CN113823456A - Flexible graphene electrode and preparation method and application thereof - Google Patents
Flexible graphene electrode and preparation method and application thereof Download PDFInfo
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- 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
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B5/00—Measuring for diagnostic purposes; Identification of persons
- A61B5/68—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient
- A61B5/6801—Arrangements of detecting, measuring or recording means, e.g. sensors, in relation to patient specially adapted to be attached to or worn on the body surface
- A61B5/683—Means for maintaining contact with the body
- A61B5/6832—Means for maintaining contact with the body using adhesives
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- H—ELECTRICITY
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- 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
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The invention provides a flexible graphene electrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: providing a graphene layer formed on a substrate; introducing carbon-containing fibers on the surface of the graphene layer through spinning treatment, and annealing to obtain a carbonized fiber layer formed on the surface of the graphene layer; coating a polymer solution on the surface of the carbonized fiber layer, and evaporating a solvent to obtain a flexible layer in which the carbonized fiber layer is partially embedded; and etching to remove the substrate to obtain the flexible graphene electrode. The flexible graphene electrode is firm and durable, has good conductivity, can be used for electrophysiological signal detection of human skin, can still maintain a high signal-to-noise ratio after repeated use, and has good application prospect.
Description
Technical Field
The invention relates to the field of sensors, in particular to a flexible graphene electrode and a preparation method and application thereof.
Background
The flexible electrode paste is an important part in a wearable device, and a signal acquisition circuit of a traditional electrophysiological sensing system is complex. The development of the electrophysiological detector which is applied to the surface of the skin of a human body, can be stretched along with the change of the skin movement and can keep the functional integrity and the wearing comfort is of great significance to the development of the fields of sports science, man-machine intelligent interaction, health monitoring, medical rehabilitation and the like. Light weight, miniature, simple operation and stable performance are indispensable functional requirements of future wearable devices, especially wearable devices (such as electromyogram, electrocardiogram and electroencephalogram) which are in direct contact with skin (skin-attached type). The graphene has excellent conductivity, light transmittance and stability, and has important practical significance for flexible integration and light-weight miniaturization development of the skin-attached electrophysiological sensor.
The traditional rigid electrode is based on metal electrode materials, and various skin electrodes can be designed and constructed. Among these skin sensors, gold (Au) is the main sensing material due to its biocompatibility and ductility. 300nm films made of gold and parylene are self-adhesive to biological surfaces, but their ultra-thin nature is not easily handled in everyday use. Furthermore, gold is expensive and visually opaque, and therefore not suitable for non-sensory detection. For example, when Au is made into a nano-mesh structure as a gas-permeable and stretchable skin sensor, the cost and visibility of Au and the expensive and time-consuming vacuum deposition process greatly limit its practical usability. However, in view of biocompatibility and ductility, few reports have been made of metals other than Au for electrophysiological signal detection in the skin electronic system. The electrodes currently in commercial use are mainly Ag/AgCl gel electrodes, which are in contact with the skin through the gel. However, under the action of movement, gravity friction and the like, the contact resistance of the traditional electrode is increased, and the electrode can gradually lose efficacy.
In order to reduce the rigidity and realize the biocompatibility, people turn the research direction to a graphene film, and the graphene is a single-atom thin conductive material and has biocompatibility, optical transparency and electrochemical stability. Among all graphene sources, the quality of growing a graphene thin film by a chemical vapor deposition method is the best in terms of conductivity and transparency. In order to make graphene thin films suitable materials for use in skin electrophysiological sensors, the electromechanical stability of graphene thin films is a challenge to overcome in the first place. It is reported that the electronic tattoo of transparent graphene held by 3M Tegaderm tape can maintain conductivity under high strain and accurately detect electrophysiological signals. However, the manufacturing process of such electronic tattoos is complicated, and the atomic thickness of graphene is fragile. Since the skin electrodes are subjected to repeated and prolonged mechanical stress, there is a strong need for a robust skin sensor for reliably measuring important electrophysiological properties of a patient under different circumstances.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
A primary objective of the present invention is to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a flexible graphene electrode, a method for manufacturing the same, and an application of the flexible graphene electrode as a skin electrode for detecting electrophysiological signals, so as to solve the problems of poor detection capability, complex manufacturing process, poor mechanical properties, and the like of the existing skin electrode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a flexible graphene electrode, which comprises the following steps: providing a graphene layer formed on a substrate; introducing carbon-containing fibers on the surface of the graphene layer through spinning treatment, and annealing to obtain a carbonized fiber layer formed on the surface of the graphene layer; coating a polymer solution on the surface of the carbonized fiber layer, and evaporating a solvent to obtain a flexible layer in which the carbonized fiber layer is partially embedded; and etching to remove the substrate to obtain the flexible graphene electrode.
