CN117700979A - Stretchable self-adhesive self-healing conductive film, and preparation method and application thereof - Google Patents
Stretchable self-adhesive self-healing conductive film, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a stretchable, self-adhesive and self-healing conductive film, a preparation method and application thereof, wherein the conductive film is prepared from a conductive polymer, a flexible polymer and a polyhydroxy compound, and the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate); the flexible polymer is polyvinylpyrrolidone or a combination of two or more of aqueous polyurethane, polyvinyl alcohol, polyvinylpyrrolidone and tannic acid. The flexible polymer or the flexible polymer and the polyhydroxy compound can be entangled together through hydrogen bonding to form physical crosslinking. The film dry electrode provided by the invention has the advantages of impedance stability, flexibility and stretchability and sweat resistance, and solves the problems of dry wet electrode and long-term wearing allergy, and the problem of difficult electric signal monitoring under large skin deformation. The film dry electrode provided by the invention can realize a self-healing function and prolong the service life of the electrode.
Description
Technical Field
The invention belongs to the technical field of biological medicine, and particularly relates to a stretchable self-adhesive self-healing conductive film, a preparation method and application thereof.
Background
The brain characteristics, heartbeat, muscle contraction and other activities of human beings are accompanied by the generation of electric signals, and corresponding electroencephalogram, electrocardio and myoelectric signals can be acquired by placing surface electrodes on the body surface. The noninvasive surface electrical signal monitoring avoids the infection risk of the implanted electrode, is widely accepted by the masses, and has obvious advantages in scientific research and daily medical treatment. The surface electrode is used as an important element of the electric signal monitoring system to directly determine the quality of the monitored signal.
The surface electrode may be divided into a wet electrode and a dry electrode. Commercial conductive gel is a viscous conductive fluid with water content higher than 80%, and is used as an interface conductive layer of skin and an electrode, and has application in electrocardio, myoelectricity and electroencephalogram monitoring, but the conductive gel has high water content, is easy to dry and harden, loses conductivity and causes monitoring failure. The commercial patch electrode seals Ag/AgCl hard electrode and conductive gel in gummed paper, and the wet electrode has three defects, and can not meet the requirement of long-term monitoring, and is specifically expressed as follows: (1) Because the water content of the conductive gel is high, the gel is dehydrated and dried to lose conductivity along with the extension of time, and the conductive gel is not suitable for long-term application scenes; (2) The commercial patch electrode has thicker thickness and harder texture, does not have stretching conductivity, and is easy to desorb with skin to cause signal loss when the myoelectricity of large deformation action is monitored; (3) Prolonged contact of the wet electrode with the skin can lead to serious skin allergy problems. The dry electrode is used as an anhydrous device, the conductivity of the dry electrode is stable for a long time, but the dry electrode is limited by the problem of long-term conformal adhesion between the electrode and the skin, and the interface impedance of the dry electrode is unstable, and the dry electrode is specifically expressed as follows: the hard dry electrode has the problems of slippage with the skin and unstable interface impedance in the monitoring process, and is not suitable for long-term monitoring; the flexible dry electrode is gradually becoming a choice scheme for long-term monitoring of body surface electric signals due to the characteristics of the flexible polymer, such as good biocompatibility with skin, softness and comfort, but in long-term monitoring, the adhesion performance between the electrode and the skin is poor and even the electrode is damaged or falls off due to body surface perspiration and movement interference. Therefore, there is an urgent need to develop a stretchable electrode capable of resisting motion disturbance and sweat adhesion in long-term monitoring.
Disclosure of Invention
The invention aims to provide a stretchable, self-adhesive and self-healing conductive film, a preparation method and application thereof, wherein the conductive film can be used for preparing a flexible bioelectric dry electrode which has biocompatibility, stretching, self-adhesion and self-healing, realizes the stability of an electrode-skin interface and can be used for monitoring long-range bioelectric signals.
The invention provides a stretchable, self-adhesive and self-healing conductive film which is prepared from a conductive polymer, a flexible polymer and polyhydroxy compounds,
the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate);
the flexible polymer is polyvinylpyrrolidone or a combination of two or more of aqueous polyurethane, polyvinyl alcohol, polyvinylpyrrolidone and tannic acid.
Preferably, the polyhydroxy compound is ethylene glycol and/or sorbitol.
Preferably, the mass fraction of the flexible polymer in the conductive film is 50-85%.
Preferably, the mass of the polyhydroxy compound is 0.2% -3.5% of the mass of the conductive polymer solution.
