CN117126429B - Gel semi-dry electrode and preparation method and application thereof - Google Patents

Gel semi-dry electrode and preparation method and application thereof Download PDF

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CN117126429B
CN117126429B CN202311388072.3A CN202311388072A CN117126429B CN 117126429 B CN117126429 B CN 117126429B CN 202311388072 A CN202311388072 A CN 202311388072A CN 117126429 B CN117126429 B CN 117126429B
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mass
gel
hydrophobic
hydrogel
hydrophilic
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CN117126429A (en
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唐弢
刘峻琛
魏依娜
冯琳清
凌伟
张秀
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Zhejiang Lab
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Zhejiang Lab
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    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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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
    • A61B5/251—Means for maintaining electrode contact with the body
    • A61B5/257—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes
    • A61B5/259—Means for maintaining electrode contact with the body using adhesive means, e.g. adhesive pads or tapes using conductive adhesive means, e.g. gels
    • A—HUMAN NECESSITIES
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    • A61B5/25—Bioelectric electrodes therefor
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Abstract

The invention relates to a gel semi-dry electrode, a preparation method and application thereof. The gel semi-dry electrode comprises a hydrophobic electronic conductive gel skeleton and hydrophilic ion conductive hydrogel filled in the hydrophobic electronic conductive gel skeleton, wherein the hydrophobic electronic conductive gel skeleton and the hydrophilic ion conductive hydrogel form a topological structure under the phase separation effect; the hydrophobic electronic conductive gel skeleton comprises a hydrophobic gel skeleton and electronic conductive materials filled in the hydrophobic gel skeleton, and the hydrophilic ion conductive hydrogel comprises a hydrophilic hydrogel network, and electrolyte and water filled in the hydrophilic hydrogel network. The gel semi-dry electrode has excellent flexibility, can slowly release electrolyte for a long time and high electronic conductivity, and can obviously reduce impedance in the transmission process of the physiological electric signal and improve the detection quality of the physiological electric signal when being used for detecting the physiological electric signal.

Description

Gel semi-dry electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of physiological electric signal detection, in particular to a gel semi-dry electrode and a preparation method and application thereof.
Background
Physiological electrical signals such as brain electricity, electrocardio and myoelectricity are taken as important information for representing various physiological states of a human body, and the data of the physiological electrical signals has important significance in the fields of clinical diagnosis, motion health detection, human-computer interaction and the like, so that the physiological electrical signals with high quality are required to be acquired.
The electrode is the most direct part of the physiological signal detection system connected with the skin of the human body, and the quality of the electrode often determines the quality of the collected physiological electric signals. In the process of collecting the physiological electric signals, the physiological electric signals pass through the stratum corneum and the electrode-skin interface layer in sequence before entering the electrode, if the stratum corneum is dry, the electrode and the skin cannot be well conformal or the conductivity of the electrode is low, the impedance can be increased, and as the stratum corneum, the electrode-skin interface layer and the electrode are in series connection, the impedance of the three parts is reduced simultaneously, so that the high-quality physiological electric signals can be obtained. However, most electrodes today only improve the impedance of one or both parts, resulting in poor quality of the detected physiological electrical signal.
Disclosure of Invention
Based on the above, it is necessary to provide a gel semi-dry electrode, and a preparation method and application thereof, wherein the gel semi-dry electrode has excellent flexibility, can slowly release electrolyte for a long time and has high electronic conductivity, and can remarkably reduce impedance in the transmission process of physiological electric signals and improve the detection quality of the physiological electric signals when being used for detecting the physiological electric signals.
According to a first aspect of the present invention, there is provided a gel semi-dry electrode comprising a hydrophobic electronically conductive gel skeleton and a hydrophilic ionically conductive hydrogel filled in the hydrophobic electronically conductive gel skeleton, the hydrophobic electronically conductive gel skeleton and the hydrophilic ionically conductive hydrogel forming a topological structure due to a phase separation effect;
the hydrophobic electronic conductive gel skeleton comprises a hydrophobic gel skeleton and electronic conductive materials filled in the hydrophobic gel skeleton, and the hydrophilic ion conductive hydrogel comprises a hydrophilic hydrogel network, and electrolyte and water filled in the hydrophilic hydrogel network.
In one embodiment, the material of the hydrophobic gel skeleton is at least one selected from polymethyl acrylate, polymethyl methacrylate and polyethyl acrylate;
and/or the electronic conductive material is selected from a two-dimensional conductive material or a conductive polymer.
In one embodiment, the two-dimensional conductive material is selected from at least one of silver nanoplates, graphene, two-dimensional titanium carbide, and two-dimensional niobium carbide;
and/or the sheet diameter of the two-dimensional conductive material is 0.5-10 mu m;
and/or the conductive polymer is selected from poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid).
In one embodiment, the material of the hydrophilic hydrogel network is selected from polyacrylamide hydrogels and/or polyacrylic hydrogels;
and/or the electrolyte is at least one selected from lithium chloride, sodium chloride, potassium chloride and calcium chloride.
