Ultra-soft high-conductivity flexible electrode patch and preparation method and application thereof

Abstract

The invention provides an ultra-soft high-conductivity flexible electrode patch and a preparation method and application thereof, the flexible electrode patch comprises the following components: a single-ion conductive storage battery brush polyelectrolyte monomer, movable ions, an alkaline solvent, a cross-linking agent and a photoinitiator, one end group of the single-ion conductive storage battery brush polyelectrolyte monomer is carboxyl, and the other end group of the single-ion conductive storage battery brush polyelectrolyte monomer is hydroxyl. One end group is a carbon-carbon double bond, the other end group is a carbon-carbon double bond, the single-ion conductive storage battery brush polyelectrolyte monomer further comprises at least one polar group, and the preparation method of the flexible electrode patch comprises the following steps: dropwise adding a flexible electrode precursor solution on the surface of a tissue in situ, and rapidly curing and forming under the irradiation of ultraviolet light to form an ultra-soft electrode adaptive to the shape of the surface of the tissue. The flexible electrode patch provided by the invention has the characteristics of extremely low modulus, low ion and water molecule leakage rate, high conductivity and the like, and can form a hydrogen bond with a tissue surface to realize high adhesive force. The flexible electrode patch is simple in preparation process, convenient to use and operate and beneficial to large-scale production and clinical application.

Description

Technical Field

[0001] The present invention relates to the field of flexible electrode technology, and in particular to an ultra-soft and highly conductive flexible electrode patch and a preparation method and application thereof. Background Art

[0002] Long-term monitoring of electrophysiological signals is crucial for early diagnosis of diseases and assessment of treatment efficacy. Conventional medical imaging devices are bulky and rigid, making their use in continuous monitoring and diagnostic applications nearly impossible. Over the past decade, stretchable bioelectronics have attracted considerable attention, enabling the sensing of various physiological and biochemical signals and facilitating early detection of health conditions.

[0003] However, existing bioelectronic devices suffer from poor stability due to leakage of components (such as water and ions), which significantly affects sensitivity and fidelity. Although the addition of encapsulation layers or non-volatile solvents can mitigate leakage, there is an inevitable trade-off: increased interfacial signal loss and reduced ionic conductivity.

[0004] In summary, there is an urgent need in this field to develop a highly conductive, ultra-soft, flexible electrode that is resistant to component leakage, so that it can accurately sense electrophysiological signals in complex environments (such as the stomach where the pH value changes dynamically). Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the defects of the existing technology. The present invention proposes an ultra-soft, highly conductive, flexible electrode patch and its preparation method and application, which can resist ion and solvent leakage, and at the same time match the skin modulus to achieve high-quality transmission of electrophysiological signals, so as to accurately perceive electrophysiological signals in complex environments.

[0006] To solve the above technical problems, the technical solution adopted by the present invention is: an ultra-soft and highly conductive flexible electrode patch, comprising: a single-ion conductive bottle brush polyelectrolyte monomer, mobile ions, an alkaline solvent, a cross-linker and a photoinitiator, wherein one end group of the single-ion conductive bottle brush polyelectrolyte monomer is a carboxyl group and the other end group is a carbon-carbon double bond, and the single-ion conductive bottle brush polyelectrolyte monomer also contains at least one polar group.

[0007] Furthermore, the single-ion conductive bottle brush polyelectrolyte monomer includes one or more of acrylic acid, β-(acryloyloxy) propionic acid, and succinic acid mono-2-(2-acryloyloxy)tetraethylene glycol.

[0008] Furthermore, the cross-linking agent is a diene, including N,N'-methylenebisacrylamide.

[0009] Furthermore, the photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

[0010] Furthermore, the polar group includes an ether bond.

[0011] A method for preparing the ultra-soft, highly conductive, flexible electrode patch comprises the following steps:

[0012] S1. A hydroxide is dissolved in ultrapure water to obtain a hydroxide solution;

[0013] S2, adding a single-ion conductive bottle brush polyelectrolyte monomer, a cross-linking agent and a photoinitiator to the hydroxide solution to obtain a flexible electrode precursor solution;

[0014] S3. Add the flexible electrode precursor solution dropwise to the target site and cure it under ultraviolet light to form a flexible electrode patch that adapts to the shape of the tissue surface.

[0015] Furthermore, the hydroxide solution and the conductive bottle brush polyelectrolyte monomer form a single ion conductive precursor solution through acid-base neutralization reaction.

[0016] Furthermore, in step S3, the ultraviolet light irradiation time is not less than 10 seconds.

[0017] Furthermore, the flexible electrode patch has only one type of movable ions as carriers.

[0018] According to the application of the ultra-soft and highly conductive flexible electrode patch described above in electrophysiological signals, the electrophysiological signals include electrocardiographic signals, electromyographic signals and gastric electrographic signals.

