High-sensitivity bicontinuous film electrode and preparation method thereof

Abstract

The invention discloses a high-sensitivity bicontinuous film electrode and a preparation method thereof, and belongs to the technical field of wearable sensing. Comprising the following steps: preparing a polymer solution: respectively adding polymer powder into a good solvent, dissolving the polymer powder, and uniformly stirring to obtain the polymer solution; preparing a liquid metal-polymer mixed solution, namely adding the liquid metal into the polymer solution, and uniformly dispersing the mixed solution by using a homogenizer to obtain the liquid metal-polymer mixed solution; and preparing the bicontinuous film electrode: removing the good solvent from the uniformly dispersed mixed solution by heating or freeze-drying and the like to obtain the bicontinuous film electrode. Compared with the prior art, the skin electrode has the beneficial effects that the stability of monitoring signals of the skin electrode in various deformation scenes and dynamic monitoring environments of the skin can be realized, and characteristic electrophysiological signals in disease scenes can be monitored at a high signal-to-noise ratio.

Description

Technical Field

[0001] The present invention relates to the field of wearable sensor technology, and more specifically, to a high-sensitivity double-continuous thin film electrode and a preparation method thereof. Background Art

[0002] As a direct reflection of the electrical activity in the body, electrophysiological signals contain rich physiological and pathological information and have irreplaceable value for clinical diagnosis and health management. These signals are usually monitored non-invasively through epidermal electrodes, and even tiny electrophysiological fluctuations can reflect the complex changes in the physiological state of the body. Early detection of certain potential micro-lesions (such as arrhythmias, early signs of myocardial infarction) can greatly reduce the risk of serious complications. Therefore, the accurate capture of electrophysiological signals, especially in the early identification of potential micro-lesions such as arrhythmias and myocardial infarction, is crucial to preventing serious complications and improving treatment outcomes. The development of highly sensitive epidermal electrodes that accurately monitor these tiny changes is the key to improving medical diagnosis and health management.

[0003] However, the current development of epidermal electrode technology faces significant challenges. The main problems are signal loss at the electrode-skin interface and attenuation of the electron transfer process. In order to achieve high-sensitivity monitoring, the ideal electrode material should have two major characteristics: high conductivity and low interfacial impedance. However, existing electrode materials have limitations in both aspects. Metal electrodes, such as gold and platinum, are known for their excellent conductivity, but in practical applications, they are difficult to form a stable and low-impedance interface with the skin, which is mainly attributed to the difference in mechanical properties between metal and skin tissue. This difference leads to interfacial instability and high interfacial impedance, which in turn affects the transmission efficiency and accuracy of the signal. On the other hand, conductive polymer electrodes (such as polypyrrole and polyaniline) and conductive composite electrodes can form a closer interface with the skin and reduce signal attenuation at the interface. However, the conductivity of these materials is relatively limited, resulting in certain losses during signal transmission, thereby limiting the sensitivity of the electrode. In the related art, for example, Chinese patent CN106798556A provides a portable ECG measurement system based on electronic epidermis, including an analog part, a main control MCU, and an electronic epidermis ECG electrode. The analog part and the main control MCU are made of flexible circuit boards and connected to the electronic epidermis ECG electrodes. The main control MCU includes a data processing and analysis circuit and a Bluetooth BLE communication part. In order to study the correlation between ECG signals and changes in human body movement, a three-axis sensor is also integrated on the flexible circuit board, and the electronic epidermis ECG electrode is a serpentine interconnected island bridge structure. This scheme aims to improve the measurement accuracy of ECG signals when the human body is in motion or at rest to suppress interference signals caused by human body movement, but the shortcoming of this scheme is that it does not provide any technical inspiration on how to reduce the loss of electrophysiological signals during transmission and across interfaces.

[0004] As can be seen from the above, although the existing technology has achieved the monitoring of electrophysiological signals to a certain extent, it is limited by the conductivity and interface impedance of the electrode material. The maximum sensitivity of the epidermal electrode reported so far is only 5μV·N-1, which is not enough to accurately capture slight characteristic signal changes. Therefore, how to improve the conductivity of the electrode material and reduce the interface impedance of the electrode material to improve the sensitivity of the electrode is an urgent problem to be solved in the current field. Summary of the invention

[0005] 1. Technical issues to be solved

[0006] In response to the signal loss at the electrode-skin interface and the signal loss during transmission in the prior art, the present invention provides a high-sensitivity dual-continuous thin-film electrode and a preparation method thereof, which can achieve the stability of the monitoring signal of the epidermal electrode in various epidermal deformation scenarios and dynamic monitoring environments, and monitor the characteristic electrophysiological signals in disease scenarios with a high signal-to-noise ratio.

[0007] 2. Technical solution

[0008] The purpose of the present invention is achieved through the following technical solutions.

[0009] The content of this application is used to introduce concepts in a brief form, which will be described in detail in the detailed implementation section below. The content of this application is not intended to identify the key features or essential features of the technical solution claimed for protection, nor is it intended to limit the scope of the technical solution claimed for protection.