In one embodiment, the mass ratio of the hydrophobic electron conductive gel skeleton to the hydrophilic ion conductive hydrogel is 1:0.5-1:3;
and/or the mass ratio of the electron conducting material to the hydrophobic gel skeleton is 1:0.025-1:2.5;
and/or the electrolyte accounts for 0.5-20wt% of the mass of the hydrophilic hydrogel network;
and/or, the water accounts for 17-65 wt% of the mass of the hydrophilic gel network.
In one embodiment, the hydrophilic hydrogel network is further filled with a water retaining agent.
In one embodiment, the water retaining agent is selected from glycerol.
According to a second aspect of the present invention, there is provided a method for preparing a gel semi-dry electrode, comprising the steps of:
preparing a hydrophobic material monomer, an organic solvent, an electronic conductive material, a first initiator and a first crosslinking agent into an organic conductive gel precursor, and crosslinking and drying to obtain the hydrophobic electronic conductive gel skeleton;
preparing a hydrogel precursor from hydrophilic material monomers, water, electrolyte, a second initiator and a second crosslinking agent, filling the hydrogel precursor into the hydrophobic electron conductive gel skeleton, and crosslinking to form the gel semi-dry electrode with a topological structure through phase separation.
In one embodiment, the organic solvent is selected from at least one of dimethyl sulfoxide or dimethylformamide;
and/or the hydrophobic material monomer is at least one selected from methyl acrylate, methyl methacrylate and ethyl acrylate, wherein the mass of the hydrophobic material monomer is 20-50% of the mass of the organic solvent;
and/or the mass of the electron conducting material is 0.5-50 wt% of the mass of the organic solvent;
and/or the first initiator is selected from at least one of azodiisobutyronitrile and azodiisoheptonitrile, wherein the mass of the first initiator is 0.2-1.5 wt% of the mass of the organic solvent;
and/or the first crosslinking agent is selected from N, N' -methylene bisacrylamide, wherein the mass of the first crosslinking agent is 0.03-1 wt% of the mass of the organic solvent;
and/or the hydrophilic material monomer is at least one selected from acrylamide and acrylic acid, wherein the mass of the hydrophilic material monomer is 20-50 wt% of the mass of the water;
and/or the mass of the electrolyte is 0.9-30 wt% of the mass of the water;
and/or the second initiator is selected from at least one of ammonium persulfate and hydrogen peroxide, wherein the mass of the second initiator is 1-5 wt% of the mass of the water;
and/or the second crosslinking agent is selected from N, N' -methylene bisacrylamide, wherein the mass of the second crosslinking agent is 0.03-0.15 wt% of the mass of the organic solvent;
and/or the hydrogel precursor also contains a water-retaining agent, wherein the mass of the water-retaining agent is 5-10 wt% of the mass of the water;
and/or in the process of filling the hydrogel precursor into the hydrophobic electron conductive gel skeleton, the filling pressure is 1000 Pa-3000 Pa.
According to a third aspect of the present invention, there is provided the use of the above-described gel semi-dry electrode in a physiological electrical signal detection system.
According to the gel semi-dry electrode, the hydrophobic electron conductive gel skeleton and the hydrophilic ion conductive hydrogel are both flexible materials, so that the gel semi-dry electrode has excellent flexibility, electrolyte and water are filled in the hydrophilic ion conductive hydrogel, the gel semi-dry electrode can slowly release electrolyte for a long time, and the hydrophobic electron conductive gel skeleton is filled with the electron conductive material, so that the gel semi-dry electrode has high electron conductivity. Therefore, the gel semi-dry electrode of the present invention has excellent flexibility, can slowly release electrolyte for a long time, and has high electron conductivity.
Furthermore, when the gel semi-dry electrode is used for detecting physiological electric signals, the gel semi-dry electrode can be conformal with skin, the impedance of an electrode-skin interface is reduced, meanwhile, the hydrophobic electron conducting gel skeleton can provide a stable electron conducting path, the hydrophilic ion conducting hydrogel can provide an auxiliary ion conducting path, the impedance of the gel semi-dry electrode is reduced, and the electrolyte slowly released by the hydrophilic ion conducting hydrogel continuously infiltrates into the stratum corneum, so that the impedance of the stratum corneum can be reduced. Therefore, the impedance in the transmission process of the physiological electric signal can be effectively reduced, and the detection quality of the physiological electric signal is improved.
In addition, compared with the semi-dry electrode which needs to be independently designed and assembled with a liquid storage system at present, the preparation method of the gel semi-dry electrode provided by the invention is simple, and the prepared semi-dry electrode is high in integration degree and convenient to use.