[0019] Compared with existing technologies, the present invention offers the following advantages: the ultra-soft, highly conductive, and leak-resistant flexible electrode patch produced by the present invention exhibits in-situ rapid prototyping, biocompatibility, and tissue adhesion, demonstrating excellent clinical application prospects. The method also offers simple operation and a controllable process, demonstrating promising industrialization prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The disclosure of the present invention is illustrated with reference to the accompanying drawings. It should be understood that the drawings are for illustrative purposes only and are not intended to limit the scope of protection of the present invention. In the accompanying drawings, the same reference numerals are used to refer to the same components. Among them:

[0021] Figure 1 Schematically shows a molecular network structure diagram of a flexible electrode patch proposed according to one embodiment of the present invention;

[0022] Figure 2 Schematic diagram showing the in-situ formation of a flexible electrode patch on the surface of a mollusk according to one embodiment of the present invention;

[0023] Figure 3Schematic diagram showing the change of water retention rate of the flexible electrode patch over time according to one embodiment of the present invention

[0024] Figure 4 A diagram schematically shows the anti-ion leakage performance of a flexible electrode patch according to one embodiment of the present invention;

[0025] Figure 5 Schematically showing a stress-strain curve diagram of a flexible electrode patch proposed according to one embodiment of the present invention;

[0026] Figure 6 The figure schematically shows a test electromyographic signal diagram of a flexible electrode patch according to one embodiment of the present invention.

[0027] Numbers in the figure: 1. Single-ion conductive bottle brush electrolyte side chain; 2. Single-ion conductive bottle brush electrolyte main chain; 3. Cross-linking agent; 4. Curve of electrode water retention rate changing with time when the single-ion conductive bottle brush electrolyte monomer is β-(acryloyloxy) propionic acid; 5. Curve of electrode water retention rate changing with time when the single-ion conductive bottle brush electrolyte monomer is acrylic acid; 6. Curve of electrode water retention rate changing with time when the single-ion conductive bottle brush electrolyte monomer is succinic acid mono-2-(2-acryloyloxy)tetraethylene glycol; 7. Stress-strain curve of the electrode when the single-ion conductive bottle brush electrolyte monomer is succinic acid mono-2-(2-acryloyloxy)tetraethylene glycol; 8. Stress-strain curve of the electrode when the single-ion conductive bottle brush electrolyte monomer is acrylic acid; 9. Stress-strain curve of the electrode when the single-ion conductive bottle brush electrolyte monomer is β-(acryloyloxy)propionic acid. DETAILED DESCRIPTION

[0028] It is easy to understand that according to the technical solution of the present invention, without changing the essential spirit of the present invention, a person skilled in the art can propose a variety of interchangeable structural modes and implementation modes. Therefore, the following specific embodiments and drawings are only exemplary descriptions of the technical solution of the present invention and should not be regarded as the entire invention or as a limitation or restriction of the technical solution of the present invention.

[0029] According to one embodiment of the present invention, Figures 1-6 Shown.

[0030] In this embodiment, an ultra-soft, highly conductive, flexible electrode patch includes: a single-ion conductive bottle brush polyelectrolyte monomer, a mobile ion, an alkaline solvent, a cross-linker, and a photoinitiator. One end group of the single-ion conductive bottle brush polyelectrolyte monomer is a carboxyl group, and the end carboxyl group undergoes an acid-base neutralization reaction with an alkaline solvent to generate a mobile ion. The other end group is a carbon-carbon double bond, which polymerizes under ultraviolet light to form a single-ion conductive polyelectrolyte. The single-ion conductive bottle brush polyelectrolyte monomer also contains at least one polar group.

[0031] Specifically, the single-ion conductive bottle brush polyelectrolyte monomer includes one or more of acrylic acid, β-(acryloyloxy) propionic acid, and succinic acid mono-2-(2-acryloyloxy)tetraethylene glycol. The crosslinker is a diene, including N,N'-methylenebisacrylamide. The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate. The polar group includes an ether bond.

[0032] The method for preparing the ultra-soft and highly conductive flexible electrode patch specifically includes the following steps:

[0033] S1. A hydroxide is dissolved in ultrapure water to obtain a hydroxide solution;

[0034] S2, adding a single-ion conductive bottle brush polyelectrolyte monomer, a cross-linking agent and a photoinitiator to the hydroxide solution to obtain a flexible electrode precursor solution;

[0035] S3. Add the flexible electrode precursor solution dropwise to the target site and cure it under ultraviolet light to form a flexible electrode patch that adapts to the shape of the tissue surface.