[0010] Some embodiments of the present application propose a high-sensitivity bicontinuous thin film electrode and a preparation method thereof to solve the technical problems mentioned in the above background technology section.

[0011] As the first aspect of the present application, some embodiments of the present application provide a method for preparing a high-sensitivity bicontinuous thin film electrode, the steps comprising: preparing a polymer solution: adding polymer powders to a good solvent respectively, dissolving them and stirring them evenly to obtain a polymer solution; preparing a liquid metal-polymer mixed solution: adding liquid metal to the polymer solution, and uniformly dispersing the mixed solution with a homogenizer to obtain a liquid metal-polymer mixed solution; preparing a bicontinuous thin film electrode: removing the good solvent from the uniformly dispersed mixed solution by heating or freeze-drying to obtain a bicontinuous thin film electrode.

[0012] Furthermore, the prepared polymer solution is an ethylene / vinyl acetate-polyethylene oxide solution.

[0013] Furthermore, the step of preparing the polymer solution includes preparing an ethylene / vinyl acetate solution and preparing a polyethylene oxide solution.

[0014] Furthermore, the process for preparing the ethylene / vinyl acetate solution is as follows: dissolving 5.0 wt% to 10.0 wt% of ethylene / vinyl acetate particles in anisole, and magnetically stirring the mixture at a temperature of 90° C. to 98° C. until the ethylene / vinyl acetate particles are dissolved to obtain the ethylene / vinyl acetate solution.

[0015] Furthermore, the process for preparing the polyethylene oxide solution is: dissolving 0.2wt% to 4.0wt% of polyethylene oxide powder in an ethylene / vinyl acetate solution, and magnetically stirring at a temperature of 25°C to 40°C until the polyethylene oxide powder is dissolved to obtain an ethylene / vinyl acetate-polyethylene oxide solution.

[0016] Furthermore, preparing the liquid metal-polymer mixed solution includes preparing a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution, a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution, and a gallium-indium-tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0017] Furthermore, the process of preparing a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is: mixing a liquid metal gallium-indium alloy with an ethylene / vinyl acetate-polyethylene oxide solution to obtain an initial mixed solution; placing the initial mixed solution at a temperature of 25°C to 40°C, and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 8000rpm to 15000rpm to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0018] Furthermore, the process of preparing a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is: mixing liquid metal gallium with an ethylene / vinyl acetate-polyethylene oxide solution to obtain an initial mixed solution; placing the initial mixed solution at a temperature of 25°C to 40°C, and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 8000rpm to 15000rpm to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0019] Furthermore, the process of preparing a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is: mixing a liquid metal gallium indium tin alloy with an ethylene / vinyl acetate-polyethylene oxide solution to obtain an initial mixed solution; placing the initial mixed solution at a temperature of 25°C to 40°C, and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 8000rpm to 15000rpm to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0020] As the second aspect of the present application, some embodiments of the present application provide a high-sensitivity bicontinuous thin film electrode prepared by a high-sensitivity bicontinuous thin film electrode preparation method, including liquid metal and a polymer network, the liquid metal serving as the fluid phase of the electrode, forming an interconnected continuum in the bicontinuous film; the polymer network presents a dispersed three-dimensional porous network structure, connecting the liquid metal oxide layer and forming adhesion with the skin surface.

[0021] 3. Beneficial effects

[0022] Compared with the prior art, the advantages of the present invention are: a new type of epidermal electrode is developed, which reduces the loss of electrophysiological signals when crossing the interface and in the transmission process; a dual-continuous structure of the epidermal electrode is constructed, which can simultaneously achieve high electronic conductivity and good adhesion to the skin; the constructed epidermal electrode can achieve high signal-to-noise ratio monitoring of characteristic signals in electrophysiological tests; the electrophysiological signals collected by the epidermal electrode can be further combined with deep learning to achieve material identification based on electrophysiological signals. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Schematic diagram of a double continuous thin film electrode structure in one embodiment of the present invention;

[0024] Figure 2 is a SEM image of a polymer network in a bicontinuous thin film electrode in one embodiment of the present invention;

[0025] Figure 3 A force diagram of liquid metal and polymer in a double continuous thin film electrode in one embodiment of the present invention;

[0026] Figure 4 This is a diagram showing the effect of liquid metal content on the electrical conductivity of a bicontinuous thin film electrode in one embodiment of the present invention;

[0027] Figure 5 is a diagram showing the adhesion force between a bicontinuous thin film electrode having different polyethylene oxide contents and skin in one embodiment of the present invention;

[0028] Figure 6 A resistance change diagram of a double continuous thin film electrode under various deformation conditions in one embodiment of the present invention;

[0029] Figure 7 This is an electrocardiogram monitoring diagram of a double continuous thin film electrode on a myocardial infarction model mouse in one embodiment of the present invention;

[0030] Figure 8 This is an electromyographic monitoring diagram of a double continuous thin film electrode when a finger touches different materials in one embodiment of the present invention;

[0031] Fig. 9A diagram of a deep learning model for material recognition based on electromyographic signals in one embodiment of the present invention;

[0032] Fig.10 The figure is a schematic flow chart of a method for preparing a high-sensitivity bicontinuous thin film electrode in one embodiment of the present invention. DETAILED DESCRIPTION

[0033] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0034] Example 1

[0035] like Figure 1 As shown, this embodiment provides a high-sensitivity bicontinuous thin film electrode, including liquid metal and polymer network.

