阅读说明：本技术 一种石墨烯心电电极片及制备无衬底的自支撑石墨烯薄膜的方法 (Graphene electrocardioelectrode plate and method for preparing substrate-free self-supporting graphene film ) 是由 田禾 任天令 于 2021-02-23 设计创作，主要内容包括：本发明涉及纳米材料技术领域。本发明公开一种石墨烯心电电极片,包括导电凝胶层、石墨烯薄膜和导电电极扣；石墨烯薄膜的一面敷设导电凝胶层,石墨烯薄膜与导电电极扣电连接。本发明还公开一种制备无衬底的自支撑石墨烯薄膜的方法,包括：将聚酰亚胺薄膜悬空布置并绷紧；用激光对聚酰亚胺薄膜进行诱导还原；切除聚酰亚胺薄膜未被还原的区域；得到的剩余部分即为无衬底的自支撑石墨烯薄膜。本发明公开的石墨烯心电电极片有效提高生理电信号的信噪比,不需要预先在人体表面涂抹导电膏,使用后石墨烯无残留；本发明公开的方法实现了不需要衬底并具有一定机械强度的石墨烯薄膜的快速制备。(The invention relates to the technical field of nano materials. The invention discloses a graphene electrocardioelectrode slice which comprises a conductive gel layer, a graphene film and a conductive electrode buckle; and a conductive gel layer is laid on one surface of the graphene film, and the graphene film is electrically connected with the conductive electrode buckle. The invention also discloses a method for preparing the substrate-free self-supporting graphene film, which comprises the following steps: the polyimide film is suspended and tightened; performing induced reduction on the polyimide film by using laser; cutting off the unreduced area of the polyimide film; and obtaining the rest part which is the self-supporting graphene film without the substrate. The graphene electrocardioelectrode plate disclosed by the invention effectively improves the signal-to-noise ratio of physiological electric signals, does not need to coat conductive paste on the surface of a human body in advance, and has no residue of graphene after use; the method disclosed by the invention realizes the rapid preparation of the graphene film which does not need a substrate and has certain mechanical strength.)

1. The utility model provides a graphite alkene electrocardioelectrode piece which characterized in that: the graphene film comprises a conductive gel layer, a graphene film and a conductive electrode buckle; one side of the graphene film is laid with the conductive gel layer, and the graphene film is electrically connected with the conductive electrode buckle.

2. The graphene electrocardioelectrode sheet according to claim 1, characterized in that: the graphene film is characterized by further comprising a medical adhesive substrate with a through hole, wherein an adhesive layer is arranged on one surface of the medical adhesive substrate, the conductive electrode buckle and the graphene film are arranged in an area covered by the adhesive layer, and the conductive electrode buckle is fixedly connected with the adhesive layer; the conductive electrode buckle is preferably a male buckle, one side of the protrusion of the conductive electrode buckle is in contact with the adhesive layer, and the protrusion penetrates through the through hole of the medical adhesive substrate.

3. The graphene electrocardioelectrode sheet according to claim 2, characterized in that: still include from the type membrane, it covers on the viscose layer of medical stickness substrate from the type membrane.

4. The graphene electrocardioelectrode sheet according to claim 3, characterized in that: the graphene film comprises any one of a graphene film prepared by laser-induced reduction, a graphene film prepared by a spraying method and a graphene film prepared by a chemical vapor deposition method.

5. A method for preparing a substrate-free self-supporting graphene thin film, comprising the following steps:

the polyimide film is suspended and tightened;

carrying out induced reduction on the polyimide film by using laser;

cutting off the unreduced area of the polyimide film;

and obtaining the rest part which is the self-supporting graphene film without the substrate.

6. The method for preparing the substrate-free self-supporting graphene thin film according to claim 5, further comprising the steps of:

fixedly connecting the edge of the polyimide film with a plurality of clamps;

and moving the positions of the plurality of clamps.

7. The method of preparing a substrate-free self-supporting graphene thin film according to claim 6, wherein:

the thickness of the polyimide film is 25 micrometers;

the wavelength of the laser is between 400 and 500 nm;

the power density of the laser is 10-50mW/cm²。

8. The method for preparing the substrate-free self-supporting graphene thin film according to claim 5, further comprising the steps of:

and performing Raman spectrum test on the upper surface and the lower surface of the polyimide film.

Technical Field

The invention relates to the technical field of nano materials, in particular to a graphene electrocardioelectrode plate and a method for preparing a substrate-free self-supporting graphene film.