According to one embodiment of the invention, the spinning process is selected from one or more of melt spinning, wet spinning and electrospinning.
According to one embodiment of the invention, the spinning process is electrospinning, and the precursor solution for electrospinning is a solution comprising a first polymer and a metal salt, the first polymer being selected from one or more of phenolic resin and polyacrylonitrile, and the metal salt being selected from one or more of copper chloride, sodium chloride and potassium chloride.
According to one embodiment of the present invention, the precursor solution further comprises a second polymer, wherein the second polymer is one or more selected from hydrogenated styrene-butadiene block copolymer, polydimethylsiloxane and Ecoflex, and the relative molecular mass of the second polymer is 50000-250000, and the mass ratio of the first polymer, the metal salt and the second polymer is 1-3: 0.1-1.
According to one embodiment of the invention, the annealing treatment is carried out under an inert atmosphere, the temperature of the annealing treatment is 600-1000 ℃, and the time of the annealing treatment is 30-60 min.
According to one embodiment of the present invention, the polymer solution to be coated is selected from one or more of a hydrogenated styrene-butadiene block copolymer solution, a polydimethylsiloxane solution, and Ecoflex, and the coating method is a dropping coating or a spin coating.
According to one embodiment of the invention, the substrate is selected from one or more of copper foil, nickel foil, copper-nickel alloy.
The present invention also provides a flexible graphene electrode, comprising: a graphene layer; the carbonized fiber layer is formed on the surface of the graphene layer; and the flexible layer is formed on the surface of the carbonized fiber layer, and the part of the carbonized fiber layer is embedded in the flexible layer.
According to one embodiment of the invention, the graphene layer has a thickness of 0.335nm to 1.675nm, the carbon fiber layer has a thickness of 1 μm to 10 μm, and the flexible substrate layer has a thickness of 50 μm to 100 μm.
The invention also provides application of the flexible graphene electrode as a skin electrode for detecting electrophysiological signals.
According to the technical scheme, the invention has the beneficial effects that:
according to the flexible graphene electrode provided by the invention, the carbon fiber layer is introduced into the flexible graphene electrode by adopting a specific process, the carbon fiber layer can interact with graphene, the overall conductivity of the electrode is improved, and in addition, the carbon fiber layer is partially embedded into the flexible elastomer layer, so that the mechanical strength of the electrode is further improved, and the flexible graphene electrode is firm and durable. The flexible graphene electrode can be used for detecting electrophysiological signals of human skin, can still maintain a high signal-to-noise ratio after repeated use, and has a good application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a flow chart of a process for preparing a flexible graphene electrode according to an embodiment of the present invention;
fig. 2 to 6 respectively show structural schematic diagrams of respective processes for preparing the flexible graphene electrode;
fig. 7 is a schematic diagram of a position where the flexible graphene electrode is used for detecting myoelectric signals on the surface of a human body according to an embodiment of the present invention;
fig. 8 is a signal diagram acquired by using the flexible graphene electrode of example 1 for detecting an electrical signal of skin on a human surface.
Wherein the reference numbers are as follows:
100: substrate
200: graphene layer
300: layer of carbon fibres
301: carbon-containing fiber
400: flexible layer
A: flexible graphene electrode
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Fig. 1 shows a flow chart of a process for preparing a flexible graphene electrode according to an embodiment of the present invention, and as shown in fig. 1, a method for preparing a flexible graphene electrode according to the present invention includes: providing a graphene layer formed on a substrate; introducing carbon-containing fibers on the surface of the graphene layer through spinning treatment, and annealing to obtain a carbonized fiber layer formed on the surface of the graphene layer; coating a polymer solution on the surface of the carbonized fiber layer, and evaporating a solvent to obtain a flexible layer in which the carbonized fiber layer is partially embedded; and etching to remove the substrate to obtain the flexible graphene electrode.