[0036] Liquid metal acts as the fluid phase of the electrode, forming an interconnected continuum in the bicontinuous film; the polymer network connects the liquid metal oxide layer and forms adhesion with the skin surface.

[0037] Specifically, liquid metal, as the fluid phase in the bicontinuous film, occupies 85.1% to 92.4% of the volume fraction of the total volume of the bicontinuous film, forming a continuum that penetrates each other in the bicontinuous film. This structure ensures that the liquid metal can flow freely inside the film without affecting the conductive properties, providing a broad and efficient channel for the transmission of electronic signals.

[0038] like Figure 2 and Figure 3 As shown, Figure 2 The microscopic morphology of the polymer network in the bicontinuous thin film electrode is shown. Figure 3 Demonstrated the interaction between liquid metal and polymer in the film.

[0039] Specifically, the polymer network presents a dispersed three-dimensional porous network structure, which can evenly and stably fix the liquid metal fluid and serve as a solid support for the liquid metal. There is a hydrogen bond interaction between the polymer network and the liquid metal, which can effectively fix the liquid metal and ensure that the liquid metal does not leak.

[0040] At the same time, the mechanical properties of the polymer network are adjustable and can be customized according to actual application requirements, thus ensuring the stability and durability of the bicontinuous film. The polymer network can also interact with proteins on the skin surface through hydrogen bonds. This unique adhesion mechanism allows the electrode to fit tightly to the skin surface and maintain good contact even when worn for a long time or in motion. This further enhances the accuracy and reliability of electrophysiological signal monitoring.

[0041] like Figure 4As shown, the effect of liquid metal content in a bicontinuous thin film electrode on its conductivity is demonstrated.

[0042] Specifically, inside the bicontinuous film, the liquid metal continuum acts as the fluid phase in the bicontinuous film, providing a good electron path for the bicontinuous film electrode. The conductivity of the film electrode is as high as 1.2×10 6 S / m, which makes it perform well in electrophysiological signal monitoring, especially the ability to capture weak signals has been significantly improved.

[0043] like Figure 5 The figure shows the adhesion force curves of bicontinuous films with different polyethylene oxide contents to the skin. By adjusting the content of polyethylene oxide in the bicontinuous film, the bicontinuous film showed different adhesion strengths, up to 45N / m. This shows that the film electrode can form a good adhesion interface with the skin, which is conducive to reducing the impedance of the electrophysiological signal across the tissue-electrode interface, thereby improving the quality and signal-to-noise ratio of the monitored electrophysiological signal.

[0044] like Figure 6 As shown, it further demonstrates the resistance change of the bicontinuous thin film electrode under various deformation conditions.

[0045] Specifically, under different cyclic deformation conditions simulating the skin, such as bending, twisting, friction, and squeezing, the resistance of the dual continuous thin film electrode hardly changes, indicating that the thin film electrode can maintain the stability of its electrical properties even during dynamic monitoring and output consistent electrophysiological signals.

[0046] like Figure 7 The figure shows the ECG monitoring image of the double-continuous thin-film electrode on the myocardial infarction model mouse. The double-continuous thin-film electrode can accurately monitor the ECG changes of the myocardial infarction mouse at different stages of myocardial damage, such as ST segment elevation, T wave elevation and P wave elevation. This shows that the double-continuous thin-film electrode has broad application potential in high-quality ECG monitoring.

[0047] like Figure 8 The figure shows the electromyographic monitoring diagram of the double continuous thin film electrode when the finger touches different materials. The double continuous thin film electrode can monitor the electrophysiological signals of the finger when it touches different materials, and each group of electrophysiological signals has similar group characteristics. This shows that even the weak electromyographic changes caused by touching different materials can still be monitored by the double continuous thin film electrode, which greatly improves the monitoring ability of the existing epidermal electrode for weak electrophysiological signals.

[0048] like Fig. 9 As shown in the figure, it demonstrates a deep learning model for material recognition based on the electromyographic signals of touching different materials.

[0049] Specifically, by using different electromyographic signals collected by dual continuous thin film electrodes and combining them with data feature processing, a deep learning model is constructed, which can achieve efficient distinction between different materials.

[0050] The dual continuous thin film electrodes in this embodiment can not only realize high-sensitivity characteristic electrophysiological signal monitoring, but also effectively improve the ability to capture weak electrophysiological signals. It has broad application prospects in wearable electronic devices and can be used for high-sensitivity monitoring of characteristic electrophysiological signals and improving the ability to monitor weak electrophysiological signals.

