CN114574040A - PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method - Google Patents
PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method Download PDFInfo
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- A61B5/24—Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof
- A61B5/25—Bioelectric electrodes therefor
- A61B5/263—Bioelectric electrodes therefor characterised by the electrode materials
- A61B5/268—Bioelectric electrodes therefor characterised by the electrode materials containing conductive polymers, e.g. PEDOT:PSS polymers
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- C09D11/00—Inks
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Abstract
The invention provides a method for preparing PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method. The PEDOT: PSS/EG/LiTFSI conductive ink is obtained by modifying a PEDOT/PSS solution by using ethylene glycol and LiTFSI, wherein the weight ratio of PEDOT: the PSS/EG/LiTFSI conductive ink has the viscosity of 1-1000cP and the surface tension of 30-40mN/m, and has no obvious change in properties after being placed for 60 days at room temperature. The total thickness of the ultra-flexible electrode is as low as 600 nanometers, and the ultra-flexible electrode is prepared from the conductive ink by an aerosol jet printing technology. By controlling the proportion of PEDOT to PSS, EG and LiTFSI, the ultrathin flexible electrode with high conductivity and high stretchability can be prepared, and the resistance of the ultrathin flexible electrode shows a negative increasing trend within a strain range of 30%.
Description
Technical Field
The invention relates to a PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method, and belongs to the technical field of conductive polymer materials.
Background
The human body can generate electrophysiological signals (electrocardio, myoelectricity, electroencephalogram, electrooculogram and the like) related to health in the process of physiological activities, and the accurate, real-time and continuous acquisition of the signals has important application value in the field of human health monitoring. Wearable electrodes are important devices for monitoring electrophysiological signals in real time. At present, Ag/AgCl gel electrodes are commonly used in clinic, but the problems of signal attenuation, skin irritation, poor stability and the like easily occur after long-time wearing. Flexible dry electrodes, which are capable of making intimate contact with the skin and exhibiting comparable performance to gel electrodes, are currently the focus of research. However, most reported dry electrodes require tape for auxiliary fixation to the skin, resulting in limited signal-to-noise ratio, significant motion artifacts, and foreign body sensation.
In order to obtain high quality electrophysiological signals and to achieve "non-inductive" wear applications, the tattoo electrodes should have high conductivity, stretchability, conformal attachment and self-adhesion, biocompatibility, etc. It is well known that conductive polymers are ideal interface materials for achieving perfect compatibility between the human body and flexible electronics. The PEDOT and PSS are applied to the field of wearable electronic equipment due to the characteristics of good solution processability, adjustable conductivity, high biocompatibility, excellent environmental stability and the like. However, intrinsic PEDOT: PSS is less conductive and less stretchable due to the inherent "core-shell" type microstructure (where hydrophobic PEDOT tends to curl "core" and hydrophilic PSS wraps around the PEDOT to form a "shell"), which limits its application to a large extent. The high conductivity and high stretchability are not both a difficult problem to be solved. In order to solve the problems, relevant work introduces organic additives such as Ethylene Glycol (EG) and the like, so that the PEDOT and the PSS can be separated from each other, the conformation of a molecular chain is changed from a curled shape (a benzene structure) into a linear (quinoid) structure which is beneficial to carrier transmission, and the conductivity is greatly improved; aiming at the problems of low stretchability and the like, the problems are mainly solved by compounding with a stretching and conductive reinforcing agent.
Therefore, there is a need in the art to prepare a high-performance flexible electrode having high conductivity, high stretchability, good biocompatibility, and the like.
Disclosure of Invention
To solve the above technical problems, an object of the present invention is to provide a PEDOT: the PSS/EG/LiTFSI conductive ink has the characteristics of high conductivity, high stretchability, good biocompatibility and the like of a high-performance super-flexible electrode made of the conductive ink, and can realize real-time accurate monitoring of important electrophysiological signals such as skin surface and subcutaneous electrocardio, myoelectricity and the like.