Detailed Description
The present invention will be described in more detail below in order to facilitate understanding of the present invention. It should be understood, however, that the invention may be embodied in many different forms and is not limited to the implementations or embodiments described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
According to a first aspect of the present invention, there is provided a gel semi-dry electrode comprising a hydrophobic electronically conductive gel skeleton and a hydrophilic ionically conductive hydrogel filled in the hydrophobic electronically conductive gel skeleton, the hydrophobic electronically conductive gel skeleton and the hydrophilic ionically conductive hydrogel forming a topology due to phase separation.
The hydrophobic electronic conductive gel skeleton comprises a hydrophobic gel skeleton and electronic conductive materials filled in the hydrophobic gel skeleton, and the hydrophilic ion conductive hydrogel comprises a hydrophilic hydrogel network, and electrolyte and water filled in the hydrophilic hydrogel network.
According to the gel semi-dry electrode, the hydrophobic electron conductive gel skeleton and the hydrophilic ion conductive hydrogel are both flexible materials, so that the gel semi-dry electrode has excellent flexibility, electrolyte and water are filled in the hydrophilic ion conductive hydrogel, the gel semi-dry electrode can slowly release electrolyte for a long time, and the hydrophobic electron conductive gel skeleton is filled with the electron conductive material, so that the gel semi-dry electrode has high electron conductivity. Therefore, the gel semi-dry electrode of the present invention has excellent flexibility, can slowly release electrolyte for a long time, and has high electron conductivity.
Furthermore, when the gel semi-dry electrode is used for detecting physiological electric signals, the gel semi-dry electrode can be conformal with skin, the impedance of an electrode-skin interface is reduced, meanwhile, the hydrophobic electron conducting gel skeleton can provide a stable electron conducting path, the hydrophilic ion conducting hydrogel can provide an auxiliary ion conducting path, the impedance of the gel semi-dry electrode is reduced, and the electrolyte slowly released by the hydrophilic ion conducting hydrogel continuously infiltrates into the stratum corneum, so that the impedance of the stratum corneum can be reduced. Therefore, the gel semi-dry electrode can simultaneously reduce the impedance of the stratum corneum, the electrode-skin interface and the electrode, further effectively reduce the impedance in the transmission process of the physiological electric signal and improve the detection quality of the physiological electric signal.
Meanwhile, the hydrophobic electronic conductive gel skeleton has excellent swelling resistance, and the hydrophilic ion conductive hydrogel has excellent water storage and support property; in addition, the gel semi-dry electrode with the topological structure formed by phase separation does not cause severe change of the hydrophobic electron conductive gel skeleton due to the water absorption of the hydrophilic ion conductive hydrogel, and antagonism of the water absorption swelling of the gel network to the permeability of the electron conductive material is reduced.
In order to ensure that the gel semi-dry electrode has good flexibility, strong water storage performance and good mechanical property and can not cause irritation to skin, the material of the hydrophobic gel skeleton is at least one selected from polymethyl acrylate, polymethyl methacrylate and polyethyl acrylate; the material of the hydrophilic hydrogel network is selected from polyacrylamide hydrogel and/or polyacrylic acid hydrogel.
In an embodiment, the electronically conductive material is selected from a two-dimensional conductive material selected from at least one of silver nanoplates, graphene, two-dimensional titanium carbide, and two-dimensional niobium carbide, or a conductive polymer selected from poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid). Because the two-dimensional conductive materials are more easily and uniformly loaded on the gel skeleton and are more easily connected to form a conductive path, the electronic conductive materials are preferably two-dimensional conductive materials such as silver nano-sheets, graphene, two-dimensional titanium carbide, two-dimensional niobium carbide and the like.
In order to improve the conductivity and stability of the hydrophobic conductive gel skeleton, the sheet diameter of the two-dimensional conductive material is selected to be 0.5-10 mu m, and optionally, the sheet diameter of the two-dimensional conductive material is selected from any value or a range of values between two values of 0.5-1 mu m, 3 mu m, 5 mu m, 7 mu m and 10 mu m, for example, the sheet diameter of a silver nano sheet is 1-10 mu m, the sheet diameter of graphene is 0.5-5 mu m, and the sheet diameters of two-dimensional titanium carbide and two-dimensional niobium carbide are 1-10 mu m. By selecting proper sheet diameter, the electron conducting materials can be uniformly loaded on the gel skeleton, and stable connection between the electron conducting materials can be realized.
In one embodiment, the electrolyte is at least one selected from lithium chloride, sodium chloride, potassium chloride and calcium chloride, and the electrolyte is dissolved in water to form an electrolyte solution.
In an embodiment, in order to make the gel semi-dry electrode have high conductivity, flexibility, water storage property and mechanical property at the same time, the mass ratio of the hydrophobic electronic conductive gel skeleton to the hydrophilic ion conductive hydrogel is 1:0.5-1:3, and optionally, the mass ratio of the hydrophobic electronic conductive gel skeleton to the hydrophilic ion conductive hydrogel is selected from any ratio of 1:0.5, 1:1, 1:1.5, 1:2 and 1:3 or a range value between any two ratios.
