CN112263255A - Graphene skin electrode based on conductive polymer transfer and preparation method thereof - Google Patents
Graphene skin electrode based on conductive polymer transfer and preparation method thereof Download PDFInfo
- Publication number
- CN112263255A CN112263255A CN202011044091.0A CN202011044091A CN112263255A CN 112263255 A CN112263255 A CN 112263255A CN 202011044091 A CN202011044091 A CN 202011044091A CN 112263255 A CN112263255 A CN 112263255A
- Authority
- CN
- China
- Prior art keywords
- graphene
- conductive polymer
- pedot
- preparation
- film
- 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.)
- Pending
Links
Images
Classifications
-
- 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
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The invention discloses a graphene skin electrode based on conductive polymer transfer and a preparation method thereof. The graphene skin electrode based on conductive polymer transfer is a dry electrode obtained by coating a conductive polymer film on a single-layer graphene film. According to the preparation method, a surfactant and an ionic liquid are added into a pure PEDOT (Poly ethylene glycol ether ketone) PSS solution, and then a light, thin, uniform and continuous conductive polymer film is formed on the surface of graphene. The crystallinity of the PEDOT main chain is improved by the graphene, and the conductivity of the electrode is remarkably improved by the interaction. The graphene skin electrode based on conductive polymer transfer, which is prepared by the invention, is an ultrathin dry electrode with high transparency and high conductivity, can be attached to the skin in a conformal manner, and can be used for electrophysiological signal detection.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a graphene skin electrode based on conductive polymer transfer and a preparation method thereof.
Background
Silver and silver chloride electrodes are widely used in clinical medical treatment to collect electrophysiological signals of human bodies, such as electrocardiogram and the like, and conductive gel is required to be added for assistance in the using process. However, the gel tends to dry up when the signal is monitored for a long time and the displacement of the electrodes relative to the skin will produce severe motion artifacts, resulting in poor electrophysiological signal resolution. In order to obtain a high-quality signal, development of an extremely thin and dry electrode is in high demand.
Thin gold films have become a promising alternative because of their high electrical conductivity and biocompatibility. However, dry electrodes made of gold films are expensive and in some cases may produce light-induced photoelectric artifacts when they are used. Low cost and optical transparency are two characteristics that are urgently needed to be added for biopotential monitoring in dry electrodes in order to make them more compatible for integration with other devices.
Graphene is the thinnest electrode material, has excellent optical transparency, high conductivity, excellent mechanical properties and low electrochemical reaction activity, and is also considered to be a skin electrode promising for electrophysiological signal detection.
Disclosure of Invention
The invention aims to provide a graphene skin electrode based on conductive polymer transfer and a preparation method thereof. The preparation method is used for detecting electrophysiological signals by using a PEDOT (polymer stabilized ethylene terephthalate) -PSS (Poly styrene) film as a polymer carrier layer to process/enhance the conductivity of graphene grown by a chemical vapor deposition method.
The graphene skin electrode based on conductive polymer transfer is a dry electrode obtained by covering a conductive polymer film on a single-layer graphene film, and the thickness of the graphene skin electrode is 80-150 nanometers.
The graphene film is single-layer graphene grown on the surface of the copper foil by a chemical vapor deposition method.
The preparation method of the graphene skin electrode based on conductive polymer transfer comprises the following steps:
1) adding surfactant to PEDOT: in the PSS solution, stirring vigorously; then adding ionic liquid and continuing stirring; finally filtering to obtain a conductive polymer solution;
2) spin-coating the conductive polymer solution prepared in the step 1) on graphene growing on the surface of a copper foil to form a three-layer structure material of PEDOT (PSS)/graphene/copper foil;
3) annealing the three-layer structure material obtained in the step 2) for 1-3 minutes at the temperature of 80-120 ℃;
4) and etching the copper foil by using a persulfate solution, transferring the residual PEDOT, namely PSS/graphene film into deionized water, rinsing for 3 times, and finally transferring the PEDOT, PSS/graphene film onto a target substrate.
The surfactant is one or two of sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.
The mass fraction of the added surfactant is 0.25-1.5%.