To achieve the above object, the present invention first provides a PEDOT: PSS/EG/LiTFSI conductive ink is obtained by modifying PEDOT: PSS solution with Ethylene Glycol (EG) and lithium bistrifluoromethanesulfonylimide (LiTFSI), wherein the weight ratio of PEDOT: the PSS/EG/LiTFSI conductive ink has the viscosity of 1-1000cP and the surface tension of 30-40 mN/m.
According to a particular embodiment of the invention, preferably, said modification comprises the following steps:
the method comprises the following steps: mixing ethylene glycol with a PEDOT/PSS solution to obtain a PEDOT/PSS/EG solution; wherein the dosage of the ethylene glycol is 2-10 wt%, preferably 5-10 wt%, more preferably 5 wt% or 10 wt% of the mass of the PEDOT PSS solution;
step two: and adding LiTFSI into the PEDOT PSS/EG solution to obtain the PEDOT PSS/EG/LiTFSI conductive ink, wherein the using amount of the LiTFSI is 5-45.5 wt%, preferably 10-45.5 wt%, and more preferably 45.5 wt% of the solid content of the PEDOT PSS solution.
According to the invention, EG and LiTFSI are simultaneously added in a PEDOT/PSS system, and the corresponding proportion is controlled, so that the conductivity and the stretchability can be synchronously and greatly improved, wherein the conductivity is obviously superior to that of a system which is modified by singly adopting EG or singly adopting LiTFSI.
According to the invention, EG, LiTFSI and PEDOT/PSS aqueous solutions with different concentrations are mixed, and the PEDOT/PSS/EG/LiTFSI conductive ink with proper viscosity, dispersity, stability and surface tension for jet printing can be obtained by controlling the proportion of EG to LiTFSI. On the basis, the good printing effect of the ink can be realized by regulating and controlling the stirring time, the filtering process and the ultrasonic time.
PSS/EG/LiTFSI conductive ink obtained by the invention has the viscosity of 1-1000cP and the surface tension of 30-40mN/m, has no obvious change in properties after being placed for 60 days at room temperature, and does not block a spray head.
According to the specific embodiment of the invention, the long-range ordered structure of the conductive domain (PEDOT) can be realized by controlling the proportion of EG and LiTFSI, and a partial crystal network is generated inside the PSS phase, so that good conductivity is still kept under high strain. Preferably, the mass ratio of ethylene glycol to LiTFSI is 0.04 to 2, preferably 0.109 to 1, more preferably 0.109, 0.167, 0.219, 0.25, 0.333, 0.5 or 1.
According to a specific embodiment of the present invention, preferably, in the first step, the ethylene glycol and the PEDOT/PSS solution are mixed by stirring, preferably, the stirring speed is controlled to be 900r/min, and the time is 15 min.
It is another object of the present invention to provide an ultra-flexible electrode formed of the PEDOT: PSS/EG/LiTFSI conductive ink.
According to a specific embodiment of the present invention, preferably, the ultra-flexible electrode is manufactured by aerosol printing or tattoo-type minimally invasive injection. The aerosol printing technology adopted by the invention is a processing means for additive manufacturing, and the solubilized functional material can be sprayed in a limited area as required, and the application of the aerosol printing technology in the preparation of the surface-attached super-flexible electrode can bring the advantages of low manufacturing cost, direct patterning, high material utilization rate, simple manufacturing process, compatibility with substrates with different dimensions and the like. The invention utilizes the high-biocompatibility conductive ink (PEDOT: PSS/EG/LiTFSI conductive ink) to replace the traditional tattoo pigment, can create a new method for acquiring high-precision electrophysiological signals from the body, and opens up a new paradigm for health management application such as chronic disease monitoring and the like.