Background

Electrocardiograms can be used to monitor and assess heart activity. A common electrocardioelectrode pad is basically composed of two parts: an electrode body and a conductive gel. The surface of the conductive body is provided with a silver/silver chloride coating to enhance the signal-to-noise ratio of the signal, and if the silver/silver chloride is replaced by graphene, the signal-to-noise ratio is improved again.

At present, the graphene electrocardioelectrode slice is generally concentrated on a dry electrode. For graphene dry electrodes, although it is helpful to obtain a high signal-to-noise ratio signal, since graphene is in direct contact with the skin surface, graphene may remain on the skin surface when the electrode is removed. Meanwhile, because of the form of the dry electrode, the electrode and the skin are more easily displaced during movement, and noise is more easily introduced.

Meanwhile, the existing method for preparing the graphene film does not necessarily ensure that the obtained graphene film has high mechanical strength, and therefore, a method for rapidly preparing the graphene film with certain mechanical strength is needed.

Disclosure of Invention

In view of the existing problems, the invention discloses a graphene electrocardioelectrode plate which comprises a conductive gel layer, a graphene film and a conductive electrode buckle; one side of the graphene film is laid with the conductive gel layer, and the graphene film is electrically connected with the conductive electrode buckle.

As an improvement, the graphene film-covered medical adhesive substrate further comprises a medical adhesive substrate with a through hole, wherein an adhesive layer is arranged on one surface of the medical adhesive substrate, the conductive electrode buckle and the graphene film are arranged in an area covered by the adhesive layer, and the conductive electrode buckle is fixedly connected with the adhesive layer; the conductive electrode buckle is preferably a male buckle, one side of the protrusion of the conductive electrode buckle is in contact with the adhesive layer, and the protrusion penetrates through the through hole of the medical adhesive substrate.

As a further improvement, the medical adhesive substrate further comprises a release film, and the release film is covered on the adhesive layer of the medical adhesive substrate.

As a further improvement, the graphene film comprises any one of a graphene film prepared by laser-induced reduction, a graphene film prepared by a spraying method and a graphene film prepared by a chemical vapor deposition method.

The invention also discloses a method for preparing the substrate-free self-supporting graphene film, which is characterized by comprising the following steps of:

the polyimide film is suspended and tightened;

carrying out induced reduction on the polyimide film by using laser;

cutting off the unreduced area of the polyimide film;

and obtaining the rest part which is the self-supporting graphene film without the substrate.

Preferably, the method further comprises the following steps:

fixedly connecting the edge of the polyimide film with a plurality of clamps;

and moving the positions of the plurality of clamps.

Preferably, the first and second electrodes are formed of a metal,

the thickness of the polyimide film is 25 micrometers;

the wavelength of the laser is between 400 and 500 nm;

the power density of the laser is 10-50mW/cm²To (c) to (d);

preferably, the method further comprises the following steps:

and performing Raman spectrum test on the upper surface and the lower surface of the polyimide film.

The graphene electrocardioelectrode plate disclosed by the invention effectively improves the signal-to-noise ratio of physiological electric signals, does not need to coat conductive paste on the surface of a human body in advance, and has no residue of graphene after use; the method disclosed by the invention realizes the rapid preparation of the graphene film which does not need a substrate and has certain mechanical strength.

Drawings

Fig. 1 is a schematic structural view of a graphene electrocardioelectrode plate in one embodiment.

Fig. 2 is an electrocardiographic signal diagram obtained by a graphene electrocardiograph sheet according to an embodiment.

FIG. 3 is a graph of an electrocardiographic signal obtained from a commercial electrode.

Fig. 4 is a schematic structural view of a graphene electrocardioelectrode plate in another embodiment.

Fig. 5 is a diagram of the apparatus structure required to prepare a substrate-free self-supporting graphene thin film in one embodiment.

Fig. 6 is a raman spectrum of the upper surface of the substrate-free self-supporting graphene thin film prepared in one embodiment.

Fig. 7 is a raman spectrum of the lower surface of the substrate-free self-supporting graphene thin film prepared in one embodiment.

Figure number and name: 1. conductive electrode is detained, 2, medical stickness substrate, 3, graphene film, 4, electrically conductive hydrogel, 5, from type membrane, 6, wire, 7, polyimide film, 8, fixture device, 8a, first anchor clamps, 8b, second anchor clamps, 8c, platform, 9, laser light source.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention.