The ionic liquid is bis (trifluoromethane) sulfimide lithium salt, and the added mass fraction of the ionic liquid is 0.25-1%.
The persulfate is ammonium persulfate or sodium persulfate, and the concentration of the persulfate solution is 1-4 wt%.
The target substrate is a silicon wafer, glass or a flexible polymer film.
The graphene electrode which can be attached to the skin in a conformal mode and is based on conductive polymer transfer is prepared, is an ultrathin dry electrode with high transparency and high conductivity, and can be used for electrophysiological signal detection. According to the invention, a light, thin, uniform and continuous conductive polymer film can be formed on the surface of graphene by adding a surfactant and an ionic liquid into a pure PEDOT (PSS) solution. The crystallinity of the PEDOT main chain is improved by the graphene, and the conductivity of the electrode is remarkably improved by the interaction.
Drawings
Fig. 1 is a flow chart of the preparation of the graphene skin electrode based on conductive polymer transfer according to the present invention.
Fig. 2 is a graph of the frequency versus impedance of the graphene skin electrode based on conductive polymer transfer prepared in example 1 (compared to a silver/silver chloride electrode).
Fig. 3 is a graph of transmittance of the graphene skin electrode based on conductive polymer transfer prepared in example 1.
Detailed Description
In order to make the technical solution of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
1. In order to optimize the vapor phase growth conditions, the typical process of graphene film growth adopted by us is as follows: (1) substrate placement: carefully placing the copper foil with the thickness of 25 microns and a clean surface in a quartz tube and in a heating area of a tube furnace; (2) vacuumizing: starting a mechanical pump to vacuumize, cleaning the gas path for several times, and introducing 20sccm of hydrogen gas after continuously vacuumizing for 30 min; (3) and (3) growing: setting the hydrogen flow at 20sccm, introducing 35sccm methane, heating to 200 deg.C at a heating rate of 10 deg.C/min, then heating to 1000 deg.C at a heating rate of 20 deg.C/min, and growing at 1000 deg.C; (4) cooling and sampling: 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;
2. sodium dodecyl sulfate was added to PEDOT: in the PSS solution (PH1000), the mass fraction of sodium dodecyl sulfate is 1 percent, and the mixture is stirred vigorously for 2 hours; then adding lithium bis (trifluoromethane) sulfonyl imide, wherein the mass fraction of the lithium bis (trifluoromethane) sulfonyl imide is 0.5%, and continuously stirring for 2 hours; finally filtering the mixture by using a 0.45 micron syringe filter to obtain a conductive polymer solution;
3. spin-coating the conductive polymer solution prepared in the step 2 on the graphene growing on the surface of the copper foil obtained in the step 1, and spin-coating at 2000 rpm for 60 seconds to form a three-layer structure material of PEDOT, PSS, graphene and copper foil;
4. annealing the three-layer structure material obtained in the step 3 at the temperature of 100 ℃ for 3 minutes;
5. and etching the copper foil for 2 hours by using a 2 wt% ammonium persulfate solution, transferring the rest PEDOT (PSS)/graphene film into deionized water, rinsing for 3 times, and finally transferring the film onto an SEBS substrate.
The total thickness of the obtained electrode was 100nm, the sheet resistance was 45. omega./sq, the light transmittance was 80%, and the stretchability was 20% as measured.
Claims (8)
1. The graphene skin electrode based on conductive polymer transfer is characterized in that the electrode is a dry electrode obtained by covering a conductive polymer film on a single-layer graphene film, and the thickness of the electrode is 80-150 nanometers.
2. The graphene skin electrode based on conductive polymer transfer according to claim 1, wherein the graphene film is a single layer graphene grown on the surface of the copper foil by chemical vapor deposition.
3. The preparation method of the graphene skin electrode based on conductive polymer transfer according to claim 1, wherein the preparation method comprises the following specific steps:
1) adding surfactant to PEDOT: in the PSS solution, stirring vigorously; then adding ionic liquid and continuing stirring; finally filtering to obtain a conductive polymer solution;
2) spin-coating the conductive polymer solution prepared in the step 1) on graphene growing on the surface of a copper foil to form a three-layer structure material of PEDOT (PSS)/graphene/copper foil;
3) annealing the three-layer structure material obtained in the step 2) for 1-3 minutes at the temperature of 80-120 ℃;
4) and etching the copper foil by using a persulfate solution, transferring the residual PEDOT, namely PSS/graphene film into deionized water, rinsing for 3 times, and finally transferring the PEDOT, PSS/graphene film onto a target substrate.