According to the specific embodiment of the present invention, preferably, before the ultra-flexible electrode (membrane) is prepared by using the conductive ink, filtration and ultrasonic treatment may be performed, wherein the filtration may be performed by using a 0.22 μm filter head, and the time of the ultrasonic treatment may be controlled to be 15 min.
According to a specific embodiment of the present invention, preferably, the ultra-flexible electrode is prepared by tattooing a micro-invasive injection method of PEDOT: PSS/EG/LiTFSI conductive ink was injected into the dermis layer (e.g., mouse). PSS/EG/LITFSI conductive ink is injected into dermis layers of mice and the like by a tattooing machine to construct an ultra-flexible tattooing electrode which is highly matched with skin tissues, so that subcutaneous electromyographic signals can be continuously, accurately and real-timely monitored.
According to the specific embodiment of the invention, the ultra-flexible electrode can be prepared by printing PEDOT: PSS/EG/LiTFSI conductive ink on temporary tattoo paper by using an aerosol jet printing technology, so that the ultra-thin flexible electrode adhered to an ultra-flexible substrate (such as an ultra-flexible substrate with the thickness of 450 nm) is obtained and is further directly attached to human skin by means of Van der Waals force. The ultra-flexible electrode has the characteristic of ultra-thin thickness, has the Young modulus which is matched with the skin (2kPa-500MPa) (the Young modulus of the flexible electrode is preferably 50-70MPa, specifically 60.42MPa for example), can be tightly attached to the texture of the skin, and can realize real-time accurate recording of parameters such as electrocardio and the like on the basis of non-inductive wearing. In addition, the conformal attaching performance of the super-flexible electrode is high, and recorded data can be prevented from being influenced by noise such as motion artifacts.
According to a specific embodiment of the present invention, preferably, the super-flexible electrode has a conductivity of 5000-.
According to a specific embodiment of the present invention, preferably, the ultra-flexible electrode has an elongation at break of 30 to 60%, more preferably 56.9%.
According to an embodiment of the present invention, the skin impedance of the ultra-flexible electrode is preferably 4-6k Ω @100Hz, and more preferably 4.7k Ω @100 Hz.
The invention also provides a monitoring method of electrophysiological signals, which is realized by a tattoo type minimally invasive conductive ink injection mode or an ultra-flexible electrode.
The invention realizes the effective preparation of the ultrathin high-performance PEDOT/PSS/EG/LiTFSI flexible electrode, and the PEDOT/PSS/EG/LiTFSI flexible electrode with high conductivity (5000-. The flexible electrode had a lower skin impedance (4-6k Ω @100Hz) than a commercial Ag/AgCl gel electrode (30k Ω @100 Hz). And furthermore, the PSS/EG/LiTFSI mixed conductive ink has good biocompatibility as proved by hematoxylin-eosin dyeing experiments, can be directly injected into a mouse dermis layer to construct a micron-sized tattooing electrode, and the contact resistance of the micron-sized tattooing electrode is further reduced to 3.2k omega.
The flexible electrode can provide two action modes of skin adhesion and subcutaneous tattoo, thereby realizing continuous real-time accurate monitoring of important electrophysiological signals of electrocardio, myoelectricity and the like. The two action modes generate lower signal noise in the static and dynamic monitoring processes, and high-resolution health monitoring on the surface of human skin and under the skin of a mouse is realized.
The flexible electrode provided by the invention can have micron-sized total thickness (can be as low as 600 nanometers) and excellent stretchability, can be directly attached to the surface of skin, flexibly attached to skin textures, and deformed along with the movement of the skin, so that the skin impedance is greatly reduced, and the interface slippage is reduced; due to good biocompatibility, the tattooing electrode can be injected into a dermis layer to form a tattooing electrode, further eliminate skin impedance and eliminate noise interference on signals caused by daily movement and the like, obtain high-resolution signals and is suitable for long-term health monitoring application.
Drawings
FIG. 1 shows the results of conductivity measurements obtained with different concentrations of EG and LiTFSI added to PEDOT: PSS in examples of the invention.