In an embodiment, in order to further improve the conductivity and stability of the hydrophobic conductive gel skeleton, the mass ratio of the electronic conductive material to the hydrophobic gel skeleton is 1:0.025-1:2.5, and optionally, the mass ratio of the electronic conductive material to the hydrophobic gel skeleton is selected from any ratio of 1:0.025, 1:1, 1:1.5, 1:2.5 or a range value between any two ratios.
In an embodiment, to further enhance the conductivity of the hydrophilic ion-conductive hydrogel, the electrolyte may be 0.5wt% to 20wt% of the hydrophilic hydrogel network mass, and optionally, the electrolyte may be any value or a range between any two values of 0.5wt%, 1wt%, 5wt%, 10wt%, 15wt%, 20wt% of the hydrophilic hydrogel network mass.
In one embodiment, to sufficiently infiltrate the stratum corneum, the air layer at the electrode-skin interface is eliminated, the water accounts for 17wt% to 65wt% of the hydrophilic gel network mass, optionally, the water accounts for any value or a range between any two values of 17wt%, 23wt%, 30wt%, 40wt%, 50wt%, 63wt%, 65wt% of the hydrophilic gel network mass.
In one embodiment, in order to prevent evaporation of water in the hydrophilic hydrogel network, which is further filled with a water-retaining agent, wherein the water-retaining agent is selected from glycerol, the gel semi-dry electrode is kept well wet.
According to a second aspect of the present invention, there is provided a method for preparing a gel semi-dry electrode, comprising the steps of:
s1, preparing a hydrophobic material monomer, an organic solvent, an electronic conductive material, a first initiator and a first crosslinking agent into an organic conductive gel precursor, and crosslinking and drying to obtain the hydrophobic electronic conductive gel skeleton;
s2, preparing a hydrogel precursor from hydrophilic material monomers, water, electrolyte, a second initiator and a second crosslinking agent, filling the hydrogel precursor into the hydrophobic electron conductive gel skeleton, and crosslinking to form a gel semi-dry electrode with a topological structure through phase separation.
The method for preparing the gel semi-dry electrode is simple and efficient, and is more suitable for industrial production.
In one embodiment, step S1 comprises the steps of: dispersing hydrophobic material monomer in organic solvent, and then adding electron conductive material to obtain suspension; and adding a first initiator and a first cross-linking agent into the suspension to obtain the organic conductive gel precursor.
In an embodiment, the hydrophobic material monomer in the step S1 is at least one selected from methyl acrylate, methyl methacrylate and ethyl acrylate; wherein the mass of the hydrophobic material monomer is 20wt% to 50wt% of the mass of the organic solvent, and optionally, the mass of the hydrophobic material monomer is any value or a range between two values selected from 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% and 50wt% of the mass of the organic solvent. By controlling the hydrophobic material monomer within the above range, the hydrophobic electronically conductive gel skeleton can be made to have both sufficient strength and sufficient pores for accommodating the hydrophilic ionically conductive hydrogel.
In an embodiment, the mass of the electronically conductive material in the step S1 is 0.5wt% to 50wt% of the mass of the organic solvent. By selecting proper sheet diameter and addition amount of the electron conductive material, the stability and conductivity of the hydrophobic electron conductive gel skeleton can be improved.
In an embodiment, the first initiator in step S1 is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile; wherein the mass of the first initiator is 0.2wt% to 1.5wt% of the mass of the organic solvent, and optionally, the mass of the first initiator is any value or a range between any two values selected from 0.2wt%, 0.5wt%, 1wt%, 1.2wt% and 1.5wt% of the mass of the organic solvent.
In an embodiment, the first crosslinking agent in step S1 is selected from N, N' -methylenebisacrylamide, wherein the mass of the first crosslinking agent is 0.03wt% to 1wt% of the mass of the organic solvent, preferably, the mass of the crosslinking agent is any value selected from 0.03wt%, 0.1wt%, 0.3wt%, 0.6wt%, 1wt% or a range between any two values of the mass of the organic solvent.
In the invention, the mechanical property and the conductivity of the hydrophobic electronic conductive gel skeleton can be improved by adding a proper amount of the first initiator and the first crosslinking agent.
In one embodiment, in step S1, the organic conductive gel precursor is required to be poured into a crosslinking mold for crosslinking, wherein the crosslinking temperature is preferably 70 ℃ to 90 ℃, the crosslinking time is preferably 0.5h to 2h, and the shape of the crosslinking mold can be selected and replaced according to the requirement.
In one embodiment, the drying in step S1 may be selected to be freeze-drying, preferably having a vacuum of 5.ltoreq. 5 Pa, and a cold trap temperature is selected according to the melting point of the organic solvent, for example, when the organic solvent is dimethyl sulfoxide, the cold trap temperature is 50 ℃ or lower, and when the organic solvent is dimethylformamide, the cold trap temperature is 70 ℃ or lower.