The invention provides a preparation method of the stretchable, self-adhesive and self-healing conductive film, which comprises the following steps:
a) Poly (ethylenedioxythiophene): uniformly mixing a poly (styrene sulfonate) solution and a polyhydroxy compound to obtain a first mixed solution;
b) Sequentially adding two or more than two flexible polymer aqueous solutions into the first mixed solution, and uniformly mixing to obtain a blending mixed solution;
c) And drying the blending mixed solution to obtain the stretchable self-adhesive self-healing conductive film.
Preferably, the drying temperature in the step C) is 50-70 ℃, and the drying time in the step C) is 2-3 hours.
The invention provides a film dry electrode which is prepared from the stretchable, self-adhesive and self-healing conductive film and a copper wire.
The invention provides application of the thin film dry electrode in preparing myoelectricity, electrocardio and electroencephalogram signal detection devices.
The invention provides a stretchable, self-adhesive and self-healing conductive film which is prepared from a conductive polymer, a flexible polymer and a polyhydroxy compound, wherein the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate); the flexible polymer is polyvinylpyrrolidone or a combination of two or more of aqueous polyurethane, polyvinyl alcohol, polyvinylpyrrolidone and tannic acid. The flexible polymer or the flexible polymer and the polyhydroxy compound can be entangled together through hydrogen bonding to form physical crosslinking. The film dry electrode provided by the invention has the advantages of impedance stability, flexibility and stretchability and sweat resistance, and solves the problems of dry wet electrode and long-term wearing allergy, and the problem of difficult electric signal monitoring under large skin deformation. The film dry electrode provided by the invention can realize a self-healing function and prolong the service life of the electrode.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a photograph showing the flexibility and self-adhesion of the conductive film prepared in example 1 of the present invention;
FIG. 2 is a photograph showing the skin safety of a conductive film prepared in example 1 of the present invention after wearing for 6 hours;
FIG. 3 is a photograph showing the self-healing function of the conductive film prepared in example 1 of the present invention;
FIG. 4 is the surface myoelectricity data measured under hand motion for the electrode prepared in example 1 of the present invention;
FIG. 5 shows the tensile properties of the conductive films obtained in the examples and comparative examples of the present invention;
fig. 6 shows adhesion properties of conductive films obtained in examples of the present invention and comparative examples.
Detailed Description
The invention provides a stretchable, self-adhesive and self-healing conductive film which is prepared from a conductive polymer, a flexible polymer and polyhydroxy compounds,
the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate);
the flexible polymer is polyvinylpyrrolidone or a combination of two or more of aqueous polyurethane, polyvinyl alcohol, polyvinylpyrrolidone and tannic acid.
In the present invention, the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT: PSS) as the primary conductive material.
In the present invention, the flexible polymer is preferably polyvinylpyrrolidone, or two or more of aqueous polyurethane (WPU), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) and tannic acid, and specifically, in the embodiment of the present invention, polyvinylpyrrolidone, a combination of aqueous polyurethane and tannic acid, or a combination of aqueous polyurethane, polyvinyl alcohol and polyvinylpyrrolidone may be used. In the invention, the aqueous polyurethane is the aqueous polyurethane commonly used in the field, and special preparation is not needed.
In the present invention, the mass fraction of the flexible polymer is preferably 50 to 85%, more preferably 60 to 70%, such as 50%,55%,60%,65%,70%,75%,80%, preferably a range having any of the above values as an upper limit or a lower limit.
In the present invention, the polyol is preferably ethylene glycol and/or sorbitol to increase the conductivity of PEDOT: PSS. The mass of the polyhydroxy compound is preferably 0.2% to 3.5% by mass of the conductive polymer solution, more preferably 0.5 to 3.5%, such as 0.5%,1%,2.5%,3%,3.5%, preferably a range having any of the above values as an upper limit or a lower limit. Since PEDOT: PSS is a liquid, the term "conductive polymer solution" as used herein is intended to define the character of "conductive polymer" and does not mean that the conductive polymer solution contains a solvent.
In the present invention, the thickness of the conductive film is preferably 70 to 80. Mu.m, more preferably 75 to 80. Mu.m.