4. The method according to claim 3, wherein the surfactant is one or two selected from sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate.
5. The method according to claim 3, wherein the surfactant is added in an amount of 0.25 to 1.5% by mass.
6. The preparation method according to claim 3, wherein the ionic liquid is lithium bis (trifluoromethane) sulfonimide, and the added mass fraction of the ionic liquid is 0.25-1%.
7. The production method according to claim 3, wherein the persulfate is ammonium persulfate or sodium persulfate, and the concentration of the persulfate solution is 1 to 4 wt%.
8. The method of claim 3, wherein the target substrate is a silicon wafer, glass or a flexible polymer film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011044091.0A CN112263255A (en) | 2020-09-28 | 2020-09-28 | Graphene skin electrode based on conductive polymer transfer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011044091.0A CN112263255A (en) | 2020-09-28 | 2020-09-28 | Graphene skin electrode based on conductive polymer transfer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112263255A true CN112263255A (en) | 2021-01-26 |
Family
ID=74349426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011044091.0A Pending CN112263255A (en) | 2020-09-28 | 2020-09-28 | Graphene skin electrode based on conductive polymer transfer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112263255A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061285A (en) * | 2021-02-26 | 2021-07-02 | 中国科学院深圳先进技术研究院 | Preparation method of ultrathin porous stretchable film electrode |
| CN113243920A (en) * | 2021-05-12 | 2021-08-13 | 北京石墨烯研究院 | Flexible attached skin electrode and preparation method and application thereof |
| CN114574040A (en) * | 2022-03-08 | 2022-06-03 | 清华大学深圳国际研究生院 | PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method |
Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102543303A (en) * | 2011-12-16 | 2012-07-04 | 苏州汉纳材料科技有限公司 | Patterned transparent electrode fabrication method |
| CN103345963A (en) * | 2013-06-28 | 2013-10-09 | 重庆墨希科技有限公司 | Graphene composite transparent electrode and preparation method and application thereof |
| CN103441065A (en) * | 2013-08-14 | 2013-12-11 | 西安交通大学 | Method for preparing P-type ohmic contact layer of high Al content AlGaN material and application of P-type ohmic contact layer |
| CN103449418A (en) * | 2013-08-19 | 2013-12-18 | 中国科学院化学研究所 | Method for transferring graphene with atomic cleanness |
| CN104797666A (en) * | 2012-10-29 | 2015-07-22 | 3M创新有限公司 | Conductive inks and conductive polymeric coatings |
| CN104860307A (en) * | 2015-05-12 | 2015-08-26 | 青岛华高能源科技有限公司 | Nondestructive transferring method of graphene film |
| CN104897316A (en) * | 2015-06-16 | 2015-09-09 | 青岛大学 | Capacitive ultrathin flexible stress sensor and producing method thereof |
| CN104919633A (en) * | 2012-11-15 | 2015-09-16 | 索尔维公司 | Film forming composition comprising graphene material and conducting polymer |
| CN104992853A (en) * | 2015-07-27 | 2015-10-21 | 南京林业大学 | Method of preparing flexible bendable thin film electrode of supercapacitor |
| CN105070352A (en) * | 2015-07-22 | 2015-11-18 | 西安交通大学 | Flexible super-flat transparent conductive film and preparing method thereof |
| CN105085937A (en) * | 2015-07-20 | 2015-11-25 | 深圳市华星光电技术有限公司 | Preparation method for fullerene/PEDOT: PSS mixed solution and preparation method for substrate of fullerene/PEDOT: PSS composite transparent conductive film |
| CN105304936A (en) * | 2015-12-10 | 2016-02-03 | 微宏动力系统（湖州）有限公司 | Lithium ion secondary cell |
| CN105489767A (en) * | 2015-12-23 | 2016-04-13 | 中国科学院重庆绿色智能技术研究院 | Graphene/polymer electrode-based flexible perovskite solar cell and preparation |