In one embodiment, the step of formulating the hydrogel precursor in step S2 comprises: dispersing hydrophilic material monomer in water, and sequentially adding electrolyte, a second initiator and a second crosslinking agent to obtain a hydrogel precursor.
In an embodiment, the hydrophilic material monomer in step S2 is at least one selected from acrylamide and acrylic acid; wherein the mass of the hydrophilic material monomer is 20wt% to 50wt% of the mass of the water, and optionally, the mass of the hydrophilic material monomer is any value or a range between any two values selected from 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% and 50wt% of the mass of the water.
In order to further enhance the conductivity of the hydrophilic ion-conductive hydrogel, the mass of the electrolyte is thus defined to be 0.9wt% to 30wt% of the mass of the water, optionally the mass of the electrolyte is selected from any value or a range between any two values of 0.9wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt% of the mass of the water.
In an embodiment, the second initiator in the step S2 is at least one of ammonium persulfate and hydrogen peroxide, wherein the mass of the second initiator is 1wt% to 5wt% of the mass of the water, and optionally, the mass of the second initiator is any value or a range between any two values of 1wt%, 2wt%, 3wt%, 4wt%, and 5wt% of the mass of the water.
The second cross-linking agent is selected from N, N' -methylene bisacrylamide, wherein the mass of the second cross-linking agent is 0.03wt% to 0.15wt% of the mass of the organic solvent, and optionally, the mass of the second cross-linking agent is any value or a range value between any two values selected from 0.03wt%, 0.06wt%, 0.09wt%, 0.12wt% and 0.15wt% of the mass of the organic solvent.
The invention controls the contents of the hydrophilic material monomer, the second initiator and the second cross-linking agent, so that the hydrophilic ion conductive hydrogel has enough strength and enough space for accommodating electrolyte.
In an embodiment, the hydrogel precursor further contains a water-retaining agent, the mass of the water-retaining agent is 5wt% to 10wt% of the mass of the water, optionally, the mass of the water-retaining agent is any value or a range between any two values of 5wt%, 7wt% and 10wt% of the mass of the water, and by adding the water-retaining agent, the water in the hydrophilic ion-conductive hydrogel can be prevented from evaporating, and the time of the hydrophilic ion-conductive hydrogel slow-release electrolyte can be further prolonged.
In an embodiment, in step S2, the hydrogel precursor may be filled into the hydrophobic electronically conductive gel skeleton by selectively dipping or injecting, preferably, the hydrogel precursor is filled into the hydrophobic electronically conductive gel skeleton by dipping, and the dipping is performed under a pressure of 1000 pa-3000 pa, so that the hydrogel precursor can quickly infiltrate into the hydrophobic electronically conductive gel skeleton, and severe polymerization and crosslinking of the hydrogel precursor in the infiltration process can be prevented, thereby affecting the uniformity of the hydrophilic electronically conductive hydrogel filler.
In one embodiment, the temperature of the crosslinking in the step S2 is preferably 30-60 ℃, and the time of the crosslinking is preferably 0.5-2 h.
In an embodiment, after the crosslinking in step S2 is completed, the gel semi-dry electrode may be further cleaned, and specifically, the cleaning steps are as follows: and (3) soaking the gel semi-dry electrode in water for 0.1-1 h, placing the gel semi-dry electrode in the environment for 1.5-2.5 h, soaking the gel semi-dry electrode in water for 0.1-1 h, and circulating for 3-5 times. Preferably, the gel semi-dry electrode is soaked in electrolyte for 0.5-1 h after being removed in water, and rapid dehydration is realized by utilizing ion osmotic pressure.
According to a third aspect of the present invention, there is provided the use of the above-described gel semi-dry electrode in a physiological electrical signal detection system. The gel semi-dry electrode provided by the invention can simultaneously reduce the impedance of the stratum corneum, the electrode, the skin interface layer and the electrode which sequentially pass through in the physiological electric signal transmission process, so that the obtained physiological electric signal has high quality.
Hereinafter, the gel semi-dry electrode, and the preparation method and application thereof will be further described by the following specific examples.
Example 1
Dispersing 10g of methyl acrylate in 60g of dimethyl sulfoxide, adding 10g of silver nano-sheets with the sheet diameter of 5 mu m into the mixture after the methyl acrylate is completely dissolved to obtain suspension, adding 0.1g of azodiisobutyronitrile and 0.2g of N, N' -methylenebisacrylamide into the suspension, mixing, and magnetically stirring the mixture to obtain the electronic conductive gel precursor. Injecting the electron conductive gel precursor into a cuboid mold, and crosslinking for 0.5h at 70 ℃ to obtain electron conductive gel, taking out, freeze-drying at-60 ℃ and 3Pa, and volatilizing the organic gel to obtain a hydrophobic electron conductive gel skeleton, wherein the mass ratio of silver nano-sheets to the hydrophobic gel skeleton in the hydrophobic electron conductive gel skeleton is 1:1.