FIG. 2 is a schematic diagram of an ultra-thin skin surface electrode constructed in an embodiment of the invention.
FIG. 3 is an SEM image of an ultrathin electrode on the skin surface in an embodiment of the invention.
Fig. 4 shows the result of the tensile-conductivity test of the ultrathin skin surface electrode in the example of the present invention.
FIG. 5 shows the results of the skin contact resistance comparison test between the ultra-thin skin surface electrode and the commercial Ag/AgCl electrode in the example of the present invention.
FIG. 6 shows the result of electrocardiosignal measurement recorded by the ultrathin skin surface electrode in the embodiment of the present invention.
FIG. 7 shows the results of biocompatibility testing of PEDOT: PSS/EG/LiTFSI conductive ink in accordance with an embodiment of the present invention.
FIG. 8 is a real-time monitoring result of the subcutaneous micron-sized tattooing electrode on the mouse electromyographic signals according to the embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Comparative example 1
The comparative example provides a method for modifying PEDOT: PSS by using ethylene glycol to obtain a PEDOT: PSS/EG solution, which comprises the following steps:
1) preparing PEDOT PSS/5 wt% EG solution
EG is added into a PEDOT PSS aqueous solution (filtering by a 0.45 mu m filter head) to make the solution account for 5 wt% of the total system, and stirring and mixing are carried out, wherein the stirring speed is 900r/min, and the stirring time is 15min, thus obtaining the PEDOT PSS/5 wt% EG solution.
2) Viscosity measurement
The viscosity of the PEDOT: PSS/5 wt% EG solution was measured using a digital viscometer and was 30.1 cP.
3) Surface tension test
PSS/5 wt% EG solution was tested for surface tension using a surface tensiometer, which had a surface tension of 37.3 mN/m.
4) Preparation of Flexible self-supporting PEDOT PSS/5 wt% EG film
Filtering the solution obtained in the step 1) by using a 0.22 mu m filter head, carrying out ultrasonic treatment for 15min, then dripping the solution into a polytetrafluoroethylene mold, and drying the polytetrafluoroethylene mold to obtain the flexible self-supporting PEDOT/PSS/5 wt% EG film with the thickness of 20 mu m.
5) Conductivity test
The conductivity of the PEDOT PSS/5 wt% EG film was measured using the four-probe method and found to be 1823S cm-1(FIG. 1).
Comparative example 2
The comparative example 2 provides a method for modifying PEDOT: PSS by using ethylene glycol to obtain a PEDOT: PSS/EG solution, which comprises the following steps:
1) preparing PEDOT PSS/10 wt% EG solution
The amount of EG added was changed to 10 wt% based on the total system, and the other steps were the same as in comparative example 1.
2) Viscosity measurement
The viscosity of the PEDOT: PSS/10 wt% EG solution was measured using a digital viscometer and was 33.6 cP.
3) Surface tension test
PSS/10 wt% EG solution was tested for surface tension using a surface tensiometer, which was 38.6 mN/m.
4) Preparation of Flexible self-supporting PEDOT PSS/10 wt% EG film
The procedure was the same as in comparative example 1.
5) Conductivity test
The conductivity of the PEDOT PSS/10 wt% EG film was measured by the four-probe method to be 1600S cm-1(FIG. 1).
Comparative example 3
The comparative example 3 provides a method for modifying PEDOT: PSS by using LiTFSI to obtain a PEDOT: PSS/LiTFSI solution, which comprises the following steps:
1) preparing PEDOT PSS/45.5 wt% LiTFSI solution
And adding LiTFSI into the PEDOT PSS solution, wherein the addition amount of the LiTFSI is 45.5 wt% of the solid content of the PEDOT PSS, stirring and dispersing are carried out, the stirring speed is 900r/min, and the stirring time is 15min, so that the LiTFSI solution with the weight percent of the PEDOT PSS/45.5 can be obtained.