[0051] Example 2

[0052] like Figures 1 to 10 As shown, this embodiment discloses a method for preparing a high-sensitivity bicontinuous thin film electrode, comprising the following steps:

[0053] Preparation of polymer solution:

[0054] The polymer solution is prepared by gradually adding the polymer into a good solvent, dissolving the polymer and then stirring the mixture to obtain a polymer solution.

[0055] Specifically, the prepared polymer solution is an ethylene / vinyl acetate-polyethylene oxide solution. The steps of preparing the polymer solution include preparing an ethylene / vinyl acetate (EVA) solution and preparing a polyethylene oxide (PEO) solution.

[0056] In a specific embodiment, the process of preparing the polymer solution is as follows:

[0057] Preparation of ethylene vinyl acetate (EVA) solution: dissolving 10.0 wt% of ethylene vinyl acetate particles in anisole liquid; performing continuous magnetic stirring at 90° C. for 3 hours until the ethylene vinyl acetate particles are dissolved, thereby obtaining an ethylene vinyl acetate solution;

[0058] Preparation of polyethylene oxide (PEO) solution: dissolving 2.0 wt% of polyethylene oxide powder in the prepared ethylene / vinyl acetate (EVA) solution; performing continuous magnetic stirring at 40° C. for 2 hours until the polyethylene oxide powder is dissolved, thereby obtaining an ethylene / vinyl acetate-polyethylene oxide solution.

[0059] Preparation of liquid metal-polymer mixed solution:

[0060] The liquid metal-polymer mixed solution is prepared by adding liquid metal into the polymer solution to obtain an initial mixed solution; and then using a homogenizer to evenly disperse the initial mixed solution to obtain a liquid metal-polymer mixed solution.

[0061] Specifically, the preparation of the liquid metal-polymer mixed solution is based on three different liquid metals, and three liquid metal-polymer mixed solutions are prepared respectively.

[0062] In a specific embodiment, the process of preparing the liquid metal-polymer mixed solution is as follows:

[0063] The liquid metal gallium-indium alloy and the ethylene / vinyl acetate-polyethylene oxide solution are mixed at a weight ratio of 8:2 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25° C., and the initial mixed solution is stirred and sheared for 5 minutes using a handheld homogenizer at a speed of 10,000 rpm to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0064] Mixing liquid metal gallium and ethylene / vinyl acetate-polyethylene oxide solution at a weight ratio of 8:2 to obtain an initial mixed solution; placing the mixed initial mixed solution at a temperature of 25° C., and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 10,000 rpm for 5 minutes to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0065] The liquid metal gallium indium tin alloy and ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 8:2 to obtain an initial mixed solution; the mixed solution is placed at a temperature of 25°C, and the initial mixed solution is stirred and sheared at a speed of 10,000 rpm for 5 minutes using a handheld homogenizer to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0066] Specifically, in the above mixing process, the liquid metal forms small droplets dispersed in the solution after undergoing high-speed stirring and shearing in the homogenizer, while the polymer network is dispersed on the metal surface and in the good solvent.

[0067] Handling of liquid metal-polymer mixed solutions:

[0068] The good solvent is removed from the uniformly dispersed mixed solution by heating or freeze drying to obtain a bicontinuous thin film electrode.

[0069] Specifically, the three liquid metal-polymer mixed solutions prepared in the process of preparing the liquid metal-polymer mixed solution were added into polytetrafluoroethylene watch glasses respectively, and placed in a vacuum environment at 80° C. to remove the good solvent, thereby obtaining three prepared bicontinuous thin film electrodes.

[0070] The three bicontinuous thin film electrodes prepared by the above steps can all achieve high electronic conductivity, ensure excellent conductivity during electron transfer, and show good adhesion to the skin, which means that they can fit tightly to the skin surface and are not easy to fall off, providing an important material basis for applications such as wearable electronic devices, biosensors or medical monitoring equipment. In addition, the excellent adhesion properties of these bicontinuous thin film electrodes also help to enhance the interface stability between the electrode and the skin, reduce signal interference, and thus improve the accuracy and reliability of the device under long-term use.

[0071] In a specific embodiment, the process of treating the liquid metal-polymer mixed solution is as follows:

[0072] The prepared gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0073] The prepared gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0074] The prepared mixed solution of gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide was added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film.

[0075] Specifically, in this step, the liquid metal droplets are initially dispersed in the form of droplets, in which the entangled polymer chains form physically cross-linked networks that simultaneously capture a large amount of good solvent; as the drying proceeds, the good solvent in these networks is gradually replaced by liquid metal, and the micropores between the liquid metal droplets that were originally filled with solvent are transformed into nanopores filled with liquid metal. Ultimately, the liquid metal fluid becomes the dominant component, forming a continuous structure, and the polymer network is embedded in this liquid metal continuum.