The invention also provides a preparation method of the stretching, self-adhesion and self-healing conductive film, which comprises the following steps:
a) Poly (ethylenedioxythiophene): uniformly mixing a poly (styrene sulfonate) solution and a polyhydroxy compound to obtain a first mixed solution;
b) Sequentially adding two or more than two flexible polymer aqueous solutions into the first mixed solution, and uniformly mixing to obtain a blending mixed solution;
c) And drying the blending mixed solution to obtain the stretchable self-adhesive self-healing conductive film.
In the present invention, when two polyols are used, the two polyols are preferably added in the form of aqueous solutions, one of the aqueous solutions is added first, and after being uniformly mixed with the PEDOT: PSS solution, the other aqueous solution is added, and the order of addition is not particularly limited.
The invention preferably mixes the PEDOT-PSS solution with the polyhydroxy compound under the stirring condition, and the invention does not limit the rotation speed and the stirring time, and can uniformly mix the PEDOT-PSS solution and the polyhydroxy compound.
After the first mixed solution is obtained, the flexible polymer aqueous solution is added into the first mixed solution, and the mixture is uniformly mixed under the stirring condition to obtain the blending mixed solution.
Preferably, two or more than two flexible polymer aqueous solutions are respectively added, one flexible polymer aqueous solution is added and uniformly mixed, the other flexible polymer aqueous solution is added, and the like until the addition is complete.
The first mixed solution and the flexible polymer aqueous solution are preferably mixed under the stirring condition, the rotation speed and the stirring time of the invention are not particularly limited, and the first mixed solution and the flexible polymer aqueous solution can be uniformly mixed.
After the blending mixed solution is obtained, the self-adhesive self-healing conductive film is preferably obtained by dripping the self-adhesive self-healing conductive film on the surface of a base material, drying and removing moisture.
In the present invention, the drying temperature is preferably 50 to 70 ℃, more preferably 60 to 65 ℃, and the drying time is preferably 2 to 3 hours.
The invention also provides a film dry electrode which is prepared from the stretchable, self-adhesive and self-healing conductive film and a copper wire. Specifically, the conductive film is preferably obtained by conducting and fixing the conductive film with copper by means of a conductive adhesive tape or the like. The fixing method is a conventional method in the art, and the present invention is not described herein.
The invention also provides application of the film dry electrode as a flexible dry electrode in myoelectricity, electrocardio and electroencephalogram signal detection.
The invention provides a stretchable, self-adhesive and self-healing conductive film which is prepared from a conductive polymer, a flexible polymer and a polyhydroxy compound, wherein the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate); the flexible polymer is polyvinylpyrrolidone or a combination of two or more of aqueous polyurethane, polyvinyl alcohol, polyvinylpyrrolidone and tannic acid. The film dry electrode provided by the invention has the advantages of impedance stability, flexibility and stretchability and sweat resistance, and solves the problems of dry wet electrode and long-term wearing allergy, and the problem of difficult electric signal monitoring under large skin deformation. The film dry electrode provided by the invention can realize a self-healing function and prolong the service life of the electrode.
In order to further illustrate the present invention, the following examples are provided to describe in detail a stretchable, self-adhesive, self-healing conductive film, its preparation method and application, but should not be construed as limiting the scope of the present invention.
Example 1
(1) The sorbitol solution was added to the PEDOT PSS solution in an amount of 0.54wt% of the PEDOT PSS solution, and the mixture was stirred at room temperature for 0.5h to mix uniformly.
(2) Ethylene glycol was added to the above solution in an amount of 2.5wt% of PEDOT: PSS solution, and stirring was continued for 0.5h.
(3) The WPU solution (10 wt% concentration) was mixed with the solution in step (2) with a WPU loading of 33.3wt% in the blend and vigorously stirred at room temperature for 1h.
(4) And (3) mixing PVP solution (with the concentration of 10 wt%) with the solution in the step (3), wherein the load of PVP in the blend is 33.3wt%, and stirring vigorously at room temperature for 1h to obtain a uniformly mixed solution.
(5) The mixed solution in step (4) was filtered using a 0.45 μm pin filter to remove large particles from the solution. And (3) dripping 250 mu L of the mixed solution obtained in the step (4) on a disposable culture dish by using a liquid-transferring gun, and drying at 60 ℃ for 2.5 hours to obtain the self-supporting substrate-free PEDOT-PSS film.
In the PEDOT: PSS film of example 1, PEDOT: PSS was the main conductive substance, and ethylene glycol and sorbitol were used to improve the conductivity of PEDOT: PSS. The nonionic WPU can be well mixed with PEDOT/PSS solution to improve the stretchability of PEDOT/PSS film. PVP is a long-chain macromolecule and has a strong-polarity lactam group, and can be physically entangled with a WPU molecular long chain to form an interpenetrating network structure, so that the stretchability of the material is further improved. Furthermore, the synergistic effect of WPU and PVP improves the self-adhesion and self-healing properties of the film.