2) Preparation of Flexible self-supporting PEDOT PSS/45.5 wt% LiTFSI films
The procedure was the same as in comparative example 1.
3) Conductivity test
PSS/45.5 wt% LiTFSI film conductivity was measured using the four-probe method and found to be 2578S cm-1。
Example 1
The embodiment provides a method for modifying PEDOT/PSS with ethylene glycol and lithium bistrifluoromethanesulfonimide to obtain a solution of PEDOT/PSS/EG/LiTFSI, which comprises the following steps:
1) preparing PEDOT PSS/5 wt% EG/10 wt% LiTFSI solution
And adding LiTFSI to make the solution account for 10 wt% of the solid content of the PEDOT PSS on the basis of the PEDOT PSS/5 wt% EG solution prepared in the comparative example 1, and stirring and dispersing at the stirring speed of 900r/min for 15min to obtain the PEDOT PSS/5 wt% EG/10 wt% LiTFSI solution.
2) Viscosity measurement
The viscosity of the PEDOT: PSS/5 wt% EG/10 wt% LiTFSI solution was measured using a digital viscometer and was 23.8 cP.
3) Surface tension test
PSS/5 wt% EG/10 wt% LiTFSI solution was tested for surface tension using a surface tensiometer, which had a surface tension of 36.7 mN/m.
4) Preparation of Flexible self-supporting PEDOT PSS/5 wt.% EG/10 wt.% LiTFSI films
And filtering the solution by using a 0.22 mu m filter head, carrying out ultrasonic treatment for 15min, then coating the solution into a polytetrafluoroethylene mold, and drying to obtain the flexible self-supporting PEDOT, PSS/5 wt% EG/10 wt% LiTFSI film with the film thickness of 20 mu m.
5) Conductivity test
PSS/5 wt% EG/10 wt% LiTFSI film conductivity was measured using a four-probe method and found to be 3658S cm-1(FIG. 1).
This example shows that the film made from LiTFSI was made to achieve a high conductivity not currently achievable with PEDOT: PSS films by adding LiTFSI to the EG-modified PEDOT: PSS/EG solution obtained in comparative example 1.
Example 2
The embodiment provides a method for modifying PEDOT/PSS with ethylene glycol and lithium bistrifluoromethanesulfonimide to obtain a solution of PEDOT/PSS/EG/LiTFSI, which comprises the following steps:
1) PSS/5 wt% EG/20 wt% LiTFSI solution
The addition amount of LiTFSI was changed to 20 wt% of the total system, and the other steps were the same as in comparative example 1.
2) Viscosity measurement
The viscosity of the PEDOT: PSS/5 wt% EG/20 wt% LiTFSI solution was measured using a digital viscometer and was 20.2 cP.
3) Surface tension test
PSS/5 wt% EG/20 wt% LiTFSI solution was tested for surface tension using a surface tensiometer, which had a surface tension of 35.5 mN/m.
4) Preparation of Flexible self-supporting PEDOT PSS/5 wt.% EG/20 wt.% LiTFSI films
The procedure was as in example 1.
5) Conductivity test
PSS/5 wt% EG/20 wt% LiTFSI film conductivity of 4095S cm-1(FIG. 1).
Example 3
The embodiment provides a method for modifying PEDOT/PSS with ethylene glycol and lithium bistrifluoromethanesulfonimide to obtain a solution of PEDOT/PSS/EG/LiTFSI, which comprises the following steps:
1) PSS/5 wt% EG/30 wt% LiTFSI solution
The addition of LiTFSI was changed to 30 wt% of the total system, and the other steps were the same as in example 1.
2) Viscosity measurement
The viscosity of the PEDOT: PSS/5 wt% EG/30 wt% LiTFSI solution was measured using a digital viscometer and was 18.7 cP.