In some embodiments, a conductive electrode clip 1 (the conductive electrode can be made of stainless steel) for connecting with a back-end collecting device is placed on a medical adhesive substrate 2 (the medical adhesive substrate is used for fixing the electrode on the skin surface). Transferring the graphene film 3 with conductive upper and lower surfaces (preferably, a graphene film prepared by laser-induced reduction) onto the conductive electrode buckle 1, preferably embedding the graphene film in the conductive electrode buckle to be in full contact with the conductive electrode buckle; if the lower surface of the graphene film is not reduced, the upper surface and the lower surface are not conductive at the moment, and electrocardiosignals cannot be collected. And preparing conductive hydrogel 4 on the surface of the graphene. Because the conductive hydrogel can be dehydrated under the exposed condition, the conductivity is reduced, and the signal to noise ratio of electrocardiosignals is reduced, a release film 5 with the same shape as the medical adhesive substrate is pasted on the hydrogel and the medical substrate. When the graphene electrocardioelectrode is not used, the release film 5 is glued with the medical adhesive substrate 2 to form a closed cavity, so that the water in the hydrogel can not be diffused into the air, and the service life of the electrocardioelectrode is prolonged. When in use, the release film is removed, and the rest part is pasted on the surface of human skin. The obtained graphene electrocardioelectrode sheet is shown in figure 1, and electrocardio is measured to obtain a signal diagram shown in figure 2. FIG. 3 is a graph of an electrocardiographic signal obtained from a commercial electrode.

In other embodiments, the graphene solution is sputtered onto the conductive electrode button to form a graphene film.

In other embodiments, the graphene film is prepared on the non-conductive substrate material by a chemical vapor deposition method, and only one surface of the graphene film 3 attached to the substrate material is conductive; the graphene layer is connected with the conductive electrode buckle 1 through silver paste or other conductive substances such as a lead 6, and the obtained graphene electrocardioelectrode plate is shown in fig. 4.

In other embodiments, graphene thin films prepared by laser-induced redox are used for electrocardio-electrodes.

The invention also discloses a method for manufacturing the substrate-free self-supporting graphene film used in the electrocardio-electrode.

Taking a polyimide film 7 with a certain thickness, cutting the polyimide film into a rectangle, and clamping the polyimide film to be flat and suspended through a clamp device 8 (the clamp device comprises a first clamp 8a, a second clamp 8b and a platform 8c, one side of the polyimide film is fixedly connected with the first clamp, the other opposite side of the polyimide film is fixedly connected with the second clamp, after the first clamp is fixed, the second clamp is translated towards the direction far away from the first clamp, and after the polyimide film is flat, the second clamp is fixed, and the polyimide film is suspended because the two clamps have a certain height from the surface of the platform); the laser light source 9 is fixed on a biaxial mobile platform, and the polyimide film is subjected to laser-induced reduction by adopting a linear scanning mode; for reducing the polyimide film with the thickness of 25 microns, the laser wavelength range is 400-500nm, and the laser power density is 10-50mW/cm²The laser light source of (1). And (3) performing Raman spectrum detection on the upper surface and the lower surface of the polyimide film, wherein the Raman spectrum represents characteristic peaks (G peak and D peak) of the graphene, and the fact that the detected parts of the upper surface and the lower surface of the polyimide film are reduced into the graphene through laser induction is confirmed (as shown in figures 6-7), and meanwhile, the film is not broken down. Cleaving the polyimideThe non-reduced area of the film; and obtaining the rest part which is the self-supporting graphene film without the substrate.

The graphene film prepared by the technical scheme has smooth and flat surface, conductive upper and lower surfaces and good mechanical strength, does not need to attach materials to any substrate in the preparation process, and can be transferred without the substrate.

The following improvements may also be made in some embodiments: marking a grid pattern on the lower surface of the polyimide film, wherein the grid pattern is a 10 × 20 array formed by small square lattices with the square of 0.5 × 0.5cm in the embodiment, and the grid pattern just completely covers the lower surface of the polyimide film; marking all two adjacent mesh points on the same mesh line on the mesh pattern, measuring the resistance between the two mesh points to judge whether the two mesh points are conductive, and if the two mesh points are conductive, marking the straight line segment between the two mesh points; the area within the maximum closed figure enclosed by all marked straight line segments is the area which has been reduced to graphene. And cutting off the unreduced area to obtain a substrate-free self-supporting graphene film.

While the invention has been described with reference to specific embodiments and applications, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.