[0076] Example 3

[0077] This embodiment discloses a method for preparing a high-sensitivity bicontinuous thin film electrode, comprising the following steps:

[0078] Preparation of polymer solution:

[0079] The polymer solution is prepared by gradually adding the polymer into a good solvent, dissolving it and then stirring it evenly to obtain a polymer solution.

[0080] Specifically, the prepared polymer solution is an ethylene / vinyl acetate-polyethylene oxide solution. The steps of preparing the polymer solution include preparing an ethylene / vinyl acetate (EVA) solution and preparing a polyethylene oxide (PEO) solution.

[0081] In a specific embodiment, the process of preparing the polymer solution is as follows:

[0082] Preparation of ethylene vinyl acetate (EVA) solution: dissolving 5.0 wt% of ethylene vinyl acetate particles in anisole liquid; performing continuous magnetic stirring for 3 hours at a temperature of 90° C. until the ethylene vinyl acetate particles are dissolved to obtain an ethylene vinyl acetate solution;

[0083] Preparation of polyethylene oxide (PEO) solution: Dissolve 0.2 wt % of polyethylene oxide powder in the prepared ethylene / vinyl acetate (EVA) solution, and perform continuous magnetic stirring at 40° C. for 2 hours until the polyethylene oxide powder is dissolved to obtain an ethylene / vinyl acetate-polyethylene oxide solution.

[0084] Preparation of liquid metal-polymer mixed solution:

[0085] The liquid metal-polymer mixed solution is prepared by adding liquid metal into the polymer solution to obtain an initial mixed solution; and then using a homogenizer to evenly disperse the initial mixed solution to obtain a liquid metal-polymer mixed solution.

[0086] Specifically, the preparation of the liquid metal-polymer mixed solution is based on three different liquid metals, and three liquid metal-polymer mixed solutions are prepared respectively.

[0087] In a specific embodiment, the process of preparing the liquid metal-polymer mixed solution is as follows:

[0088] The liquid metal gallium-indium alloy and the ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 1:1 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25° C., and the initial mixed solution is stirred and sheared for 3 minutes at a speed of 8000 rpm using a handheld homogenizer to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0089] Mixing liquid metal gallium and ethylene / vinyl acetate-polyethylene oxide solution in a weight ratio of 1:1 to obtain an initial mixed solution; placing the mixed initial mixed solution at a temperature of 25° C., and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 8000 rpm for 3 minutes to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0090] The liquid metal gallium indium tin alloy and ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 1:1 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25°C, and the initial mixed solution is stirred and sheared at a speed of 8000 rpm for 3 minutes using a handheld homogenizer to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0091] Specifically, in the above mixing process, the liquid metal forms small droplets dispersed in the solution after undergoing high-speed stirring and shearing in the homogenizer, while the polymer network is dispersed on the metal surface and in the good solvent.

[0092] Handling of liquid metal-polymer mixed solutions:

[0093] The good solvent is removed from the uniformly dispersed mixed solution by heating or freeze drying to obtain a bicontinuous thin film electrode.

[0094] Specifically, the three liquid metal-polymer mixed solutions prepared in the process of preparing the liquid metal-polymer mixed solution were added into polytetrafluoroethylene watch glasses respectively, and placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining three bicontinuous thin film electrodes.

[0095] In a specific embodiment, the process of treating the liquid metal-polymer mixed solution is as follows:

[0096] The prepared gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0097] The prepared gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0098] The prepared mixed solution of gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide was added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film.

[0099] Specifically, in this step, the liquid metal droplets are initially dispersed in the form of droplets, in which the entangled polymer chains form a physically cross-linked network that simultaneously captures a large amount of good solvent; as the drying proceeds, the good solvent in these networks is gradually replaced by liquid metal, and the micropores between the liquid metal droplets that were originally filled with solvent are transformed into nanopores filled with liquid metal. Ultimately, the liquid metal fluid becomes the dominant component, forming a continuous structure, and the polymer network is embedded in this liquid metal continuum.

[0100] Example 4

[0101] This embodiment discloses a method for preparing a high-sensitivity bicontinuous thin film electrode, comprising the following steps:

[0102] Preparation of polymer solution:

[0103] The polymer solution is prepared by gradually adding the polymer into a good solvent, dissolving it and then stirring it evenly to obtain a polymer solution.

[0104] Specifically, the prepared polymer solution is an ethylene / vinyl acetate-polyethylene oxide solution. The steps of preparing the polymer solution include preparing an ethylene / vinyl acetate (EVA) solution and preparing a polyethylene oxide (PEO) solution.

[0105] In a specific embodiment, the process of preparing the polymer solution is as follows:

[0106] Preparation of ethylene vinyl acetate (EVA) solution: dissolving 10.0 wt% of ethylene vinyl acetate particles in anisole liquid, and stirring with magnetic force for 3 hours at a temperature of 90° C. until the ethylene vinyl acetate particles are dissolved to obtain an ethylene vinyl acetate solution;

[0107] Preparation of polyethylene oxide (PEO) solution: 4.0 wt% polyethylene oxide powder was dissolved in the prepared ethylene / vinyl acetate (EVA) solution, and continuous magnetic stirring was performed at 40° C. for 2 hours until the polyethylene oxide powder was dissolved to obtain an ethylene / vinyl acetate-polyethylene oxide solution.