3) Surface tension test
PSS/5 wt% EG/30 wt% LiTFSI solution was tested for surface tension using a surface tensiometer, which had a surface tension of 34.2 mN/m.
4) Preparation of Flexible self-supporting PEDOT PSS/5 wt.% EG/30 wt.% LiTFSI films
The procedure was as in example 1.
5) Conductivity test
PSS/5 wt% EG/30 wt% LiTFSI film conductivity was measured using a four-probe method and found to be 4744S cm-1(FIG. 1).
Example 4
The embodiment provides a method for modifying PEDOT: PSS by using Ethylene Glycol (EG) and lithium bistrifluoromethanesulfonylimide (LiTFSI) to obtain a PEDOT: PSS/EG/LiTFSI solution, which comprises the following steps:
1) PSS/5 wt% EG/45.5 wt% LiTFSI solution
The addition of LiTFSI was changed to 45.5 wt% based on the total system, and the other steps were the same as in example 1.
2) Viscosity measurement
PSS/5 wt% EG/45.5 wt% LiTFSI solution was tested for viscosity using a digital viscometer, which was 16.9 cP.
3) Surface tension test
PSS/5 wt% EG/45.5 wt% LiTFSI solution was tested for surface tension using a surface tensiometer, which had a surface tension of 32.3 mN/m.
4) Preparation of Flexible self-supporting PEDOT PSS/5 wt.% EG/45.5 wt.% LiTFSI films
The procedure was as in example 1.
5) Conductivity test
PSS/5 wt% EG/45.5 wt% LiTFSI film conductivity of 5165S cm using the four-probe method-1(FIG. 1).
6) Evaluation of dispersibility and stability
PSS/5 wt% EG/45.5 wt% LiTFSI solution is placed for 60 days, viscosity, surface tension and conductivity of the prepared film are not obviously changed, and the condition of blocking a spray head in the printing process is avoided.
As can be seen from comparative examples 1 to 2 and examples 1 to 4: according to the invention, the PEDOT and PSS are modified by ethylene glycol and lithium bistrifluoromethanesulfonylimide, and the synergistic effect of the ethylene glycol and the lithium bistrifluoromethanesulfonylimide enables the improvement amount of the composite conductivity to be over-increasedAfter passing EG (1823S cm)-1) And LiTFSI (2578S. cm)-1) The sum of the conductivity increases that can be achieved by modification alone. According to the invention, EG and LiTFSI are adopted to carry out synergistic modification on PEDOT PSS, so that the performance of the prepared PEDOT PSS/EG/LiTFSI is obviously superior to that of a product obtained by singly adopting ethylene glycol or lithium bistrifluoromethanesulfonylimide for modification.
Example 5
This example provides a method for preparing a PEDOT/5 wt% EG/45.5 wt% LiTFSI surface-mounted electrode, comprising the steps of:
1. preparation of PEDOT PSS/5 wt% EG/45.5 wt% LiTFSI skin-attached electrode.
As shown in figure 2, a PEDOT/PSS/5 wt% EG/45.5 wt% LiTFSI solution is used as ink, and an aerosol printing technology is utilized to realize the printing of a thin film electrode on temporary tattoo paper, so as to prepare a skin-attached ultrathin flexible electrode.
The structure of the above-mentioned ultrathin flexible electrode with skin-attached structure was observed by scanning electron microscope, and its SEM image is shown in fig. 3. As can be seen from fig. 3, the surface of the ultra-thin flexible electrode with skin-attached structure prepared in this example is in the form of nanoparticles with a thickness of about 600 nm.
2. The tensile-conductive properties of the above-described skin-attached type ultrathin flexible electrode were tested, and the results are shown in fig. 4. As can be seen from fig. 4, the elongation at break of the skin-attached ultrathin flexible electrode was as high as 56.9%, and the resistance showed a negative increase in the strain range of 30%. From this, it is understood that the skin-attached ultrathin flexible electrode obtained by modifying EG and LiTFSI has excellent stretch-conductivity properties.
