392165 A CN 201911392165A CN 111029162 B CN111029162 B CN 111029162B
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graphene
polypyrrole
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CN111029162A (en
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王振洋
李年
江海河
张淑东
刘翠
蒋长龙
刘变化
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Hefei Institutes of Physical Science of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a graphene/polypyrrole composite electrode material and preparation and application thereof in a supercapacitor. The electrode material can be used for manufacturing a super capacitor and has excellent energy storage density, charge-discharge power density and cycle stability. The method is simple to operate, the raw materials are easy to obtain, and different application requirements can be met, so that the method is convenient to popularize.

Description

Graphene/polypyrrole composite electrode material, preparation and application thereof in super capacitor
Technical Field
The invention relates to a graphene/polypyrrole composite electrode material, a preparation method thereof and application thereof in a super capacitor, and belongs to the technical field of preparation of nano composite materials and super capacitor electrode materials.
Background
At present, the key point of the application research of the super capacitor in the field of energy storage is to design an electrode material with a novel microstructure so as to improve the specific capacity of the super capacitor. In all the materials studied at present, the graphene/pseudocapacitance composite material is considered to be a very promising new electrode material. In the composite electrode material, graphene has a large specific surface area, excellent conductivity and excellent mechanical properties, while the pseudocapacitance material can provide higher specific capacity, and the interaction of the graphene and the pseudocapacitance material can enable the composite electrode to have ideal high specific capacitance, high power density and long cycle life.
The most commonly used pseudocapacitive materials include transition metal oxides (such as RuO2, mnO2, and Co3O 4) and conductive polymers (such as polyaniline, polypyrrole, and polythiophene), among others. Where the metal oxide has a larger theoretical specific capacity, but its lower conductivity limits the power density and the volume change during oxidation-reduction makes its cycle life lower. And the polymer has better conductivity and flexibility, so that the polymer becomes an ideal pseudocapacitance material for the super capacitor (especially in the field of flexible thin film super capacitors).
Among various conductive polymer materials, polypyrrole has the advantages of simple preparation, low cost, stable performance and the like, and can be synthesized at submicron precision by an electrochemical deposition method. Polypyrrole and graphene are combined to uniformly grow on the surface of the graphene, the graphene with a large specific surface area is used as a framework, so that the electrolyte can be fully infiltrated, the reaction activity is improved, and the volume change of the polypyrrole in the cyclic charge-discharge process can be reduced, so that the cyclic stability of an electrode material system is improved.
However, the preparation of the graphene/polypyrrole composite electrode material system still faces some critical problems which are not well solved. For example, since graphene is very prone to agglomeration, polypyrrole is usually difficult to be uniformly loaded on the surface of graphene, and only by uniform compounding, the electrode material can fully exert the dual advantages of large specific surface area and high conductivity of graphene and high pseudocapacitance of polypyrrole, so as to provide guarantee for the electrochemical performance of the composite electrode. On the other hand, in order to obtain higher capacitance performance and energy storage density, it is necessary to increase the ratio of polypyrrole in the entire composite electrode as much as possible while ensuring the conductivity and cycle performance of the composite electrode.
Disclosure of Invention
In order to solve the problem of preparation of the graphene composite electrode material in the prior art, the invention provides a graphene/polypyrrole composite electrode material, and preparation and application thereof in a supercapacitor.
In order to achieve the purpose, the invention adopts the following scheme:
the preparation method of the graphene/polypyrrole composite electrode material is characterized in that laser-induced graphene is subjected to hydrophilic treatment and then is immersed in water-based electroplating solution containing pyrrole to carry out electrodeposition of polypyrrole.
In the preparation method of the graphene/polypyrrole composite electrode material, the hydrophilic contact angle range of the graphene after hydrophilic treatment is preferably 0-30 degrees.
In the preparation method of the graphene/polypyrrole composite electrode material, preferably, the method used for the hydrophilic treatment includes, but is not limited to, any one or a combination of the following: oxygen plasma treatment, oxidant treatment, and acid treatment.
In the preparation method of the graphene/polypyrrole composite electrode material, preferably, the concentration range of pyrrole in the pyrrole-containing aqueous electroplating solution is 0.001 to 1mol/L, and the concentration range of the surfactant is 0 to 1mol/L; more preferably, the pyrrole concentration ranges from 0.01 to 0.5mol/L and the surfactant concentration ranges from 0 to 1mol/L.
In the preparation method of the graphene/polypyrrole combined electrode material, preferably, the electrodeposition mode of the polypyrrole includes but is not limited to: one or the combination of constant voltage, variable voltage, pulse voltage, constant current, variable current, pulse current and the like; the voltage range is 0.01 to 100V, the current range is 1mA to 100A, the electrodeposition time is 1min to 72 hours, and the reaction temperature is controlled to be 0 to 90 ℃.
The preparation method of the graphene/polypyrrole composite electrode material can specifically adopt the following steps:
a. laser-induced preparation of graphene on flexible substrate
Exposing the polymer film to laser irradiation in an air atmosphere, thereby obtaining a graphene pattern electrode on the surface of the polymer;
b. hydrophilic treatment of graphene electrodes
Carrying out hydrophilic treatment on the graphene electrode obtained in the step a to enable the hydrophilic contact angle range to be 0-30 degrees;
c. and c, immersing the graphene electrode obtained in the step b into an aqueous electroplating solution containing pyrrole monomer, carrying out electrodeposition of polypyrrole, cleaning and drying.
The loading amount of polypyrrole in the graphene/polypyrrole composite electrode material prepared by the preparation method is 50-99.5% by mass.
The graphene/polypyrrole composite electrode material can be used as a supercapacitor electrode, and the application method can be as follows: the prepared graphene/polypyrrole patterned electrode is used as the positive electrode and the negative electrode of the supercapacitor. Then preparing PVA/H2SO4 electrolyte according to the conventional operation in the field, wherein the preparation method comprises the steps of adding 2ml of concentrated sulfuric acid into 20ml of deionized water, then adding 2 g of PVA (polyvinyl alcohol), and stirring for 60min at 85 ℃. The above electrolyte was dropped into the active region of the electrolyte and dried in a vacuum oven at 60 ℃ for 6 hours. And (3) the copper foil is used as an electrode lead-out wire, and the copper foil and the graphene/polypyrrole electrode are connected by conductive silver adhesive, so that the flexible all-solid-state supercapacitor can be assembled. The specific capacitance of the assembled supercapacitor is 1 to 10000mF/cm 2 The energy remained > 80% after 10000 cycles.
According to the invention, the hydrophilic treatment of the graphene electrode can enable aqueous electroplating solution in a subsequent polypyrrole electrodeposition process to fully enter the three-dimensional grid of the graphene, so that the polypyrrole can uniformly grow on the surface of the graphene. On the other hand, the hydrophilic treatment of the graphene electrode is also beneficial to the infiltration of electrolyte when the capacitor is applied, and the capacitance performance is improved. The hydrophilic treatment may be oxygen plasma treatment, oxidant treatment, acid treatment, or the like, or may be other necessary treatment methods such as ultrasonic treatment, light treatment, or the like as auxiliary means to facilitate uniform growth of polypyrrole on the surface of graphene. The inventor finds that polypyrrole can not enter the graphene grids without adopting the hydrophilic treatment step of the invention and can be accumulated on the surface in a large amount, so that the specific capacitance of the composite material is low and the cycle performance is poor.
The polymer substrate does not have polypyrrole deposition and does not change before and after the reaction because it is not conductive.
In the present invention, the polymer used for the laser-induced preparation of graphene is generally preferably a flexible material, and the polymer is not electrically conductive, and may preferably be one or a combination of polyimide, polyether ether ketone, carbon chain polymer, polyethylene, polystyrene, polyvinyl chloride, heterochain polymer, polyimide, polyetherimide, aromatic polymer, cyclic polymer, polyether ether ketone, polyether, polyester, polyamide, polyurethane, and polysulfide rubber. The laser processing parameters are preferably: CO2 infrared laser with wavelength of 10.6 microns, power of 0.1-10W and energy density of 0.1-10J/cm 2 The frequency is 0-100KHz, and the scanning linear velocity is 1-2000mm/s. The graphene electrode pattern is obtained by pre-compiling a scanning route of a laser beam by using a computer matched with a laser, and the electrode pattern can be two unconnected poles on the same polymer film plane as the positive pole and the negative pole of a super capacitor; or one polymer plane can be the same electrode, and the anode and the cathode are assembled in a film laminating mode subsequently. The laser-induced preparation of the graphene has been described in literature methods, and can be referred to as NATURE COMMUNICATIONS | 5.
In the present invention, an aqueous plating solution containing pyrrole, that is, an aqueous solution of pyrrole is prepared by: firstly, a certain amount of deionized water is measured by using a measuring cylinder and is led into a container, and then pyrrole monomers and a surfactant are added, wherein the concentration range of pyrrole is 0.001-1 mol/L, and the concentration range of the surfactant is 0-1 mol/L. The addition of the surfactant can better improve the combination uniformity of pyrrole and graphene, which can be attributed to the structure that one end of the surfactant is hydrophilic and the other end is lipophilic, so the invention is not limited to a great amount, and the invention can be realized at low cost by selecting anionic, cationic, nonionic and other surfactants, and selecting common industrial surfactants such as sodium dodecyl benzene sulfonate and the like.
In the polypyrrole electrodeposition process, the preferable voltage range is 0.01 to 100V, the current range is 1mA to 100A, the electrodeposition time is 1min to 72 hours, and the reaction temperature is controlled to be 0 to 90 ℃; more preferably, the voltage is in the range of 0.1 to 20V, the current is in the range of 100mA to 10A, the electrodeposition time is in the range of 1h to 20h, and the reaction temperature is in the range of 10 to 40 ℃. And after the electrodeposition is finished, taking out the electrode material from the solution, washing the electrode material by using deionized water and ethanol, and then putting the electrode material into a dryer or a vacuum oven for drying treatment to obtain the final graphene/polypyrrole composite electrode material.
The graphene/polypyrrole composite electrode material provided by the invention is prepared by directly obtaining a patterned graphene electrode with a three-dimensional porous structure by using laser induction and taking a flexible polymer as a substrate, and then performing electrodeposition of polypyrrole after hydrophilic treatment. By the method, polypyrrole can be uniformly filled in the three-dimensional grid of the graphene to form a uniform composite material, and the advantages of the graphene and the polypyrrole in the application field of the super capacitor are fully exerted. Meanwhile, in the composite material, the mass ratio of polypyrrole is very high, so that the capacitance performance of the prepared super capacitor is guaranteed. The graphene/polypyrrole composite material prepared by the method has the characteristics of high specific surface area, good conductivity, good reproducibility, simple and feasible process and the like, and the prepared supercapacitor has the advantages of high specific capacity, good cycle stability and the like, so that the popularization value is high.
Drawings
Fig. 1 scanning electron microscope images of (a) laser-induced graphene and (b) graphene after hydrophilic treatment of example 1;
fig. 2 shows (a) a scanning electron microscope picture and (b) a high-resolution transmission electron microscope picture of the graphene/polypyrrole composite material of example 1;
FIG. 3 is a cross-sectional element distribution of graphene/polypyrrole in example 1;
FIG. 4 example 1 shows (a) cyclic voltammogram of graphene/polypyrrole at a scan rate of 100mV/s and (b) at constantCurrent charge and discharge curve, current density 1mA/cm 2 ；
FIG. 5A photograph of a supercapacitor made in example 4.
Detailed Description
Example 1
A preparation method of a graphene/polypyrrole composite electrode material comprises the following steps:
a. laser-induced preparation of graphene on flexible substrate
The preparation method comprises the steps of selecting polyimide with the thickness of 125 mu m as a substrate, utilizing laser induction to prepare graphene, using a CO2 infrared laser marking machine with the equipment wavelength of 10.6 mu m, selecting 6W of power, and selecting the scanning speed of 200mm/s and the frequency of 20kHz. Polyimide is placed on a workbench of a laser marking machine in an air atmosphere, and laser induced graphene (marked as LIG) is obtained after scanning according to a set line.
b. Hydrophilic treatment of graphene electrodes
And c, placing the graphene electrode obtained in the step a in a low-temperature plasma reaction chamber, wherein the oxygen flow is 50mL/min, the treatment time is 20s, the discharge power is 200W, and the vacuum degree is 80Pa, and performing oxygen plasma treatment to improve the hydrophilicity of the electrode material.
c. And c, immersing the graphene electrode obtained in the step b into water-based electroplating solution containing pyrrole monomers, wherein the formula of the electroplating solution is that the concentration of pyrrole is 0.05mol/L, and the concentration of surfactant sodium dodecyl benzene sulfonate is 0.02mol/L. In the electroplating solution, a graphene electrode is used as a positive electrode, a platinum sheet is used as a counter electrode, constant-voltage electrodeposition is carried out by using a voltage-stabilized power supply, the voltage is 1.5V, and the deposition time is 3 hours. And washing and drying to obtain a sample LIG/Ppy-3h.
As can be clearly seen from the scanning electron microscope picture of the graphene obtained in step a of example 1 in fig. 1 (a), the three-dimensional porous lattice structure of the graphene has a hydrophilic angle (contact angle) of about 65 °, which may prevent the aqueous electroplating solution from entering the inner lattice of the graphene. Fig. 1 (b) is an electron microscope photograph after hydrophilic treatment, and the hydrophilic angle is close to 0 °, so that polypyrrole is uniformly deposited on the surface of graphene to form a uniform composite material.
FIG. 2 (a) shows the scanning electron micrograph of LIG/Ppy-3h in example 1, and comparing with FIG. 1 (a), it can be seen that polypyrrole has been deposited into the graphene grid to form a uniform composite material. FIG. 2 (b) shows a high resolution TEM image of LIG/Ppy-3h, which shows the binding details of graphene and polypyrrole.
Fig. 3 is a cross-sectional element distribution diagram of graphene/polypyrrole tested by electron spectroscopy in example 1, wherein C element is mainly from graphene and N element is from polypyrrole. It can be seen from the figure that the cross-sectional element distributions of the two elements tend to be consistent, which indicates that the graphene and the polypyrrole are very uniformly combined, thereby providing guarantee for the composite material to exert the advantages of the two elements.
The LIG and LIG/Ppy-3h obtained in example 1 were respectively scraped from the polymer substrate and then weighed, and the mass proportion of polypyrrole in the composite material was calculated to be 96%, and the high proportion of polypyrrole would allow the composite to have a higher energy storage capacity.
Fig. 4 shows the capacitance performance of graphene/polypyrrole in example 1, and the test instrument is chenhua electrochemical workstation 660D, and the test is performed in a sulfuric acid electrolyte, and it can be seen that, compared with simple graphene LIG, the capacitance performance of the composite material is greatly enhanced. According to the capacitance calculation formula, the specific capacitance of LIG/Ppy-3h can be calculated to reach 941mF/cm 2 。
Example 2
The preparation method of the graphene/polypyrrole composite material is the same as that of example 1, but the electrodeposition time in the step c is changed to 2 hours. The composite material is tested to be 1mA/cm through cyclic charge and discharge 2 The specific capacitance of the capacitor is 622mF/cm at the current density of (2) 2 。
Example 3
The preparation method of the graphene/polypyrrole composite material is the same as that of example 1, but the electrodeposition time in the step c is changed to 1h. The specific capacitance is 180mF/cm under the current density of 1mA/cm < 2 > through the test of cyclic charge and discharge 2 。
Example 4
The preparation method of the graphene/polypyrrole composite material of this example is the same as that of example 1, but the step b is hydrophilicAnd b, the treatment mode is changed into that the graphene electrode composite material obtained in the step a is placed in 70% concentrated nitric acid at 115 ℃ for treatment for 30min. The composite material is tested to be 1mA/cm through cyclic charge and discharge 2 At a current density of 732mF/cm in specific capacitance 2 。
Example 5
In this embodiment, the graphene/polypyrrole composite material obtained in example 1 is assembled into an all-solid-state supercapacitor, and fig. 5 is a real photograph. The positive and negative electrode patterns are designed into interdigital electrodes, and PVA/H2SO4 is used as electrolyte. The preparation method comprises adding 2ml of concentrated sulfuric acid into 20ml of deionized water, adding 2 g of PVA (polyvinyl alcohol), and stirring at 85 ℃ for 60min. 0.5ml of the above electrolyte was dropped into the active region and dried in a vacuum oven at 60 ℃ for 6 hours. And (3) the copper foil is used as an electrode lead-out wire, and the copper foil and the graphene/polypyrrole electrode are connected by conductive silver adhesive, so that the flexible all-solid-state supercapacitor can be assembled.
The super capacitor is tested by adopting an electrochemical workstation, and the current density is 1mA/cm 2 When the specific capacitance reaches 562.MF/cm 2 After 10000 times of circulation, the capacity can be kept to 92.6%.
The invention provides a preparation method of a graphene/polypyrrole composite electrode material. The composite material thus exhibits very good capacitive properties. The flexible all-solid-state supercapacitor prepared from the composite material also has good energy storage performance.
It should be noted that the technical contents described above are only explained and illustrated to enable those skilled in the art to know the technical spirit of the present invention, and therefore, the technical contents are not to limit the scope of the present invention. The scope of the invention is defined by the appended claims. It should be understood by those skilled in the art that any modification, equivalent replacement, and improvement made based on the spirit of the present invention should be considered to be within the spirit and scope of the present invention.

Claims (6)

1. A preparation method of a graphene/polypyrrole composite electrode material is characterized in that laser-induced graphene is subjected to hydrophilic treatment, then the graphene is immersed in water-based electroplating solution containing pyrrole to carry out polypyrrole electrodeposition, and the hydrophilic contact angle range of the graphene after the hydrophilic treatment is 0-30 degrees; the polypyrrole is uniformly filled in the three-dimensional grid of the graphene, and the loading amount of the polypyrrole in the composite electrode material is 50-99.5%; the hydrophilic treatment is carried out by oxygen plasma treatment under the conditions of oxygen flow rate of 50mL/min, treatment time of 20s, discharge power of 200W and vacuum degree of 80 Pa.
2. The method for producing a graphene/polypyrrole composite electrode material according to claim 1, wherein a concentration of pyrrole in the aqueous plating solution containing pyrrole is in a range of 0.001 to 1mol/L, and a concentration of the surfactant is in a range of 0 to 1mol/L.
3. The method for preparing the graphene/polypyrrole composite electrode material according to claim 1, wherein the electrodeposition manner of the polypyrrole includes but is not limited to: one or the combination of constant voltage, variable voltage, pulse voltage, constant current, variable current and pulse current; the electrodeposition time is 1min to 72 hours, and the reaction temperature is controlled to be 0 to 90 ℃.
4. The method for preparing the graphene/polypyrrole composite electrode material according to any one of claims 1 to 3, wherein the following steps are adopted:
a. laser-induced preparation of graphene on a flexible substrate: exposing the polymer film to laser irradiation in an air atmosphere, thereby obtaining a graphene pattern electrode on the surface of the polymer;
b. hydrophilic treatment of graphene electrodes: carrying out hydrophilic treatment on the graphene electrode obtained in the step a to enable the hydrophilic contact angle range to be 0-30 degrees;
c. polypyrrole electrodeposition: and c, immersing the graphene electrode obtained in the step b into an aqueous electroplating solution containing pyrrole monomers, performing electrodeposition of polypyrrole, cleaning and drying.
5. The application of the graphene/polypyrrole composite electrode material obtained by the preparation method of claim 1 in a supercapacitor is characterized in that the graphene/polypyrrole composite electrode material is used as a supercapacitor electrode and is assembled into a flexible all-solid-state supercapacitor according to a conventional assembly method of the supercapacitor, and the specific capacitance of the supercapacitor is 1-10000 mF/cm 2 Energy remained greater than 80% after 10000 cycles.
6. A supercapacitor, which is characterized by comprising the graphene/polypyrrole composite electrode material obtained by the preparation method of claim 1.
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CN207966756U (en) * 2018-01-12 2018-10-12 纳智源科技（唐山）有限责任公司 A kind of graphene ultracapacitor

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