[0108] Preparation of liquid metal-polymer mixed solution:

[0109] The liquid metal-polymer mixed solution is prepared by adding the liquid metal into the polymer solution, and the mixed solution is evenly dispersed by a homogenizer to obtain the liquid metal-polymer mixed solution.

[0110] Specifically, the preparation of the liquid metal-polymer mixed solution is based on three different liquid metals, and three liquid metal-polymer mixed solutions are prepared respectively.

[0111] In a specific embodiment, the process of preparing the liquid metal-polymer mixed solution is as follows:

[0112] The liquid metal gallium-indium alloy and the ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 8:2 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25° C., and the initial mixed solution is stirred and sheared for 15 minutes using a handheld homogenizer at a speed of 15000 rpm to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0113] Mixing liquid metal gallium and ethylene / vinyl acetate-polyethylene oxide solution in a weight ratio of 8:2 to obtain an initial mixed solution; placing the mixed initial mixed solution at a temperature of 25° C., and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 15000 rpm for 15 minutes to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0114] The liquid metal gallium indium tin alloy and ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 8:2 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25°C, and the initial mixed solution is stirred and sheared at a speed of 15000 rpm for 15 minutes using a handheld homogenizer to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0115] Specifically, in the above mixing process, the liquid metal forms small droplets dispersed in the solution after undergoing high-speed stirring and shearing in the homogenizer, while the polymer network is dispersed on the metal surface and in the good solvent.

[0116] Handling of liquid metal-polymer mixed solutions:

[0117] The good solvent is removed from the uniformly dispersed mixed solution by heating or freeze drying to obtain a bicontinuous thin film electrode.

[0118] Specifically, the three liquid metal-polymer mixed solutions prepared in the process of preparing the liquid metal-polymer mixed solution were added into polytetrafluoroethylene watch glasses respectively, and placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining three bicontinuous thin film electrodes.

[0119] In a specific embodiment, the process of treating the liquid metal-polymer mixed solution is as follows:

[0120] The prepared gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0121] The prepared gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0122] The prepared mixed solution of gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide was added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film.

[0123] Example 5

[0124] This embodiment discloses a method for preparing a high-sensitivity bicontinuous thin film electrode, comprising the following steps:

[0125] Preparation of polymer solution:

[0126] The polymer solution is prepared by gradually adding the polymer into a good solvent, dissolving it and then stirring it evenly to obtain a polymer solution.

[0127] Specifically, the prepared polymer solution is an ethylene / vinyl acetate-polyethylene oxide solution. The steps of preparing the polymer solution include preparing an ethylene / vinyl acetate (EVA) solution and preparing a polyethylene oxide (PEO) solution.

[0128] In a specific embodiment, the process of preparing the polymer solution is as follows:

[0129] Preparation of ethylene vinyl acetate (EVA) solution: dissolving 10.0 wt% of ethylene vinyl acetate particles in anisole liquid, and continuously stirring with magnetic force at 90° C. for 3 hours until the ethylene vinyl acetate particles are dissolved to obtain an ethylene vinyl acetate solution;

[0130] Preparation of polyethylene oxide (PEO) solution: Dissolve 2.0 wt% of polyethylene oxide powder in the prepared ethylene / vinyl acetate (EVA) solution, and perform continuous magnetic stirring for 2 hours at a temperature of 40° C. until the polyethylene oxide powder is dissolved to obtain an ethylene / vinyl acetate-polyethylene oxide solution.

[0131] Preparation of liquid metal-polymer mixed solution:

[0132] The liquid metal-polymer mixed solution is prepared by adding the liquid metal into the polymer solution, and the mixed solution is evenly dispersed by a homogenizer to obtain the liquid metal-polymer mixed solution.

[0133] Specifically, the preparation of the liquid metal-polymer mixed solution is based on three different liquid metals, and three liquid metal-polymer mixed solutions are prepared respectively.

[0134] In a specific embodiment, the process of preparing the liquid metal-polymer mixed solution is as follows:

[0135] The liquid metal gallium-indium alloy and the ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 7:3 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25° C., and the initial mixed solution is stirred and sheared for 5 minutes at a speed of 10,000 rpm using a handheld homogenizer to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0136] Mixing liquid metal gallium and ethylene / vinyl acetate-polyethylene oxide solution in a weight ratio of 7:3 to obtain an initial mixed solution; placing the mixed initial mixed solution at a temperature of 25° C., and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 10,000 rpm for 5 minutes to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0137] The liquid metal gallium indium tin alloy and ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 7:3 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 25°C, and the initial mixed solution is stirred and sheared at a speed of 10000 rpm for 5 minutes using a handheld homogenizer to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0138] Specifically, in the above mixing process, the liquid metal forms small droplets dispersed in the solution after undergoing high-speed stirring and shearing in the homogenizer, while the polymer network is dispersed on the metal surface and in the good solvent.