Fig. 2 to 6 respectively show structural schematic diagrams of respective processes for preparing a flexible graphene electrode, and the following describes a process for preparing a flexible graphene electrode according to the present invention in detail with reference to fig. 1 and fig. 2 to 6.
As shown in fig. 2, a graphene layer 200 formed on a substrate 100 is provided. For the present invention, the graphene layer 200 is preferably high quality single layer graphene or few layer graphene.
In one embodiment, the graphene layer is prepared by chemical vapor deposition. The substrate can be copper foil, nickel foil, copper-nickel alloy and the like, taking the substrate as the copper foil as an example, the preparation of the high-quality graphene depends on a clean growth substrate firstly, in the embodiment, an acetone treatment method is adopted on the copper foil substrate, the main condition is that the copper foil is soaked in acetone for 1h, the possibly residual oil stain is removed, then the copper foil is washed by isopropanol, then the copper foil is washed by deionized water, and finally nitrogen is blown and dried. Of course, other methods conventional in the art may be used to perform the cleaning process of the substrate according to actual needs, and the present invention is not limited thereto.
Further, the cleaned copper foil is cut into small pieces and annealed in a high temperature tube furnace to improve crystallinity and flatness and to relieve stress, the main annealing conditions being: under normal pressure, the gas is argon gas of 200sccm, the temperature is slowly raised to 200 ℃, then the temperature is quickly raised to 1000 ℃, annealing is carried out for 30 minutes, and the temperature is naturally reduced to the room temperature. Before being used for a graphene segregation growth substrate, the graphene segregation growth substrate needs to be soaked in dilute nitric acid for thirty seconds for a short time and then washed clean by deionized water, so that a surface oxide layer is removed.
The graphene film is grown by a typical chemical vapor deposition process, which includes:
(1) substrate placement: placing a copper sheet in a quartz tube at the position of a probe of a heating area of a tube furnace; (2) vacuumizing: starting a mechanical pump to vacuumize, cleaning the gas path for a plurality of times, and introducing hydrogen gas after continuous vacuumizing; (3) and (3) growing: introducing a carbon source and heating to a growth temperature, for example, 1000 ℃ to grow graphene at a high temperature under the condition of keeping introducing hydrogen; (4) cooling and sampling: and after the growth is finished, the tube furnace is pushed open, the copper foil with the graphene is rapidly cooled to room temperature, the hydrogen atmosphere is kept, the copper foil is naturally cooled and then vacuumized, and the sample is taken out, so that the graphene layer 200 formed on the copper foil substrate is obtained.
Next, carbon-containing fibers 301 are introduced to the surface of the graphene layer 200 by a spinning process. The spinning treatment method can be melt spinning, dry spinning, wet spinning, electrostatic spinning and the like.
As shown in fig. 3, in the present embodiment, the carbonaceous fibers are introduced by the electrospinning method. The copper foil with the high-quality graphene layer 200 grown thereon was placed on a grounded metal receiving plate, and an electrostatic spinning positive nozzle was placed at a distance of about 10cm from the copper foil with the graphite layer 200 grown thereon.
The precursor solution for electrospinning is a solution comprising a first polymer and a metal salt, wherein the first polymer provides a carbon source selected from one or more of phenolic resin, polyacrylonitrile, and the metal salt is used to promote the conductivity of the material, and the metal salt is generally selected from one or more of copper chloride, sodium chloride, and potassium chloride. Further, the precursor solution may further comprise a second polymer for adjusting the viscosity of the precursor solution to meet the requirement of electrospinning. The second polymer is selected from one or more of hydrogenated styrene-butadiene block copolymer, Polydimethylsiloxane (PDMS), and Ecoflex, preferably hydrogenated styrene-butadiene block copolymer, and may form a transparent flexible electrode. The second polymer has a relative molecular mass of 50000-250000, and the mass ratio of the first polymer, the metal salt and the second polymer is 1-3: 0.1-1, preferably 1:1: 1. The solvent in the precursor solution is preferably tetrahydrofuran or the like, and the present invention is not limited thereto.