| WO2016143666A1 (en) * | 2015-03-12 | 2016-09-15 | タツタ電線株式会社 | Biomedical electrode device |
| CN106477570A (en) * | 2016-10-14 | 2017-03-08 | 天津大学 | The method that small molecule paraffin shifts Graphene |
| CN107189083A (en) * | 2017-06-21 | 2017-09-22 | 中国科学院广州能源研究所 | Conducting polymer PEDOT organic dispersions system and preparation method thereof |
| CN108389977A (en) * | 2018-04-26 | 2018-08-10 | 西南石油大学 | A kind of perovskite solar cell and preparation method thereof |
| US20190298891A1 (en) * | 2018-04-02 | 2019-10-03 | Shin-Etsu Chemical Co., Ltd. | Bio-electrode composition, bio-electrode, and method for manufacturing a bio-electrode |
| CN111261883A (en) * | 2020-02-21 | 2020-06-09 | 河北工业大学 | Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material |
| CN111627613A (en) * | 2020-06-04 | 2020-09-04 | 武汉理工大学 | Preparation method of silver nanowire flexible transparent conductive film based on phenoxy resin |
-
2020
- 2020-09-28 CN CN202011044091.0A patent/CN112263255A/en active Pending
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102543303A (en) * | 2011-12-16 | 2012-07-04 | 苏州汉纳材料科技有限公司 | Patterned transparent electrode fabrication method |
| CN104797666A (en) * | 2012-10-29 | 2015-07-22 | 3M创新有限公司 | Conductive inks and conductive polymeric coatings |
| CN104919633A (en) * | 2012-11-15 | 2015-09-16 | 索尔维公司 | Film forming composition comprising graphene material and conducting polymer |
| CN103345963A (en) * | 2013-06-28 | 2013-10-09 | 重庆墨希科技有限公司 | Graphene composite transparent electrode and preparation method and application thereof |
| CN103441065A (en) * | 2013-08-14 | 2013-12-11 | 西安交通大学 | Method for preparing P-type ohmic contact layer of high Al content AlGaN material and application of P-type ohmic contact layer |
| CN103449418A (en) * | 2013-08-19 | 2013-12-18 | 中国科学院化学研究所 | Method for transferring graphene with atomic cleanness |
| WO2016143666A1 (en) * | 2015-03-12 | 2016-09-15 | タツタ電線株式会社 | Biomedical electrode device |
| CN104860307A (en) * | 2015-05-12 | 2015-08-26 | 青岛华高能源科技有限公司 | Nondestructive transferring method of graphene film |
| CN104897316A (en) * | 2015-06-16 | 2015-09-09 | 青岛大学 | Capacitive ultrathin flexible stress sensor and producing method thereof |
| CN105085937A (en) * | 2015-07-20 | 2015-11-25 | 深圳市华星光电技术有限公司 | Preparation method for fullerene/PEDOT: PSS mixed solution and preparation method for substrate of fullerene/PEDOT: PSS composite transparent conductive film |
| CN105070352A (en) * | 2015-07-22 | 2015-11-18 | 西安交通大学 | Flexible super-flat transparent conductive film and preparing method thereof |
| CN104992853A (en) * | 2015-07-27 | 2015-10-21 | 南京林业大学 | Method of preparing flexible bendable thin film electrode of supercapacitor |
| CN105304936A (en) * | 2015-12-10 | 2016-02-03 | 微宏动力系统（湖州）有限公司 | Lithium ion secondary cell |
| CN105489767A (en) * | 2015-12-23 | 2016-04-13 | 中国科学院重庆绿色智能技术研究院 | Graphene/polymer electrode-based flexible perovskite solar cell and preparation |
| CN106477570A (en) * | 2016-10-14 | 2017-03-08 | 天津大学 | The method that small molecule paraffin shifts Graphene |
| CN107189083A (en) * | 2017-06-21 | 2017-09-22 | 中国科学院广州能源研究所 | Conducting polymer PEDOT organic dispersions system and preparation method thereof |
| US20190298891A1 (en) * | 2018-04-02 | 2019-10-03 | Shin-Etsu Chemical Co., Ltd. | Bio-electrode composition, bio-electrode, and method for manufacturing a bio-electrode |
| CN108389977A (en) * | 2018-04-26 | 2018-08-10 | 西南石油大学 | A kind of perovskite solar cell and preparation method thereof |
| CN111261883A (en) * | 2020-02-21 | 2020-06-09 | 河北工业大学 | Preparation method and application of ionic liquid functionalized graphene oxide loaded nano cobaltosic oxide composite material |