Example 2
(1) Ethylene glycol was added to the PEDOT/PSS solution in an amount of 3.5wt% based on the PEDOT/PSS solution, and the mixture was stirred at room temperature for 0.5h to mix the mixture uniformly.
(2) The WPU solution (10 wt% concentration) was mixed with the solution in step (1) with a WPU loading of 40wt% in the blend and vigorously stirred at room temperature for 1h.
(3) And (3) mixing the tannic acid solution (with the concentration of 10 wt%) with the solution in the step (2), wherein the loading of tannic acid in the blend is 40wt%, and stirring vigorously at room temperature for 1h to obtain a uniformly mixed solution.
(4) And (3) dripping 250 mu L of the mixed solution obtained in the step (3) on a disposable culture dish by using a liquid-transferring gun, and drying at 60 ℃ for 2.5 hours to obtain the self-supporting substrate-free PEDOT-PSS film.
In the PEDOT: PSS film of example 2, tannic acid contains a large amount of phenolic hydroxyl groups, forms physical cross-links with the WPU main chain through hydrogen bonds, is an adhesive between polymer chains, improves the tensile properties of the conductive film, and forms firm adhesion with various attachments through Van der Waals forces. The film has self-healing function due to the synergistic effect of tannic acid and WPU.
Example 3
(1) Ethylene glycol was added to the PEDOT/PSS solution in an amount of 3.5wt% based on the PEDOT/PSS solution, and the mixture was stirred at room temperature for 0.5h to mix the mixture uniformly.
(2) The PVA solution (10 wt% concentration) was mixed with the solution in step (2), wherein the PVA was supported in the blend at 20wt% and vigorously stirred at room temperature for 1 hour.
(3) And (3) mixing PVP solution (with the concentration of 10 wt%) with the solution in the step (3), wherein the load of PVP in the blend is 60wt%, and stirring vigorously at room temperature for 1h to obtain a uniformly mixed solution.
(4) mu.L of the mixed droplets of step (4) were taken out using a pipette and dried on a disposable dish at 60℃for 2.5 hours to obtain a self-supporting substrate-free PEDOT: PSS film.
In the PEDOT: PSS film of example 3, hydrogen bond interaction is formed between PVA and PVP, physical entanglement of two molecular long chains occurs, stretchability of the film is improved, and self-healing is achieved. Meanwhile, PVP molecular chains form firm adhesive force with different attachments through Van der Waals force.
Example 4
(1) Sorbitol was added to the PEDOT/PSS solution in an amount of 2.6wt% based on the PEDOT/PSS solution, and the mixture was stirred at room temperature for 0.5h to mix the mixture uniformly.
(2) Ethylene glycol was added to the PEDOT/PSS solution in an amount of 0.9wt% based on the PEDOT/PSS solution, and the mixture was stirred at room temperature for 0.5h to mix the mixture uniformly.
(3) And (3) mixing PVP solution (with the concentration of 10 wt%) with the solution in the step (3), wherein the load of PVP in the blend is 40wt%, and stirring vigorously at room temperature for 1h to obtain a uniformly mixed solution.
(4) mu.L of the mixed droplets of step (4) were taken out using a pipette and dried on a disposable dish at 60℃for 2.5 hours to obtain a self-supporting substrate-free PEDOT: PSS film.
In the PEDOT-PSS film of example 4, PVP has strong physical force on the substrate, has good adhesion, and a small amount of sorbitol can effectively adjust the hygroscopicity and the softness of PVP and improve the tensile property of the conductive film. The film of example 4 was subjected to a tensile test using an electronic universal tester at a test rate of 5mm/min and an elongation at break of 77.9%. The adhesion of the film to the glass was evaluated by interfacial adhesion according to the standard 90 degree peel test method and was 0.35N/cm. And the sheet resistance of the film is 108.3 omega/≡is measured by a four-probe resistivity tester.
Example 5
A PEDOT PSS film was prepared as in example 1, except that the PVP loading in the blend was 16.7wt% and the WPU loading in the blend was 49.9wt% in example 5.
Comparative example 1
A PEDOT PSS film was prepared as in example 1, except that the PVP loading in the blend was 0wt% and the WPU loading in the blend was 66.6wt% in example 4.