The Young modulus value of the skin-attached ultrathin flexible electrode is 60.42MPa, and is remarkably reduced compared with that of a traditional PEDOT-PSS electrode (279.73 MPa). Therefore, the epidermis attaching type ultrathin flexible electrode is more matched with human skin (0.2kPa-500MPa), and conformal contact can be realized.
Test example 1
This test example 1 shows the results of an electrode-skin contact resistance test of PEDOT: PSS/5 wt% EG/45.5 wt% LiTFSI ultrathin flexible electrodes prepared in example 5 with a commercial Ag/AgCl electrode as shown in FIG. 5.
As can be seen from FIG. 5, the electrode-skin contact resistance of PSS/5 wt% EG/45.5 wt% LiTFSI ultrathin flexible electrode of example 5 of the present invention was 4.7k Ω and the electrode-skin contact resistance of the commercial Ag/AgCl electrode was 30k Ω at 100 Hz; PSS/5 wt% EG/45.5 wt% LiTFSI ultrathin flexible electrodes of inventive example 5 had an electrode-skin contact resistance of 0.68 kOmega and a commercial Ag/AgCl electrode had an electrode-skin contact resistance of 4.37 kOmega at a frequency of 1000 Hz. It can be seen that the electrode-skin contact resistance of the PEDOT: PSS/5 wt% EG/45.5 wt% LiTFSI ultrathin flexible electrode of inventive example 5 is lower than that of the commercial Ag/AgCl electrode at both 100Hz and 1000Hz frequencies.
Test example 2
In the test example 2, the PEDOT/PSS/EG 5 wt%/EG 45.5 wt% LiTFSI ultrathin flexible electrode prepared in the example 5 and a commercialized Ag/AgCl electrode are used for monitoring electrocardiograms of a human body in vitro in real time, and the test result is shown in FIG. 6.
By comparing the monitoring signal graphs of the PEDOT PSS and the EG 5 wt% and the LiTFSI 45.5 wt% ultra-thin flexible electrode, PQRST waves are clear and distinguishable in electrocardiosignals obtained by the ultra-thin flexible electrode, and the electrocardiosignals have higher signal-to-noise ratio and lower mean square error. The method is obviously superior to the commercialized Ag/AgCl gel electrode in the aspect of spectrum signal quality.
Test example 3
The test example 3 tests the properties of the PEDOT PSS/5 wt% EG/45.5 wt% LiTFSI solution after subcutaneous injection, including biocompatibility test and skin tissue Young modulus change; and preparing a micron-sized tattooing electrode by using PEDOT (PSS)/5 wt% EG/45.5 wt% LiTFSI solution as tattooing ink, and monitoring myoelectric signals in real time.
The correlation results are as follows:
1. biocompatibility test of PEDOT PSS/5 wt% EG/45.5 wt% LiTFSI solution.
PSS/5 wt% EG/45.5 wt% LiTFSI solution was injected into the dermis layer of mice, and after one week and one month, tissue sections were taken and stained with hematoxylin-eosin and observed under the mirror, and the results are shown in FIG. 7.
As can be seen from fig. 7: the tissue slice has a complete structure, and PEDOT, PSS/5 wt% EG/45.5 wt% LiTFSI solution is uniformly diffused, which shows that the PEDOT, PSS/EG/LiTFSI mixed solution has good biocompatibility.
2. Young's modulus values of skin tissues of mice before and after injection of PEDOT: PSS/5 wt% EG/45.5 wt% LiTFSI solution were measured, respectively, and the results are shown in Table 1.
TABLE 1
| Sample(s) | Young's modulus (MPa) |
| Skin tissue (blank) | 4.01 |
| Skin tissue (injection ink) | 4.15 |
As can be seen from Table 1, the Young's modulus values of mouse skin tissues did not change significantly before and after injection of the PEDOT: PSS/5 wt% EG/45.5 wt% LiTFSI solution, indicating that the PEDOT: PSS/5 wt% EG/45.5 wt% LiTFSI solution is highly matched to the skin tissues.