[0139] Handling of liquid metal-polymer mixed solutions:

[0140] The good solvent is removed from the uniformly dispersed mixed solution by heating or freeze drying to obtain a bicontinuous thin film electrode.

[0141] Specifically, the three liquid metal-polymer mixed solutions prepared in the process of preparing the liquid metal-polymer mixed solution were added into polytetrafluoroethylene watch glasses respectively, and placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining three bicontinuous thin film electrodes.

[0142] In a specific embodiment, the process of treating the liquid metal-polymer mixed solution is as follows:

[0143] The prepared gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0144] The prepared gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0145] The prepared mixed solution of gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide was added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 80° C. to remove the good solvent, thereby obtaining a bicontinuous film.

[0146] Example 6

[0147] This embodiment discloses a method for preparing a high-sensitivity bicontinuous thin film electrode, comprising the following steps:

[0148] Preparation of polymer solution:

[0149] The polymer solution is prepared by gradually adding the polymer into a good solvent, dissolving it and then stirring it evenly to obtain a polymer solution.

[0150] Specifically, the prepared polymer solution is an ethylene / vinyl acetate-polyethylene oxide solution. The steps of preparing the polymer solution include preparing an ethylene / vinyl acetate (EVA) solution and preparing a polyethylene oxide (PEO) solution.

[0151] In a specific embodiment, the process of preparing the polymer solution is as follows:

[0152] Preparation of ethylene vinyl acetate (EVA) solution: dissolving 5.0 wt% of ethylene vinyl acetate particles in anisole liquid; performing continuous magnetic stirring at 98° C. for 3 hours until the ethylene vinyl acetate particles are dissolved to obtain an ethylene vinyl acetate solution;

[0153] Preparation of polyethylene oxide (PEO) solution: Dissolve 0.2 wt % of polyethylene oxide powder in the prepared ethylene / vinyl acetate (EVA) solution, and perform continuous magnetic stirring for 2 hours at a temperature of 25° C. until the polyethylene oxide powder is dissolved to obtain an ethylene / vinyl acetate-polyethylene oxide solution.

[0154] Preparation of liquid metal-polymer mixed solution:

[0155] The liquid metal-polymer mixed solution is prepared by adding liquid metal into the polymer solution to obtain an initial mixed solution; and then using a homogenizer to evenly disperse the initial mixed solution to obtain a liquid metal-polymer mixed solution.

[0156] Specifically, the preparation of the liquid metal-polymer mixed solution is based on three different liquid metals, and three liquid metal-polymer mixed solutions are prepared respectively.

[0157] In a specific embodiment, the process of preparing the liquid metal-polymer mixed solution is as follows:

[0158] The liquid metal gallium-indium alloy and the ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 1:1 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 40° C., and the initial mixed solution is stirred and sheared for 3 minutes at a speed of 8000 rpm using a handheld homogenizer to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0159] Mixing liquid metal gallium and ethylene / vinyl acetate-polyethylene oxide solution in a weight ratio of 1:1 to obtain an initial mixed solution; placing the mixed initial mixed solution at a temperature of 40° C., and using a handheld homogenizer to stir and shear the initial mixed solution at a speed of 8000 rpm for 3 minutes to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution;

[0160] The liquid metal gallium indium tin alloy and ethylene / vinyl acetate-polyethylene oxide solution are mixed in a weight ratio of 1:1 to obtain an initial mixed solution; the mixed initial mixed solution is placed at a temperature of 40°C, and the initial mixed solution is stirred and sheared at a speed of 8000 rpm for 3 minutes using a handheld homogenizer to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

[0161] Specifically, in the above mixing process, the liquid metal forms small droplets dispersed in the solution after undergoing high-speed stirring and shearing in the homogenizer, while the polymer network is dispersed on the metal surface and in the good solvent.

[0162] Handling of liquid metal-polymer mixed solutions:

[0163] The good solvent is removed from the uniformly dispersed mixed solution by heating or freeze drying to obtain a bicontinuous thin film electrode.

[0164] Specifically, the three liquid metal-polymer mixed solutions prepared in the process of preparing the liquid metal-polymer mixed solution were added into polytetrafluoroethylene watch glasses respectively, and placed in a vacuum environment at a temperature of 25° C. to remove the good solvent, thereby obtaining three bicontinuous thin film electrodes.

[0165] In a specific embodiment, the process of treating the liquid metal-polymer mixed solution is as follows:

[0166] The prepared gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution is added to a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 25° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0167] The prepared gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 25° C. to remove the good solvent, thereby obtaining a bicontinuous film;

[0168] The prepared mixed solution of gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide was added into a polytetrafluoroethylene watch glass, and then placed in a vacuum environment at a temperature of 25° C. to remove the good solvent, thereby obtaining a bicontinuous film.