Other specific parameters and methods of electrospinning can be performed according to the conventional manner in the art, and generally, the diameter of the single carbon-containing fiber obtained after the spinning treatment is about 1 μm.
As shown in fig. 4, after the carbon-containing fiber 301 is obtained, it is further annealed. The annealing treatment is preferably carried out under an inert atmosphere, and specifically, an inert gas such as argon or the like may be introduced into a tube furnace, and then the temperature is raised to 600 to 1000 ℃, for example, 600 ℃, 700 ℃, 750 ℃, 800 ℃, 900 ℃, 1000 ℃ or the like, preferably 600 ℃, and maintained for 30 to 60 minutes. The annealing temperature should not be too high or too low, and if the temperature is too high, the fibers are easily broken, and if the temperature is too low, part of the fibers cannot be carbonized, thereby affecting the conductivity of the finally obtained electrode. Therefore, the annealing temperature is preferably 600 ℃ to 700 ℃, more preferably 600 ℃, and the annealing time is preferably 30 min.
As shown in fig. 5, after annealing treatment, a carbon fiber layer 300 is formed on the surface of the graphene layer 200, a polymer solution is applied to the surface of the carbon fiber layer 300, and the solvent is evaporated to form a flexible layer 400 (as shown in fig. 6) in which the carbon fiber layer is partially embedded.
Specifically, the polymer solution to be coated is selected from one or more of hydrogenated styrene-butadiene block copolymer solution, polydimethylsiloxane solution (PDMS), and Ecoflex, and the coating method may be a dropping or spin coating method, etc. The polymer in the polymer solution applied here may be the same as or different from the second polymer described above, and the present invention is not limited thereto. The solvent in the polymer solution may be toluene, tetrahydrofuran, or the like, and after the coating is completed, the solvent is removed by natural evaporation, so that the flexible layer 400 is obtained. In the flexible layer 400 obtained by this method, among others, a part of the carbon fiber layer 300 is embedded therein.
Further, the substrate 100 is etched and removed, and the etching method may be a dry etching method or a wet etching method such as electroplating etching, chemical etching, and the like, and the present invention is not limited thereto, for example, the foregoing obtained material is placed in an etchant solution, such as an ammonium persulfate solution, to be etched and removed from the substrate 100, and the flexible graphene electrode shown in fig. 6 is obtained, and includes the graphene layer 200, the carbon fiber layer 300, and the flexible layer 400, where the carbon fiber layer 300 is partially embedded in the flexible layer 400. In some embodiments, the number of graphene layers is 1-5, the thickness is about 0.335-1.675 nm, the thickness of the carbon fiber layer is 1-10 μm, and the thickness of the flexible substrate layer is 50-100 μm.
According to the flexible graphene electrode obtained by the preparation method, the interwoven carbon fibers formed on the graphene layer are tightly adhered to the surface of the graphene through pi-pi interaction, when the first polymer adopts phenolic resin, the interaction between the phenol side group and the metal cations is beneficial to promoting the growth of a crystalline graphene structure, and the benzene part in the polymer is also beneficial to forming highly crystalline graphene, so that the conductivity of the electrode is improved. In addition, the carbon fiber network part of the flexible graphene electrode is embedded into the polymer elastomer, so that the bonding force between layers of the electrode is further improved, and the mechanical property of the flexible graphene electrode is improved. Through the design, the obtained flexible graphene electrode can be applied as a firm skin electrode for detecting electrophysiological signals.