30g of acrylamide was dispersed in 100g of water, and after dissolution, 15g of sodium chloride, 7g of glycerol, 3g of ammonium persulfate and 0.1g of N, N' -methylenebisacrylamide were added to obtain a hydrogel precursor.
Immersing a hydrophobic electronic conductive gel skeleton into a hydrogel precursor in an environment of 2000 and Pa atmospheric pressure, recovering to the environment atmospheric pressure after 5 minutes, and standing for 2 hours to obtain a topological structure gel semi-dry electrode obtained by phase separation, wherein the mass ratio of the hydrophobic electronic conductive gel skeleton to the hydrophilic ion conductive hydrogel is 1:3, and in the hydrophilic ion conductive hydrogel, electrolyte accounts for 9wt% of the mass of a hydrophilic hydrogel network; water represents 65wt% of the mass of the hydrophilic hydrogel network.
The gel semi-dry electrode is put into water, the gel is stirred continuously during the period of time, so as to be fully cleaned, the gel is taken out after ten minutes, is naturally dried in the air, is soaked in water for ten minutes after two hours, is circulated for three times, and is sealed and stored for standby.
Example 2
10g of methyl methacrylate is dispersed in 60g of dimethylformamide, after the methyl methacrylate is completely dissolved, 10g of two-dimensional titanium carbide with a sheet diameter of 5 mu m is added into the mixture to obtain a suspension, 0.2g of azodiisoheptanenitrile and 0.06g of N, N' -methylenebisacrylamide are added into the suspension to be mixed, and magnetic stirring is assisted in the mixing process to obtain the electronic conductive gel precursor. Injecting the electron conductive gel precursor into a cuboid mold, crosslinking for 1h at 70 ℃ to obtain electron conductive gel, taking out, freeze-drying at-70 ℃ and 3Pa, and volatilizing the organic gel to obtain a hydrophobic electron conductive gel skeleton, wherein the mass ratio of the two-dimensional titanium carbide in the hydrophobic electron conductive gel skeleton to the hydrophobic gel skeleton is 1:1.
30g of acrylic acid was dispersed in 100g of water, and after dissolution, 15g of potassium chloride, 7g of glycerol, 3g of ammonium persulfate and 0.1g of N, N' -methylenebisacrylamide were added to obtain a hydrogel precursor.
Immersing a hydrophobic electronic conductive gel skeleton into a hydrogel precursor in an environment of 2000 and Pa atmospheric pressure, recovering to the environment atmospheric pressure after 5 minutes, and standing for 2 hours to obtain a topological structure gel semi-dry electrode obtained by phase separation, wherein the mass ratio of the hydrophobic electronic conductive gel skeleton to the hydrophilic ion conductive hydrogel is 1:3, and in the hydrophilic ion conductive hydrogel, electrolyte accounts for 9wt% of the mass of a hydrophilic hydrogel network; water represents 65wt% of the mass of the hydrophilic hydrogel network.
The gel semi-dry electrode is put into water, the gel is stirred continuously during the period of time, so as to be fully cleaned, the gel is taken out after ten minutes, is naturally dried in the air, is soaked in water for ten minutes after two hours, is circulated for three times, and is sealed and stored for standby.
Example 3
10g of ethyl acrylate is dispersed in 40g of dimethylformamide, after the ethyl acrylate is completely dissolved, 0.2g of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) is added into the mixture to obtain a solution, 0.1g of azodiisobutyronitrile and 0.3g of N, N' -methylenebisacrylamide are added into the suspension to be mixed, and magnetic stirring is assisted in the mixing process to obtain the electronically conductive gel precursor. Injecting the electron conductive gel precursor into a cuboid mold, crosslinking for 0.5h at 80 ℃ to obtain electron conductive gel, taking out, freeze-drying at-70 ℃ and 3Pa, and volatilizing the organic gel to obtain a hydrophobic electron conductive gel skeleton, wherein the mass ratio of poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonic acid) to the hydrophobic gel skeleton in the hydrophobic electron conductive gel skeleton is 1:0.02.
30g of acrylic acid was dispersed in 100g of water, and after dissolution, 20g of potassium chloride, 8g of glycerol, 3g of ammonium persulfate and 0.1g of N, N' -methylenebisacrylamide were added to obtain a hydrogel precursor.
Immersing a hydrophobic electronic conductive gel skeleton into a hydrogel precursor in an environment of 2000 and Pa atmospheric pressure, recovering to the environment atmospheric pressure after 5 minutes, and standing for 2 hours to obtain a topological structure gel semi-dry electrode obtained by phase separation, wherein the mass ratio of the hydrophobic electronic conductive gel skeleton to the hydrophilic ion conductive hydrogel is 1:3, and in the hydrophilic ion conductive hydrogel, electrolyte accounts for 12wt% of the mass of a hydrophilic hydrogel network; water represents 63wt% of the mass of the hydrophilic hydrogel network.