| CN111627613A (en) * | 2020-06-04 | 2020-09-04 | 武汉理工大学 | Preparation method of silver nanowire flexible transparent conductive film based on phenoxy resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061285A (en) * | 2021-02-26 | 2021-07-02 | 中国科学院深圳先进技术研究院 | Preparation method of ultrathin porous stretchable film electrode |
| CN113061285B (en) * | 2021-02-26 | 2021-10-22 | 中国科学院深圳先进技术研究院 | Preparation method of ultrathin porous stretchable film electrode |
| WO2022179252A1 (en) * | 2021-02-26 | 2022-09-01 | 中国科学院深圳先进技术研究院 | Method for preparing ultra-thin porous stretchable thin-film electrode |
| CN113243920A (en) * | 2021-05-12 | 2021-08-13 | 北京石墨烯研究院 | Flexible attached skin electrode and preparation method and application thereof |
| CN114574040A (en) * | 2022-03-08 | 2022-06-03 | 清华大学深圳国际研究生院 | PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112263255A (en) | Graphene skin electrode based on conductive polymer transfer and preparation method thereof | |
| KR101271249B1 (en) | N-doped Transparent Graphene Film and Method for Preparing the Same | |
| Tong et al. | Self-supported one-dimensional materials for enhanced electrochromism | |
| Pradhan et al. | Vertical growth of two-dimensional zinc oxide nanostructures on ITO-coated glass: effects of deposition temperature and deposition time | |
| CN103991862B (en) | Electrochemistry efficiently peels off the method preparing high-quality graphene | |
| US8247950B2 (en) | Flexible energy conversion device | |
| Fan et al. | Graphene networks for high-performance flexible and transparent supercapacitors | |
| EP1876607A1 (en) | Conductive material and conductive film and process for producing them | |
| CN113243920B (en) | Flexible skin-adhering electrode and preparation method and application thereof | |
| CN102127243A (en) | Conductive and antibacterial polytetrafluoroethylene composite thin film and manufacturing method thereof | |
| CN103199020A (en) | Preparing method and detecting method of liquid grid type grapheme field-effect tube based on polyimide (PI) | |
| KR20170014966A (en) | 2-Dimensional laminated composite structured bistable non-volatile memory device and methods of manufacturing the same | |
| Antohe et al. | Self-seeded electrochemical growth of ZnO nanorods using textured glass/Al-doped ZnO substrates | |
| Mudusu et al. | Multifunctional metal‐oxide integrated monolayer graphene heterostructures for planar, flexible, and skin‐mountable device applications | |
| Lim et al. | A facile fabrication and transfer method of vertically aligned carbon nanotubes on a Mo/Ni bilayer for wearable energy devices | |
| CN108766630B (en) | Flexible sensor based on metal nanowires and preparation method thereof | |
| Zhao et al. | Aramid nanodielectrics for ultraconformal transparent electronic skins | |
| CN107601468A (en) | A kind of preparation method of graphene film | |
| Mohanty et al. | Potential soluble substrates for transient electronics applications: A review | |
| WO2017074867A1 (en) | Transfer of vertically aligned ultra-high density nanowires onto flexible substrates | |
| CN103928533B (en) | Application and energy collection and motion sensing method of graphene in motion liquid drop energy conversation | |
| KR101999488B1 (en) | Method for removal of polymer residues on a graphene film | |
| CN114778618A (en) | Preparation process of graphene/tungsten disulfide gas sensor and sensor thereof | |
| Afroz et al. | A Biocompatible SiC RF Antenna for In-vivo Sensing Applications | |
| CN110693480B (en) | Implantable neural electrode based on metal-MOF (Metal-organic framework) micro-morphology features and preparation method thereof |
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 |