As shown in fig. 7, the skin-attached conductive surface (i.e., one surface of the graphene layer) of the flexible graphene electrode a is connected with the copper wire by using silver paste, so as to reduce contact resistance, and when the flexible graphene electrode a is in contact with the skin, the insulating tape is used to block the direct contact between the connection part and the exposed part of the copper wire and the skin, so as to reduce the signal-to-noise ratio and improve the stability of the electrode. The flexible graphene electrode can be used for human body electrophysiological signal detection, and can still keep a high signal-to-noise ratio after repeated use.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
1) Soaking a copper foil in acetone for 1h, removing residual oil stains, washing with isopropanol, washing with deionized water, blow-drying with nitrogen gas to obtain a copper foil with a clean surface, cutting the copper foil into small pieces (1 cm in width and 2cm in length), annealing in a high-temperature tube furnace under the conditions of normal pressure and argon gas of 200sccm, slowly heating to 200 ℃, quickly heating to 1000 ℃, annealing for 30 minutes, and naturally cooling to room temperature. Before being used for a graphene segregation growth substrate, the graphene segregation growth substrate needs to be soaked in dilute nitric acid for thirty seconds for a short time and then washed clean by deionized water, so that a surface oxide layer is removed.
2) Placing the copper foil obtained in the step 1) in a quartz tube, and positioning the copper foil at the position of a probe in a heating area of a tube furnace. Starting a mechanical pump to vacuumize, cleaning the gas circuit for a plurality of times, and introducing 20sccm of hydrogen gas after continuously vacuumizing for 30 min. Then, setting the hydrogen flow rate to be 20sccm, introducing 35sccm methane, raising the temperature to 200 ℃ at the temperature raising rate of 10 ℃/min, then raising the temperature to 1000 ℃ at the temperature raising rate of 20 ℃/min, and growing the graphene at the high temperature of 1000 ℃. And after the growth is finished, pushing the tube furnace open, quickly cooling the copper foil with the graphene to room temperature, keeping the hydrogen atmosphere, naturally cooling, vacuumizing, and taking out the sample.
3) Placing the copper foil with the graphene film obtained in the step 2) on a grounded metal receiving plate, and placing a positive nozzle of an electrostatic spinning machine (DT-1005) at a distance of 10cm from the graphene/copper foil. The spinning precursor solution comprises the following components in a mass ratio of 1:1:1, absorbing the precursor solution into an injector of an electrostatic spinning machine, closing a cabin door, and applying 9kv high voltage, wherein the pump speed of electrostatic spinning is 0.01mL/h, and the spinning time is 2-5 minutes, so as to obtain the carbon-containing fiber formed on the surface of the graphene layer.
4) And (3) placing the sample obtained in the step 3) into a tubular furnace, raising the temperature to 600 ℃ at the speed of 10 ℃/min under the argon gas with the flow rate of 200sccm, and keeping the temperature for 30 minutes to obtain the carbonized fiber layer. And then the sample is quickly cooled to the room temperature, and the furnace body is also cooled to the room temperature.
5) Taking out the sample obtained in the step 4), carrying out drop casting by using a hydrogenated styrene-butadiene block copolymer solution (toluene as a solvent) and embedding the whole graphene copper foil attached with the carbonized fiber layer, after the polymer solvent is evaporated, putting the graphene copper foil into a 5.4% ammonium persulfate aqueous solution to etch the lower copper foil, after the copper foil is completely etched, changing the solution by deionized water and cleaning for 3 times, taking out the copper foil and naturally drying the copper foil to obtain the flexible graphene electrode.
Comparative example 1
The preparation was carried out by the method of example 1, except that the spinning precursor solution of step 3) was a solution containing, by mass, 0.5: 1:1, copper chloride and a hydrogenated styrene-butadiene block copolymer. It was found that continuous filaments could not be spun by the electrospinning process.
Comparative example 2
Prepared by the method of example 1 except that the annealing temperature of step 4) was 1000 ℃. Experiments show that the annealing temperature is too high, the fiber atrophy is serious, and some fibers are broken and cannot form a net structure.
Comparative example 3
The preparation method of the embodiment 1 is adopted, except that the product of the step 4) is firstly put into 5.4 percent ammonium persulfate aqueous solution to etch away the lower copper foil, and then the carbonized fiber layer and the graphene film after the copper foil is etched away are directly fished out by a hydrogenated styrene-butadiene block copolymer film. Experiments show that the carbonized fiber and graphene are directly fished by the film, the carbonized fiber is not embedded into the copolymer film, and the finally obtained electrode is slightly weak in structure and cannot be reused for multiple times.