Comparative example 2
A PEDOT PSS film was prepared as in example 1, except that the PVP loading in the blend was 49.9wt% and the WPU loading in the blend was 16.7wt% in example 4.
Comparative example 3
A PEDOT PSS film was prepared as in example 1, except that the PVP loading in the blend was 66.6wt% and the WPU loading in the blend was 0wt% in example 4.
Performance tests were performed on the PEDOT: PSS films prepared in example 1, example 5, and comparative examples 1 to 3. The tensile test was performed using an electronic universal tester at an experimental rate of 5mm/min. The results are shown in Table 1 and FIGS. 5-6, and it can be seen from the test results that the addition of PVP can greatly improve the tensile properties of the film and the elongation at break. The adhesion of the film to the glass was evaluated by interfacial adhesion according to standard 90 degree peel test methods, and the addition of PVP resulted in improved adhesion. And measuring the sheet resistance of the film by adopting a four-probe resistivity tester. In example 1, the elongation at break of the film was 60.1% and the adhesion was 0.38N/cm.
The conductive film of the present invention is applied to human skin, and needs to conform to the deformation of human skin, so the elongation at break is not too low, and besides the elongation at break and the adhesion performance, the softness and the conductivity performance of the conductive film are also considered, and the PVP content of comparative example 3 is higher, and although the elongation at break and the adhesion performance are better, the conductivity performance is poorer, and the hardness is higher, so the conductive film is not suitable for adhesion to the surface of human body.
TABLE 1 Performance test of PEDOT: PSS films prepared in examples and comparative examples
| Sheet resistance | Tensile Strength (MPa) | Modulus of elasticity (MPa) | Elongation at break | |
| Example 1 | 179.4Ω/□ | 3.64 | 10.6 | 60.1％ |
| Example 4 | 108.3Ω/□ | 5.18 | 9.3 | 77.9％ |
| Example 5 | 105.5Ω/□ | 3.40 | 13.1 | 25.8％ |
| Comparative example 1 | 25.1Ω/□ | 1.58 | 17.2 | 16.3％ |
| Comparative example 2 | 1.02kΩ/□ | 3.32 | 12.8 | 64.3％ |
| Comparative example 3 | 3.75kΩ/□ | 5.32 | 19.1 | 48.9％ |
TABLE 2 adhesion of PEDOT: PSS films prepared in examples and comparative examples
| Adhesion (N/cm) | |
| Example 1 | 0.38 |
| Example 5 | 0.20 |
| Comparative example 1 | 0.12 |
| Comparative example 2 | 0.24 |
| Comparative example 3 | 0.39 |
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A stretchable, self-adhesive, self-healing conductive film is prepared from conductive polymer, flexible polymer and polyhydroxy compound,
the conductive polymer is poly (ethylenedioxythiophene): poly (styrene sulfonate);
the flexible polymer is polyvinylpyrrolidone or a combination of two or more of aqueous polyurethane, polyvinyl alcohol, polyvinylpyrrolidone and tannic acid.
2. The stretchable, self-adhesive, self-healing conductive film according to claim 1, wherein the polyhydroxy compound is ethylene glycol and/or sorbitol.
3. The stretchable, self-adhesive, self-healing conductive film according to claim 1, wherein the mass fraction of the flexible polymer in the conductive film is 50 to 85%.
4. The stretchable, self-adhesive, self-healing conductive film according to claim 1, wherein the mass of the polyhydroxy compound is 0.2% to 3.5% of the mass of the conductive polymer solution.
5. The method for preparing the stretchable, self-adhesive, self-healing conductive film according to claim 1, comprising the steps of:
a) Poly (ethylenedioxythiophene): uniformly mixing a poly (styrene sulfonate) solution and a polyhydroxy compound to obtain a first mixed solution;
b) Sequentially adding two or more than two flexible polymer aqueous solutions into the first mixed solution, and uniformly mixing to obtain a blending mixed solution;
c) And drying the blending mixed solution to obtain the stretchable self-adhesive self-healing conductive film.
6. The method according to claim 5, wherein the drying temperature in the step C) is 50 to 70℃and the drying time in the step C) is 2 to 3 hours.
7. A thin film dry electrode prepared from the stretchable, self-adhesive, self-healing conductive thin film of any one of claims 1-4 and copper wire.
8. The use of the dry film electrode according to claim 7 for preparing myoelectric, electrocardiographic and electroencephalogram signal detection devices.
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