3. PSS/5 wt% EG/45.5 wt% LiTFSI solution of PEDOT is used as tattooing ink, a micron-sized tattooing electrode is manufactured in a tattooing mode and placed under the skin of a mouse, and gold is introduced to serve as an external connection line to transmit signals, so that real-time monitoring of electromyographic signals is achieved. The micron-scale tattooing electrode and the monitoring pattern are shown in fig. 8.
Claims (10)
1. A PEDOT: PSS solution is modified by ethylene glycol and lithium bis (trifluoromethanesulfonylimide), and the modified conductive ink is obtained by the modification of PEDOT: the PSS/EG/LiTFSI conductive ink has the viscosity of 1-1000cP and the surface tension of 30-40 mN/m.
2. The PEDOT according to claim 1: PSS/EG/LiTFSI conductive ink, wherein the modification comprises the steps of:
the method comprises the following steps: mixing ethylene glycol with a PEDOT/PSS solution to obtain a PEDOT/PSS/EG solution; preferably, the ethylene glycol is mixed with the PEDOT and PSS solution by stirring, more preferably, the stirring speed is controlled to be 900r/min, and the time is 15 min;
step two: adding lithium bistrifluoromethanesulfonimide into the PEDOT, PSS/EG solution to obtain the PEDOT, PSS/EG/LiTFSI conductive ink;
wherein the dosage of the ethylene glycol is 2-10 wt%, preferably 5-10 wt%, more preferably 5 wt% or 10 wt% of the mass of the PEDOT PSS solution;
the amount of the lithium bis (trifluoromethanesulfonylimide) is 5 to 45.5 wt%, preferably 10 to 45.5 wt%, and more preferably 45.5 wt% of the solid content of the PEDOT/PSS solution.
3. PEDOT according to claim 1 or 2: PSS/EG/LiTFSI conductive ink, wherein the mass ratio of ethylene glycol to lithium bis (trifluoromethanesulfonylimide) is 0.04-2, preferably 0.109-1, more preferably 0.109, 0.167, 0.219, 0.25, 0.333, 0.5 or 1.
4. An ultra-flexible electrode formed from PEDOT according to any one of claims 1 to 3: PSS/EG/LiTFSI conductive ink.
5. The ultra-flexible electrode according to claim 4, wherein the ultra-flexible electrode is manufactured by aerosol printing or tattoo-type minimally invasive injection; preferably, the ultra-flexible electrode is prepared by tattooing the PEDOT: PSS/EG/LiTFSI conductive ink was injected into the dermis layer.
6. The ultra-flexible electrode according to claim 4, wherein the Young's modulus of the ultra-flexible electrode is 50-70 MPa.
7. The ultra-flexible electrode according to claim 4, wherein the ultra-flexible electrode has an electrical conductivity of 5000-.
8. The ultra-flexible electrode according to claim 4, wherein the ultra-flexible electrode has an elongation at break of 30 to 60%.
9. The ultra-flexible electrode of claim 4, wherein the skin impedance of the ultra-flexible electrode is 4-6k Ω @100 Hz.
10. A method for monitoring electrophysiological signals obtained by tattooing a minimally invasive injection of PEDOT according to any one of claims 1 to 3: PSS/EG/LiTFSI conductive ink or by the ultra-flexible electrode of any of claims 4 to 9.
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| CN202210227885.3A CN114574040A (en) | 2022-03-08 | 2022-03-08 | PEDOT: PSS/EG/LiTFSI conductive ink, super-flexible electrode and electrophysiological signal monitoring method |
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| US20100025703A1 (en) * | 2004-12-29 | 2010-02-04 | Cambridge Display Technology Limited | Conductive Polymer Compositions in Opto-Electrical Devices |
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