Test example
The electrode of example 1 was connected to the copper wire with silver paste on the skin conductive surface, and when contacting the skin, the connection and the exposed portion of the copper wire were blocked by the tape from directly contacting the skin. And connecting the copper wire with an electromyographic data acquisition device. The tester holds the grip dynamometer, makes the dynamics of making a fist each time keep unanimous as far as possible, adopts and makes a fist 1s, relaxes the interval time of 3s and tests.
Fig. 8 shows a signal diagram of the flexible graphene electrode of embodiment 1, which is acquired when the flexible graphene electrode is used for detecting an electrical signal of skin on the surface of a human body, as shown in fig. 3, the flexible graphene electrode of the present invention can still maintain a high signal-to-noise ratio after being repeatedly used for many times.
In conclusion, the carbon fiber layer is introduced into the flexible graphene electrode by adopting a specific process, the carbon fiber layer can interact with graphene, the overall conductivity of the electrode is improved, and in addition, the carbon fiber layer is partially embedded into the flexible elastomer layer, so that the mechanical strength of the electrode is further improved, and the flexible graphene electrode is firm and durable. The flexible graphene electrode can be used for electrophysiological signal detection of human skin, can still maintain a high signal-to-noise ratio after repeated use, and has a good application prospect.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
1. A preparation method of a flexible graphene electrode is characterized by comprising the following steps:
providing a graphene layer formed on a substrate;
introducing carbon-containing fibers on the surface of the graphene layer through spinning treatment, and annealing to obtain a carbonized fiber layer formed on the surface of the graphene layer;
coating a polymer solution on the surface of the carbonized fiber layer, and evaporating a solvent to obtain a flexible layer in which the carbonized fiber layer is partially embedded; and
and etching to remove the substrate to obtain the flexible graphene electrode.
2. The method of claim 1, wherein the spinning process is selected from one or more of melt spinning, wet spinning, and electrospinning.
3. The preparation method according to claim 1, wherein the spinning treatment is electrospinning, the electrospinning precursor solution is a solution containing a first polymer and a metal salt, the first polymer is selected from one or more of phenolic resin and polyacrylonitrile, and the metal salt is selected from one or more of copper chloride, sodium chloride and potassium chloride.
4. The method according to claim 2, wherein the precursor solution further comprises a second polymer, the second polymer is one or more selected from the group consisting of a hydrogenated styrene-butadiene block copolymer, polydimethylsiloxane, and Ecoflex, and has a relative molecular mass of 50000 to 250000, and the mass ratio of the first polymer, the metal salt, and the second polymer is 1 to 3:0.1 to 1.
5. The method according to claim 1, wherein the annealing is performed in an inert atmosphere at a temperature of 600 ℃ to 1000 ℃ for 30min to 60 min.
6. The method of claim 1, wherein the polymer solution to be coated is selected from one or more of a hydrogenated styrene-butadiene block copolymer solution, a polydimethylsiloxane solution, and Ecoflex, and the coating method is a dropping coating or a spin coating.
7. The method of claim 1, wherein the substrate is selected from one or more of copper foil, nickel foil, and copper-nickel alloy.
8. A flexible graphene electrode prepared according to the method of any one of claims 1 to 7, comprising:
a graphene layer;
the carbonized fiber layer is formed on the surface of the graphene layer; and
the flexible layer is formed on the surface of the carbonized fiber layer, and the carbonized fiber layer is partially embedded in the flexible layer.
9. The flexible graphene electrode of claim 8, wherein the graphene layer has a thickness of 0.335nm to 1.675nm, the carbon fiber layer has a thickness of 1 μm to 10 μm, and the flexible substrate layer has a thickness of 50 μm to 100 μm.
10. Use of a flexible graphene electrode according to claim 8 or 9 as a skin electrode for detecting electrophysiological signals.
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| CN114734452A (en) * | 2022-05-17 | 2022-07-12 | 浙江理工大学 | Mechanical arm collision monitoring method based on piezoresistive signals |
| CN114734452B (en) * | 2022-05-17 | 2024-02-23 | 浙江理工大学 | Mechanical arm collision monitoring method based on piezoresistive signals |
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