An electrode patch with self-cooling and self-repairing functions, its preparation method and application

Abstract

The present invention belongs to the technical field of gel electrode materials. The present invention discloses an electrode patch with self-cooling and self-healing functions, its preparation method and applications. In the present invention, polydimethylsiloxane, water-soluble particles and a curing agent are mixed, and are sequentially cured and dissolved to obtain a porous polydimethylsiloxane skeleton; the porous polydimethylsiloxane skeleton, a hydrogel precursor solution and micro-nano particles are mixed and then cured to obtain the electrode patch. The hydrogel precursor can form dynamic chemical bonds during the curing process, endowing it with self-healing function, which can avoid damage caused by pulling and cutting during daily use. The porous polydimethylsiloxane skeleton and the hydrogel mixed with micro-nano particles embedded therein as a whole have high visible light reflectivity and high infrared emissivity. At the same time, due to the evaporation of water in the hydrogel precursor, the electrode patch has an evaporation-radiation hybrid cooling function, which can significantly improve the comfort level of wearing physiological electrodes.

Description

Technical Field

[0001] The present invention relates to the technical field of gel electrode materials, and particularly to an electrode patch with self-cooling and self-healing functions, its preparation method and application. Background Art

[0002] In recent years, flexible wearable electrode patches for physiological electrical signal monitoring have been widely developed. However, traditional dry electrode patches and gel wet electrode patches still have problems in terms of wearing comfort and mechanical properties. Especially during long-term wearing and use, due to poor breathability and lack of cooling function, local heat accumulation often occurs, causing discomfort to the wearer. At the same time, during daily use, the electrodes are often damaged by external forces, which all limit the application of flexible wearable electrodes.

[0003] Therefore, there is an urgent need in this field to develop an electrode patch that can autonomously cool down to ensure wearing comfort and can self-heal to avoid damage caused by external forces. Summary of the Invention

[0004] The purpose of the present invention is to provide an electrode patch with self-cooling and self-healing functions, its preparation method and application, so as to solve the problems of poor wearing comfort of existing electrode patches and easy damage by external forces.

[0005] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0006] The present invention provides a preparation method of an electrode patch with self-cooling and self-healing functions, including the following steps:

[0007] (1) Mix polydimethylsiloxane, water-soluble particles and a curing agent, and successively carry out curing and dissolution to obtain a porous polydimethylsiloxane skeleton;

[0008] (2) Mix the porous polydimethylsiloxane skeleton, a hydrogel precursor solution and micro-nano particles and then cure to obtain the electrode patch.

[0009] Preferably, the water-soluble particles are sucrose, sodium chloride, potassium chloride or sodium bicarbonate; the particle size of the water-soluble particles is 200 nm to 800 μm; the mass ratio of polydimethylsiloxane, water-soluble particles and the curing agent is 1:2 to 12:9 to 11.

[0010] Preferably, in step (1), the curing temperature is 50 to 70 °C, and the curing time is 0.5 to 2 h; the reagent used for dissolution is water, the dissolution temperature is 70 to 90 °C, and the dissolution time is 4 to 6 h.

[0011] Preferably, in step (2), the mixing includes the following steps: mixing the hydrogel precursor solution and the micro-nano particles to obtain a mixed solution; then immersing the porous polydimethylsiloxane framework in the mixed solution.

[0012] Preferably, the hydrogel precursor solution is an aqueous solution of a hydrogel precursor; the mass concentration of the hydrogel precursor solution is 2-8%; the hydrogel precursor in the hydrogel precursor solution is polyvinyl alcohol or sodium alginate; the micro-nano particles are silicon dioxide, polytetrafluoroethylene or barium sulfate; the mass of the micro-nano particles is 10-50% of the mass of the hydrogel precursor solution.

[0013] Preferably, in step (2), the curing is carried out in an ionic crosslinking agent; the ionic crosslinking agent is an aqueous solution of sodium borate or an aqueous solution of calcium chloride; the mass concentration of the ionic crosslinking agent is 2-8%.

[0014] Preferably, in step (2), the curing time is 0.5-2 h.

[0015] The present invention also provides an electrode patch with self-cooling and self-healing prepared by the preparation method of the electrode patch with self-cooling and self-healing.

[0016] The present invention also provides the application of the electrode patch with self-cooling and self-healing in a flexible wearable electrode.

[0017] It can be seen from the above technical solutions that, compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] (1) The electrode patch obtained by the present invention has a hybrid cooling system of radiative cooling and latent heat of evaporation, can play the role of a dual cooling mechanism, can effectively achieve cooling, improve the wearing comfort, and at the same time the electrode patch has a self-healing function, significantly improving the durability of the electrode patch;

[0019] (2) The manufacturing process of the electrode patch obtained by the present invention is simple, easy to mass-produce, and the size is controllable;

[0020] (3) The electrode patch obtained by the present invention can realize the controllable adjustment of the visible light reflectivity and infrared emissivity of the electrode patch by adjusting the pore size and density of the porous polydimethylsiloxane framework and the content of the micro-nano particles, and further realize the adjustment of the cooling function. Description of the Drawings

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained according to the provided drawings.

[0022] Figure 1 It is a schematic diagram of the overall structure of the electrode patch obtained by the present invention;

[0023] