CN112366023A - High-conductivity and high-stability flexible graphene electrode and preparation method thereof - Google Patents

High-conductivity and high-stability flexible graphene electrode and preparation method thereof Download PDF

Info

Publication number
CN112366023A
CN112366023A CN202011410014.2A CN202011410014A CN112366023A CN 112366023 A CN112366023 A CN 112366023A CN 202011410014 A CN202011410014 A CN 202011410014A CN 112366023 A CN112366023 A CN 112366023A
Authority
CN
China
Prior art keywords
graphene
film
electrode
graphene oxide
flexible
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011410014.2A
Other languages
Chinese (zh)
Other versions
CN112366023B (en
Inventor
何大平
晋慧慧
王哲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Jinhai Investment Development Co ltd
Original Assignee
Wuhan Hanene Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Hanene Technology Co Ltd filed Critical Wuhan Hanene Technology Co Ltd
Priority to CN202011410014.2A priority Critical patent/CN112366023B/en
Publication of CN112366023A publication Critical patent/CN112366023A/en
Application granted granted Critical
Publication of CN112366023B publication Critical patent/CN112366023B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • General Physics & Mathematics (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Nanotechnology (AREA)
  • Analytical Chemistry (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a high-conductivity high-stability flexible graphene membrane electrode and a preparation method thereof. The graphene film electrode obtained by the invention has good stability and conductivity, can be suitable for various electrochemical operating environments, and has good stability.

Description

High-conductivity and high-stability flexible graphene electrode and preparation method thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to a high-conductivity high-stability flexible graphene electrode and a preparation method thereof.
Background
Graphene is a two-dimensional monolayer of carbon atoms having a hexagonal packing structure. Passage of carbon atoms in plane by sp2The hybrid forms a covalent sigma bond with one of the strongest bonds in the material of three adjacent carbon atoms, each contributing an unbound electron lying on the pz orbital, forming a pi bond in the direction perpendicular to the plane. The stable benzene six-membered ring structure and the freely moving pi electrons bring a number of excellent and special properties to graphene. On the electrical aspect, due to the special movement behavior of pi electrons in graphene, excellent conductivity is shown. Meanwhile, the Dirac cone energy band structure of the graphene enables the semiconductor characteristic of zero band gap to have a dual-polarized electric field effect. In the aspect of mechanics, the special hexagonal honeycomb structure and sp of graphene2The hybrid bonding mode enables the material to show excellent mechanical properties and have extremely high tensile and compressive capacities. When graphene is subjected to an external force, carbon atoms do not need to be rearranged, but are adapted to the external force through bending deformation, so that the stability of the structure is maintained. Thermally, the thermal conductivity of single layer graphene was experimentally determined to be about (4.84 ± 0.44) × 103WmK-1To (5.30. + -. 0.48). times.103WmK-1On the other hand, the material is far higher than materials such as graphite, diamond and carbon nanotube, and is the best material with heat conductivity reported at present.
Graphene is considered to be an ideal electrode in an electrochemical environment in view of its excellent electronic, chemical and mechanical material properties. Graphene can be made into macroscopic membrane materials, and electrodes can be designed by patterning the graphene membrane or creating the desired size and shape as desired. So far, the Chemical Vapor Deposition (CVD) method is still an excellent way to obtain high-quality large-size graphene thin films, but the graphene films are grown on metal substrates and must be transferred to a target substrate for application, however, the graphene films prepared by the CVD method have low macroscopic strength, are very easy to break during the transfer process, the metal substrate is difficult to remove, and the CVD method has high cost, thereby limiting the application of the graphene films. Currently, printing graphene electrodes directly on a substrate by conventional processing techniques such as inkjet, screen printing and roll coating has tremendous application potential. However, graphene electrodes prepared by this method are generally poor in electrical conductivity and have an effect on the properties of the graphene film due to the re-stacking of graphene sheets and the presence of binders and/or additives.
Disclosure of Invention
In view of the above, the invention provides a flexible graphene electrode with high conductivity and high stability, which can avoid the problems of damage to a graphene film in a transfer process, low conductivity of the graphite film and the like, and a preparation method thereof.
The technical scheme of the invention is realized as follows: the invention provides a preparation method of a flexible graphene membrane electrode with high conductivity and high stability, which comprises the following steps:
step one, mixing graphene oxide and ultrapure water to obtain a graphene oxide suspension, and stirring the graphene oxide suspension to obtain graphene oxide gel;
step two, uniformly blade-coating the graphene oxide gel on the surface of the polyethylene terephthalate film, and drying to obtain the graphene oxide film;
taking the graphene oxide film off the polyethylene terephthalate film, placing the film in a high-temperature furnace for high-temperature reduction under the protection of argon flow, and cooling to obtain the graphene film;
step four, mechanically flattening the graphene film obtained in the step three for later use;
step five, carving and molding the graphene film obtained in the step four by using a laser carving machine for later use;
and step six, fixedly connecting one end of the carved and molded graphene film obtained in the step five with a copper foil to obtain the flexible graphene electrode.
On the basis of the above technical solution, preferably, in the step one, the graphene oxide: the mass ratio of the ultrapure water is 1: (24-49).
On the basis of the above technical scheme, preferably, in the step one, the stirring time is 20-40min, and the stirring speed is 800-.
On the basis of the above technical solution, preferably, in step three, the method for high-temperature reduction specifically includes: under the protection of argon flow, the temperature is raised to 1250-.
Still more preferably, in the fourth step, the mechanical flattening method includes roll forming, hot press forming and cold press forming.
On the basis of the technical scheme, preferably, the conductivity of the prepared flexible graphene membrane electrode is 2 x 10 by adjusting the solid content and the membrane thickness of graphene oxide5S/m-1*106S/m。
The invention also provides the flexible graphene membrane electrode prepared by the method.
The flexible graphene membrane electrode prepared by the method can be used in the fields of batteries, electrochemical sensors, electrocatalysis and the like.
When the flexible graphene film electrode is applied to the field of electrochemistry, one end of the flexible graphene film electrode is fixedly connected with the copper foil.
Compared with the prior art, the high-conductivity high-stability flexible graphene membrane electrode and the preparation method thereof have the following beneficial effects:
(1) the graphene film electrode prepared by the method has good electrical conductivity, namely, the graphene film electrode can be activated for the fifth time and can freely transfer electrons, a Schottky energy barrier at the section of an active substance-electrolyte in an electrochemical reaction is eliminated, high-efficiency energy conversion efficiency is ensured, meanwhile, the graphene film has good thermal conductivity, heat generated in the electrochemical reaction can be taken away, and hot spots are prevented from being generated;
(2) the prepared graphene film has the advantages that the surface micro-folds can be beneficial to the fixation and film formation of active substances on the surface of an electrode and the generation of a coffee ring effect is reduced, the dispersion of the active substances on the surface of the electrode is effectively improved due to the large specific surface area provided by the micro-folds, the active substances can be promoted to be fully contacted with an electrolyte solution, and in addition, the excellent flexibility, corrosion resistance, mechanical stability and thermal stability of the graphene film can not only improve the stability of the active substances, but also bear various electrochemical operating environments.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a raman spectrum of the graphene film prepared in example 1;
FIG. 2 is a scanning electron microscope image of the surface of the graphene film prepared in example 1;
FIG. 3 is a pictorial representation of a graphene film prepared in example 1;
FIG. 4 is a diagram of a graphene film electrode according to an embodiment;
FIG. 5 is a redox cycling voltammogram of potassium ferricyanide on the graphene film electrode prepared in example 3;
FIG. 6 is a graph showing comparative results of hydrogen evolution electrocatalytic linear voltammetry tests performed in an alkaline environment after the graphene membrane electrode prepared in examples 3-5 is loaded with a platinum-carbon catalyst;
FIG. 7 is a graph comparing the results of hydrogen evolution electrocatalytic linear voltammetry tests for an acidic environment after loading a platinum carbon catalyst for comparative example and example 3;
FIG. 8 is a graph of the results of hydrogen evolution electrocatalytic linear voltammetry tests for example 3 in a neutral environment after loading a platinum carbon catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1.
Weighing 2g of graphene oxide powder and 98g of ultrapure water, mixing and stirring to obtain a graphene suspension, stirring for 20min at a stirring speed of 800r/min to obtain graphene oxide gel, scraping the graphene oxide gel on the surface of a PET film, drying at room temperature to obtain a graphene oxide film, taking the graphene oxide film off the PET film, placing the graphene oxide film in a high-temperature furnace for high-temperature reduction under the protection of argon gas flow, heating to 1250 ℃ from room temperature in the first stage, keeping the temperature for 1.5h, continuing heating to 2900 ℃, keeping the temperature for 0.5h, naturally cooling to room temperature to obtain a graphene film, and carrying out Raman spectrum detection on the obtained graphene film, wherein the graphene oxide film has a high reduction degree as shown in figure 1, the surface of the obtained graphene oxide film is detected by a scanning electron microscope, and the surface state is slightly wrinkled as shown in figure 2.
And flattening the obtained graphene film by using a roller until the macroscopic surface of the graphene film is smooth, as shown in fig. 3.
And (3) engraving the pressed graphene film into an electrode shape as shown in fig. 4 by using a laser engraving machine, wherein the circular area is used for loading active substances, one end of the square is fixedly connected with a copper foil, and the copper foil is used for connecting an electrochemical workstation.
Example 2
Weighing 3g of graphene oxide powder and 97g of ultrapure water, mixing and stirring to obtain a graphene suspension, stirring for 30min at a stirring speed of 1000r/min to obtain graphene oxide gel, scraping the graphene oxide gel on the surface of a PET (polyethylene terephthalate) film, drying at room temperature to obtain a graphene oxide film, taking the graphene oxide film off the PET film, placing the graphene oxide film in a high-temperature furnace for high-temperature reduction under the protection of argon gas flow, heating to 1300 ℃ from room temperature in the first stage, keeping the temperature for 2h, continuing heating to 3000 ℃, keeping the temperature for 1h, and naturally cooling to room temperature to obtain the graphene film.
And (3) carrying out cold pressing treatment on the obtained graphene film for 15min under the pressure of 40MPa until the macroscopic surface of the graphene film is smooth.
And (3) engraving the pressed graphene film into an electrode shape as shown in fig. 4 by using a laser engraving machine, wherein the circular area is used for loading active substances, one end of the square is fixedly connected with a copper foil, and the copper foil is used for connecting an electrochemical workstation.
Example 3
Weighing 4g of graphene oxide powder and 96g of ultrapure water, mixing and stirring to obtain a graphene suspension, stirring for 40min at a stirring speed of 1200r/min to obtain graphene oxide gel, scraping the graphene oxide gel on the surface of a PET (polyethylene terephthalate) film, drying at room temperature to obtain a graphene oxide film, taking the graphene oxide film off the PET film, placing the graphene oxide film in a high-temperature furnace for high-temperature reduction under the protection of argon gas flow, heating to 1350 ℃ from room temperature in the first stage, keeping the temperature for 2.5h, continuing heating to 3100 ℃, keeping the temperature for 1.5h, and naturally cooling to room temperature to obtain the graphene film.
And carrying out hot-pressing treatment on the obtained graphene film for 15min at the pressure of 40MPa and the temperature of 80 ℃ until the macroscopic surface of the graphene film is smooth.
Engraving the pressed graphene film into an electrode shape as shown in fig. 4 by using a laser engraving machine, wherein a circular area is used for loading active substances, one end of a square is fixedly connected with a copper foil, the copper foil is used for connecting an electrochemical workstation, and the conductivity of the obtained flexible graphene film electrode is 1 x 106S/m。
Example 4
Weighing 4g of graphene oxide powder and 96g of ultrapure water, mixing and stirring to obtain a graphene suspension, stirring for 40min at a stirring speed of 1200r/min to obtain graphene oxide gel, scraping the graphene oxide gel on the surface of a PET (polyethylene terephthalate) film, drying at room temperature to obtain a graphene oxide film, taking the graphene oxide film off the PET film, placing the graphene oxide film in a high-temperature furnace for high-temperature reduction under the protection of argon gas flow, heating to 1350 ℃ from room temperature in the first stage, keeping the temperature for 2.5h, continuing heating to 3100 ℃, keeping the temperature for 1.5h, and naturally cooling to room temperature to obtain the graphene film.
And (3) carrying out cold pressing treatment on the obtained graphene film for 15min under the pressure of 40MPa until the macroscopic surface of the graphene film is smooth.
Engraving the pressed graphene film into an electrode shape as shown in fig. 4 by using a laser engraving machine, wherein a circular area is used for loading active substances, one end of a square is fixedly connected with a copper foil, the copper foil is used for connecting an electrochemical workstation, and the conductivity of the obtained flexible graphene film electrode is 6 x 105S/m。
Example 5
Weighing 4g of graphene oxide powder and 96g of ultrapure water, mixing and stirring to obtain a graphene suspension, stirring for 40min at a stirring speed of 1200r/min to obtain graphene oxide gel, scraping the graphene oxide gel on the surface of a PET (polyethylene terephthalate) film, drying at room temperature to obtain a graphene oxide film, taking the graphene oxide film off the PET film, placing the graphene oxide film in a high-temperature furnace for high-temperature reduction under the protection of argon gas flow, heating to 1350 ℃ from room temperature in the first stage, keeping the temperature for 2.5h, continuing heating to 3100 ℃, keeping the temperature for 1.5h, and naturally cooling to room temperature to obtain the graphene film.
And carrying out hot-pressing treatment on the obtained graphene film for 15min at the pressure of 40MPa and the temperature of 80 ℃ until the macroscopic surface of the graphene film is smooth.
Engraving the pressed graphene film into an electrode shape as shown in fig. 4 by using a laser engraving machine, wherein a circular area is used for loading active substances, one end of a square is fixedly connected with a copper foil, the copper foil is used for connecting an electrochemical workstation, and the conductivity of the obtained flexible graphene film electrode is 2 x 105S/m。
Comparative example
A commercial carbon paper electrode was used as a comparative example.
Redox test of potassium ferricyanide:
164.6mg of potassium ferricyanide and 1491mg of potassium chloride are weighed and prepared into 200ml of mixed solution for standby by using ultrapure water as a solvent, wherein the concentration of the potassium ferricyanide is 2.5mmol/L, and the concentration of the potassium chloride is 0.1 mol/L.
A platinum wire is used as a counter electrode, Ag/AgCl is used as a reference electrode, a graphene membrane electrode is used as a working electrode, an Autolab electrochemical workstation is used under a three-electrode test system, a potential interval is set to be-0.2-0.6V, cyclic voltammetry is carried out in a potassium ferricyanide solution, as shown in figure 5, the test chart is an oxidation-reduction test chart of example 2, and potassium ferricyanide can undergo obvious reversible oxidation-reduction on the graphene membrane, so that the graphene membrane can freely transfer electrons to be used as the electrode.
Electrolytic water hydrogen evolution test:
and (3) preparing a working electrode, namely weighing 5mg of commercial platinum-carbon with the mass fraction of 20 percent, dispersing the platinum-carbon into 980 mu L of ethanol and 20 mu L of Nafion solution with the mass fraction of 5 percent, coating 40 mu L of the dispersed platinum-carbon ink on the graphene membrane electrode in the example 3 and the commercial carbon paper electrode in the comparative example, and drying in the air to prepare the working electrode.
The electrolytic water hydrogen evolution test is carried out in an alkaline environment:
selecting a carbon rod as a counter electrode, Ag/AgCl as a reference electrode, using 1mol/L KOH solution as electrolyte, setting a potential range of-0.8 to-1.2V by using an Autolab electrochemical workstation under a three-electrode test system, and performing cyclic voltammetry and linear voltammetry tests, wherein the test results are shown in FIG. 6, the graphene electrode prepared in the embodiment 3-5 is tested, and the performance of the prepared graphene electrode in an alkaline environment for hydrogen evolution by electrolysis water is improved along with the improvement of the conductivity of the graphene film.
Electrolytic water hydrogen evolution test in acidic environment
Selecting a carbon rod as a counter electrode, saturated calomel as a reference electrode, and 0.5mol/L electrolyte of H2SO4And (3) setting a potential range of 0 to-0.4V by using an Autolab electrochemical workstation under a three-electrode test system, and carrying out cyclic voltammetry and linear voltammetry tests. As shown in fig. 7, the performance of the graphene electrode of example 3 in hydrogen evolution by electrolysis in an acidic environment is significantly higher than that of commercial carbon paper.
Electrolytic water evolution of hydrogen test in neutral environment
Selecting carbon rods as pairsElectrode, Ag/AgCl as reference electrode, electrolyte 0.5mol/L H2SO4And (3) setting a potential range of 0 to-0.4V by using an Autolab electrochemical workstation under a three-electrode test system, and carrying out cyclic voltammetry and linear voltammetry tests. As shown in fig. 8, the graphene membrane electrode prepared in example 3 can perform efficient hydrogen evolution by electrolyzing water in a neutral environment.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A preparation method of a flexible graphene membrane electrode with high conductivity and high stability is characterized by comprising the following steps:
step one, mixing graphene oxide and ultrapure water to obtain a graphene oxide suspension, and stirring the graphene oxide suspension to obtain graphene oxide gel;
step two, uniformly blade-coating the graphene oxide gel on the surface of the polyethylene terephthalate film, and drying to obtain the graphene oxide film;
taking the graphene oxide film off the polyethylene terephthalate film, placing the film in a high-temperature furnace for high-temperature reduction under the protection of argon flow, and cooling to obtain the graphene film;
step four, mechanically flattening the graphene film obtained in the step three for later use;
step five, carving and molding the graphene film obtained in the step four by using a laser carving machine for later use;
and step six, fixedly connecting one end of the carved and molded graphene film obtained in the step five with a copper foil to obtain the flexible graphene electrode.
2. The method for preparing the flexible graphene film electrode with high conductivity and high stability according to claim 1, wherein in the first step, the graphene oxide: the mass ratio of the ultrapure water is 1: (24-49).
3. The method for preparing the flexible graphene membrane electrode with high conductivity and high stability as claimed in claim 1, wherein in the step one, the stirring time is 20-40min, and the stirring speed is 800-.
4. The method for preparing the highly-conductive and highly-stable flexible graphene film electrode according to claim 1, wherein in the third step, the high-temperature reduction method specifically comprises: under the protection of argon flow, the temperature is raised to 1250-.
5. The method for preparing the highly conductive and highly stable flexible graphene film electrode according to claim 1, wherein in the fourth step, the mechanical flattening method comprises roll forming, hot press forming and cold press forming.
6. The flexible graphene film electrode prepared by the preparation method of the flexible graphene film electrode with high conductivity and high stability as claimed in any one of claims 1 to 5.
7. The flexible graphene membrane electrode of claim 6, for use in the fields of batteries, electrochemical sensors, electrocatalysis.
CN202011410014.2A 2020-12-06 2020-12-06 High-conductivity and high-stability flexible graphene electrode and preparation method thereof Expired - Fee Related CN112366023B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011410014.2A CN112366023B (en) 2020-12-06 2020-12-06 High-conductivity and high-stability flexible graphene electrode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011410014.2A CN112366023B (en) 2020-12-06 2020-12-06 High-conductivity and high-stability flexible graphene electrode and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112366023A true CN112366023A (en) 2021-02-12
CN112366023B CN112366023B (en) 2022-08-19

Family

ID=74535753

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011410014.2A Expired - Fee Related CN112366023B (en) 2020-12-06 2020-12-06 High-conductivity and high-stability flexible graphene electrode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112366023B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116716726A (en) * 2023-08-03 2023-09-08 武汉理工大学三亚科教创新园 Polylactic acid/reduced graphene oxide coaxial coated conductive fiber and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130045427A1 (en) * 2011-08-19 2013-02-21 Nanoteck Instruments, Inc. Prelithiated current collector and secondary lithium cells containing same
CN105883781A (en) * 2016-03-09 2016-08-24 王祉豫 Preparation method of large-area reduced graphene oxide membrane
US20170076833A1 (en) * 2013-02-21 2017-03-16 Nanotek Instruments, Inc. Graphene Oxide-Metal Nanowire Transparent Conductive Film
CN108178148A (en) * 2015-08-07 2018-06-19 常州富烯科技股份有限公司 The preparation method and graphene film of a kind of graphene film
CN209571337U (en) * 2018-10-15 2019-11-01 南京邮电大学 A kind of flexible-paper-base Graphene electrodes
CN111661838A (en) * 2020-04-03 2020-09-15 武汉汉烯科技有限公司 Light high-conductivity flexible lithium battery current collector material and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130045427A1 (en) * 2011-08-19 2013-02-21 Nanoteck Instruments, Inc. Prelithiated current collector and secondary lithium cells containing same
US20170076833A1 (en) * 2013-02-21 2017-03-16 Nanotek Instruments, Inc. Graphene Oxide-Metal Nanowire Transparent Conductive Film
CN108178148A (en) * 2015-08-07 2018-06-19 常州富烯科技股份有限公司 The preparation method and graphene film of a kind of graphene film
CN105883781A (en) * 2016-03-09 2016-08-24 王祉豫 Preparation method of large-area reduced graphene oxide membrane
CN209571337U (en) * 2018-10-15 2019-11-01 南京邮电大学 A kind of flexible-paper-base Graphene electrodes
CN111661838A (en) * 2020-04-03 2020-09-15 武汉汉烯科技有限公司 Light high-conductivity flexible lithium battery current collector material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116716726A (en) * 2023-08-03 2023-09-08 武汉理工大学三亚科教创新园 Polylactic acid/reduced graphene oxide coaxial coated conductive fiber and application thereof
CN116716726B (en) * 2023-08-03 2023-10-24 武汉理工大学三亚科教创新园 Polylactic acid/reduced graphene oxide coaxial coated conductive fiber and application thereof

Also Published As

Publication number Publication date
CN112366023B (en) 2022-08-19

Similar Documents

Publication Publication Date Title
Kang et al. Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells
WO2007061248A1 (en) Catalyst for fuel cell electrode and method of preparing the same
CN110565112B (en) Method for changing cathode oxygen reduction activity by regulating hydrophilicity and hydrophobicity
JP2006134630A (en) Electrode structure of polymer electrolyte fuel cell
Yue et al. MnO2 nanorod catalysts for magnesium–air fuel cells: influence of different supports
Chen et al. Investigation of the Pt–Ni–Pb/C ternary alloy catalysts for methanol electrooxidation
CN112366023B (en) High-conductivity and high-stability flexible graphene electrode and preparation method thereof
US10483555B2 (en) Fuel cells using vertically free standing graphene and carbon nanosheets
Yasutake et al. Catalyst-integrated gas diffusion electrodes for polymer electrolyte membrane water electrolysis: porous titanium sheets with nanostructured TiO2 surfaces decorated with Ir electrocatalysts
Yang et al. Favorable morphology and electronic conductivity of functional sublayers for highly efficient water splitting electrodes
CN108597903B (en) Novel preparation method for compounding magnetic oxide and vertical graphene array and application of novel preparation method in supercapacitor
Yang et al. Polymer electrolyte fuel cell with vertically aligned carbon nanotubes as the electrocatalyst support
JP5574765B2 (en) Catalyst layer for fuel cell and use thereof
CN111313045A (en) Platinum-copper alloy nanowire and preparation method and application thereof
CN113394411B (en) Preparation and application of perovskite nanofiber electrocatalyst for rechargeable zinc-air battery
JP2008235156A (en) Electrode catalyst layer for fuel cell, and fuel cell using it
CN114695904A (en) Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster
JP2008153052A (en) Membrane electrode assembly for fuel cell and fuel cell using it
Hameed Tin oxide species as promotive additives to Ni-P/C electrocatalysts for ethanol electro-oxidation in NaOH solution
CN114068958A (en) Method for preparing carbon nano tube by catalytic pyrolysis of waste plastics and applying carbon nano tube to low-temperature fuel cell
CN112701299A (en) Gas diffusion layer of fuel cell and preparation method and application thereof
CN112151818A (en) Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof
Narayanamoorthy et al. Tenfold catalytic activity enhancement of Pt∕ C by doping with single walled carbon nanotube for methanol oxidation
CN117476960B (en) Nano porous Pt film, preparation method thereof and application thereof in fuel cell electrode
Parkash et al. Platinum on oxidized graphene sheets: a bifunctional electrocatalyst for hydrogen oxidation reaction and methanol oxidation reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20220907

Address after: East 3rd Floor, No. 1275 Meichuan Road, Putuo District, Shanghai 200333

Patentee after: Shanghai Jinhai Investment Development Co.,Ltd.

Address before: 430000 room 02, 1st floor, building 10, daijiashan science and technology venture City, 888 Hanhuang Road, Jiang'an District, Wuhan City, Hubei Province

Patentee before: Wuhan hanene Technology Co.,Ltd.

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20220819