[0036] In this embodiment, specifically, the hydroxide solution in step 1 can be prepared by adding hydroxide powder to ultrapure water at room temperature and dissolving it uniformly by ultrasonication. More specifically, the amount of hydroxide added is preferably 2-20 wt %, more preferably 9 wt %, in the solution.

[0037] The cross-linking agent in step 2 is specifically: a diene cross-linking agent, such as N,N'-methylenebisacrylamide, and the specific photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate (LAP), which has good biocompatibility; more specifically, the amount of the cross-linking agent added is 0.1-1wt% of the mass of the single-ion conductive bottle brush polyelectrolyte monomer, more preferably 0.5wt%; more specifically, the amount of the photoinitiator added is 0.5-2wt% of the mass of the monomer acrylamide, more preferably 1wt%.

[0038] In step 3, the flexible electrode precursor solution can be added dropwise to the target site and rapidly formed under 365nm ultraviolet light for 10 seconds. Specifically, the resulting solution can be injected into a mold of any shape and photocured into a gel.

[0039] Similarly, the practical application of the ultra-soft and highly conductive flexible electrode patch provided above can include high-precision capture of myoelectric, electrocardiographic, and gastric electrocardiographic signals.

[0040] like Figure 2 and Figure 6As shown, the ultra-soft, highly conductive, flexible electrode patch provided by the present invention can be rapidly formed in situ under light to form electrode patches that adapt to various shapes. The electrode is quickly formed after 10 seconds of light exposure and can be seamlessly attached to the skin of mollusks or humans.

[0041] like Figure 3 As shown, the ultra-soft and highly conductive flexible electrode patch provided by the present invention has excellent resistance to water molecule leakage, and the water retention rate of the electrode is greater than 50% after 7 days.

[0042] like Figure 4 As shown, the ultra-soft and highly conductive flexible electrode patch provided by the present invention has excellent resistance to ion leakage, and the conductivity of the electrode does not change significantly after being immersed in PBS buffer.

[0043] like Figure 5 As shown, the ultra-soft, highly conductive, flexible electrode patch provided by the present invention has an extremely low modulus and a large tensile fracture rate. The modulus of the electrode is <20 kPa, and the tensile fracture rate is >440%.

[0044] The technical scope of the present invention is not limited to the contents of the above description. Those skilled in the art can make various deformations and modifications to the above embodiments without departing from the technical idea of ​​the present invention, and these deformations and modifications should all fall within the protection scope of the present invention.

Claims

1. An ultra-soft, highly conductive, flexible electrode patch, characterized in that: include: A single-ion conductive bottle brush polyelectrolyte monomer, a mobile ion, an alkaline solvent, a crosslinking agent and a photoinitiator, wherein one end group of the single-ion conductive bottle brush polyelectrolyte monomer is a carboxyl group and the other end group is a carbon-carbon double bond, and the single-ion conductive bottle brush polyelectrolyte monomer further contains at least one polar group.

2. The ultra-soft, highly conductive, flexible electrode patch according to claim 1, characterized in that: The single-ion conductive bottle brush polyelectrolyte monomer includes one or more of acrylic acid, β-(acryloyloxy) propionic acid, and succinic acid mono-2-(2-acryloyloxy)tetraethylene glycol.

3. The ultra-soft, highly conductive, flexible electrode patch according to claim 1, characterized in that: The cross-linking agent is a diene, including N,N'-methylenebisacrylamide.

4. The ultra-soft, highly conductive, flexible electrode patch according to claim 1, characterized in that: The photoinitiator is lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

5. The ultra-soft, highly conductive, flexible electrode patch according to claim 1, characterized in that: The polar group includes an ether bond.

6. A method for preparing the ultra-soft, highly conductive, flexible electrode patch according to any one of claims 1 to 5, characterized in that: The steps include: S1. A hydroxide is dissolved in ultrapure water to obtain a hydroxide solution; S2, adding a single-ion conductive bottle brush polyelectrolyte monomer, a cross-linking agent and a photoinitiator to the hydroxide solution to obtain a flexible electrode precursor solution; S3. Add the flexible electrode precursor solution dropwise to the target site and cure it under ultraviolet light to form a flexible electrode patch that adapts to the shape of the tissue surface.

7. The preparation method according to claim 6, characterized in that: The hydroxide solution and the conductive bottle brush polyelectrolyte monomer undergo acid-base neutralization reaction to form a single ion conductive precursor solution.

8. The preparation method according to claim 6, characterized in that: In step S3, the ultraviolet light irradiation time is not less than 10 seconds.

9. The preparation method according to claim 6, characterized in that: The flexible electrode patch has only one type of movable ions as carriers.

10. Application of the ultra-soft and highly conductive flexible electrode patch according to any one of claims 1 to 5 in electrophysiological signals, wherein the electrophysiological signals include electrocardiographic signals, electromyographic signals, and electrogastric signals.

Images