[0169] Specifically, in this step, the liquid metal droplets are initially dispersed in the form of droplets, in which the entangled polymer chains form a physically cross-linked network that simultaneously captures a large amount of good solvent; as the drying proceeds, the good solvent in these networks is gradually replaced by liquid metal, and the micropores between the liquid metal droplets that were originally filled with solvent are transformed into nanopores filled with liquid metal. Ultimately, the liquid metal fluid becomes the dominant component, forming a continuous structure, and the polymer network is embedded in this liquid metal continuum.

[0170] The above schematically describes the invention and its implementation methods, which is not restrictive. Without departing from the spirit or basic features of the invention, the invention can be implemented in other specific forms. What is shown in the accompanying drawings is only one of the implementation methods of the invention. The actual structure is not limited to this, and any figure mark in the claims should not limit the claims involved. Therefore, if a person of ordinary skill in the art is inspired by it, without departing from the purpose of the invention, a structural method and an embodiment similar to the technical solution are designed without creativity, which should all fall within the scope of protection of this patent. In addition, the word "including" does not exclude other elements or steps, and the word "one" before the element does not exclude the inclusion of "multiple" elements. The multiple elements stated in the product claim can also be implemented by one element through software or hardware. The words first, second, etc. are used to indicate names, and do not indicate any specific order.

Claims

1. A method for preparing a high-sensitivity bicontinuous thin film electrode, comprising: Prepare polymer solution: add polymer powders to good solvents respectively, dissolve them and stir them evenly to obtain polymer solution; Preparing a liquid metal-polymer mixed solution: adding liquid metal to a polymer solution, and uniformly dispersing the mixed solution with a homogenizer to obtain a liquid metal-polymer mixed solution; Preparation of bicontinuous thin film electrodes: removing the good solvent from the uniformly dispersed mixed solution by heating or freeze drying to obtain a bicontinuous thin film electrode.

2. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 1, characterized in that: The prepared polymer solution is ethylene / vinyl acetate-polyethylene oxide solution.

3. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 1, characterized in that: The steps of preparing the polymer solution include preparing an ethylene / vinyl acetate solution and preparing a polyethylene oxide solution.

4. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 3, characterized in that: The process of preparing the ethylene / vinyl acetate solution is as follows: dissolving 5.0wt% to 10.0wt% of ethylene / vinyl acetate particles in anisole, and performing magnetic stirring at a temperature of 90°C to 98°C until the ethylene / vinyl acetate particles are dissolved to obtain the ethylene / vinyl acetate solution.

5. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 3, characterized in that: The process for preparing the polyethylene oxide solution is as follows: dissolving 0.2 wt% to 4.0 wt% of polyethylene oxide powder in an ethylene / vinyl acetate solution, and magnetically stirring the mixture at a temperature of 25° C. to 40° C. until the polyethylene oxide powder is dissolved to obtain an ethylene / vinyl acetate-polyethylene oxide solution.

6. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 1, characterized in that: The preparation of liquid metal-polymer mixed solution includes the preparation of gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution, gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution and gallium-indium-tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

7. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 6, characterized in that: The process of preparing the mixed solution of gallium indium alloy-ethylene / vinyl acetate-polyethylene oxide is as follows: Mixing a liquid metal gallium-indium alloy with an ethylene / vinyl acetate-polyethylene oxide solution to obtain an initial mixed solution; The initial mixed solution is placed at a temperature of 25° C. to 40° C., and a handheld homogenizer is used to stir and shear the initial mixed solution at a speed of 8000 rpm to 15000 rpm to obtain a gallium-indium alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

8. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 6, characterized in that: The process for preparing the gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution is as follows: mixing liquid metal gallium with ethylene / vinyl acetate-polyethylene oxide solution to obtain an initial mixed solution; The initial mixed solution is placed at a temperature of 25° C. to 40° C., and a handheld homogenizer is used to stir and shear the initial mixed solution at a speed of 8000 rpm to 15000 rpm to obtain a gallium-ethylene / vinyl acetate-polyethylene oxide mixed solution.

9. The method for preparing a high-sensitivity bicontinuous thin film electrode according to claim 6, characterized in that: The process of preparing the mixed solution of gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide is as follows: Mixing a liquid metal gallium indium tin alloy with an ethylene / vinyl acetate-polyethylene oxide solution to obtain an initial mixed solution; The initial mixed solution is placed at a temperature of 25° C. to 40° C., and a handheld homogenizer is used to stir and shear the initial mixed solution at a speed of 8000 rpm to 15000 rpm to obtain a gallium indium tin alloy-ethylene / vinyl acetate-polyethylene oxide mixed solution.

10. The high-sensitivity bicontinuous thin film electrode prepared by the method for preparing a high-sensitivity bicontinuous thin film electrode according to any one of claims 1 to 9, characterized in that: It includes liquid metal and polymer network. The liquid metal serves as the fluid phase of the electrode, forming a mutually penetrating continuum in the bicontinuous film; the polymer network presents a dispersed three-dimensional porous network structure, connecting the liquid metal oxide layer and forming adhesion with the skin surface.

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