The gel semi-dry electrode is put into water, the gel is stirred continuously during the period of time, so as to be fully cleaned, the gel is taken out after ten minutes, is naturally dried in the air, is soaked in water for ten minutes after two hours, is circulated for three times, and is sealed and stored for standby.
Test case
(1) Flexible test
The specific test data for the gel semi-dry electrodes in examples 1 to 3 of the present invention are shown in table 1 according to the test method of D412 by measuring the stress required for stretching the gel semi-dry electrode having a cross section of 2mm x 10mm to 30% beyond the original length according to the test standard of ASTM;
TABLE 1
(2) Electrolyte slow release time test
According to the test method of F2900-11, the water loss of the gel semi-dry electrodes in examples 1 to 3 after 10 hours at a temperature of 30℃was measured according to the test standard of ASTM, and the water loss of the gel semi-dry electrodes in examples 1 to 3 of the present invention is shown in Table 2;
TABLE 2
(3) Conductivity test
The electrical resistance values of the gel semi-dry electrodes prepared in examples 1 to 3 were measured using a multimeter according to the test method of B193-20 using the test standard of ASTM, and electrical conductivities were obtained, and the electrical conductivity data of the gel semi-dry electrodes in examples 1 to 3 of the present invention are shown in table 3;
TABLE 3 Table 3
From the data of tables 1 to 3, it is apparent that the gel semi-dry electrode of the present invention has excellent flexibility, can slowly release an electrolyte for a long time, and has high electron conductivity.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (8)

1. The gel semi-dry electrode is characterized by comprising a hydrophobic electronic conductive gel skeleton and hydrophilic ion conductive hydrogel filled in the hydrophobic electronic conductive gel skeleton, wherein the hydrophobic electronic conductive gel skeleton and the hydrophilic ion conductive hydrogel form a topological structure due to a phase separation effect;
the hydrophilic ion-conductive hydrogel comprises a hydrophilic hydrogel network, and electrolyte, water and a water-retaining agent filled in the hydrophilic hydrogel network;
the material of the hydrophobic gel skeleton is at least one of polymethyl acrylate, polymethyl methacrylate and polyethyl acrylate, the electronic conductive material is two-dimensional conductive material or conductive polymer, the sheet diameter of the two-dimensional conductive material is 0.5-10 mu m, and the material of the hydrophilic hydrogel network is polyacrylamide hydrogel and/or polyacrylic hydrogel;
the mass ratio of the hydrophobic electron conductive gel skeleton to the hydrophilic ion conductive hydrogel is 1:0.5-1:3, the electrolyte accounts for 0.5-20wt% of the mass of the hydrophilic hydrogel network, and the water accounts for 17-65wt% of the mass of the hydrophilic gel network.
2. The gel semi-dry electrode according to claim 1, wherein the two-dimensional conductive material is selected from at least one of silver nanoplates, graphene, two-dimensional titanium carbide, two-dimensional niobium carbide;
and/or the conductive polymer is selected from poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid).
3. The gel semi-dry electrode according to claim 1, wherein the electrolyte is selected from at least one of lithium chloride, sodium chloride, potassium chloride, calcium chloride.
4. The gel semi-dry electrode according to claim 1, wherein the mass ratio of the electron conducting material to the hydrophobic gel skeleton is 1:0.025-1:2.5.
5. The gel semi-dry electrode according to claim 1, wherein the water retaining agent is selected from glycerol.
6. A method for preparing a gel semi-dry electrode according to any one of claims 1 to 5, comprising the steps of:
preparing a hydrophobic material monomer, an organic solvent, an electronic conductive material, a first initiator and a first crosslinking agent into an organic conductive gel precursor, and crosslinking and drying to obtain the hydrophobic electronic conductive gel skeleton;
preparing a hydrogel precursor from hydrophilic material monomers, water, electrolyte, a second initiator and a second crosslinking agent, filling the hydrogel precursor into the hydrophobic electron conductive gel skeleton, and crosslinking to form the gel semi-dry electrode with a topological structure through phase separation.
7. The method for preparing a gel semi-dry electrode according to claim 6, wherein the organic solvent is selected from at least one of dimethyl sulfoxide or dimethylformamide;
and/or the hydrophobic material monomer is at least one selected from methyl acrylate, methyl methacrylate and ethyl acrylate, wherein the mass of the hydrophobic material monomer is 20-50% of the mass of the organic solvent;
and/or the mass of the electron conducting material is 0.5-50 wt% of the mass of the organic solvent;
and/or the first initiator is selected from at least one of azodiisobutyronitrile and azodiisoheptonitrile, wherein the mass of the first initiator is 0.2-1.5 wt% of the mass of the organic solvent;
and/or the first crosslinking agent is selected from N, N' -methylene bisacrylamide, wherein the mass of the first crosslinking agent is 0.03-1 wt% of the mass of the organic solvent;
and/or the hydrophilic material monomer is at least one selected from acrylamide and acrylic acid, wherein the mass of the hydrophilic material monomer is 20-50 wt% of the mass of the water;
and/or the mass of the electrolyte is 0.9-30 wt% of the mass of the water;
and/or the second initiator is selected from at least one of ammonium persulfate and hydrogen peroxide, wherein the mass of the second initiator is 1-5 wt% of the mass of the water;
and/or the second crosslinking agent is selected from N, N' -methylene bisacrylamide, wherein the mass of the second crosslinking agent is 0.03-0.15 wt% of the mass of the organic solvent;
and/or the hydrogel precursor also contains a water-retaining agent, wherein the mass of the water-retaining agent is 5-10 wt% of the mass of the water;
and/or in the process of filling the hydrogel precursor into the hydrophobic electron conductive gel skeleton, the filling pressure is 1000 Pa-3000 Pa.
8. Use of a gel semi-dry electrode according to any one of claims 1 to 5 in a physiological electrical signal detection system.
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1559437A2 (en) * 1998-07-31 2005-08-03 First Water Limited Bioadhesive compositions comprising hydrophobic polymers
CN1680482A (en) * 2005-02-04 2005-10-12 武汉大学 Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof
CN101862462A (en) * 2004-04-22 2010-10-20 积水化成品工业株式会社 Electrode
WO2013181508A1 (en) * 2012-05-31 2013-12-05 Zoll Medical Corporation Long term wear multifunction biomedical electrode
CN112886304A (en) * 2021-01-08 2021-06-01 清华大学 Flexible non-embedded semi-dry electrode for brain-computer interface, preparation method thereof and brain-computer interface module
CN113603902A (en) * 2021-07-21 2021-11-05 厦门大学 Conductive hydrogel electrode material and application thereof
CN113801265A (en) * 2021-09-30 2021-12-17 华中科技大学 Electrode, signal detection system, hydrogel applied to electrode and preparation method of hydrogel
CN114940729A (en) * 2022-06-27 2022-08-26 燕山大学 High-strength microphase separation ionic gel with anti-swelling characteristic and preparation method thereof
CN115340103A (en) * 2022-09-01 2022-11-15 安徽大学 Boron alkene-bismuth alkene derived micro-nano topological structure flexible electrode, preparation method and application thereof
CN115337011A (en) * 2022-10-19 2022-11-15 季华实验室 Metal-coated hydrogel electrode and preparation method thereof
CN115515493A (en) * 2020-04-14 2022-12-23 日商爱医疗电子股份有限公司 Bioelectrode capable of being worn for long time
CN116269404A (en) * 2023-02-15 2023-06-23 大连理工大学 Hydrogel electrode with conductive-substrate adhesion double layers and used for long-term noninvasive electroencephalogram acquisition and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT520779B1 (en) * 2017-12-21 2020-03-15 Erba Tech Austria Gmbh Reference electrode for potentiometric measurement of ion concentrations

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1559437A2 (en) * 1998-07-31 2005-08-03 First Water Limited Bioadhesive compositions comprising hydrophobic polymers
CN101862462A (en) * 2004-04-22 2010-10-20 积水化成品工业株式会社 Electrode
CN1680482A (en) * 2005-02-04 2005-10-12 武汉大学 Non-aqueous/aqueous two-phase gel electrolyte, preparation and battery thereof
WO2013181508A1 (en) * 2012-05-31 2013-12-05 Zoll Medical Corporation Long term wear multifunction biomedical electrode
CN115515493A (en) * 2020-04-14 2022-12-23 日商爱医疗电子股份有限公司 Bioelectrode capable of being worn for long time
CN112886304A (en) * 2021-01-08 2021-06-01 清华大学 Flexible non-embedded semi-dry electrode for brain-computer interface, preparation method thereof and brain-computer interface module
CN113603902A (en) * 2021-07-21 2021-11-05 厦门大学 Conductive hydrogel electrode material and application thereof
CN113801265A (en) * 2021-09-30 2021-12-17 华中科技大学 Electrode, signal detection system, hydrogel applied to electrode and preparation method of hydrogel
CN114940729A (en) * 2022-06-27 2022-08-26 燕山大学 High-strength microphase separation ionic gel with anti-swelling characteristic and preparation method thereof
CN115340103A (en) * 2022-09-01 2022-11-15 安徽大学 Boron alkene-bismuth alkene derived micro-nano topological structure flexible electrode, preparation method and application thereof
CN115337011A (en) * 2022-10-19 2022-11-15 季华实验室 Metal-coated hydrogel electrode and preparation method thereof
CN116269404A (en) * 2023-02-15 2023-06-23 大连理工大学 Hydrogel electrode with conductive-substrate adhesion double layers and used for long-term noninvasive electroencephalogram acquisition and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Hydrogel electrodes with conductive and substrate-adhesive layers for noninvasive long-term EEG acquisition;Hailing Xue等;《 microsystems & nanoengineering》;全文 *

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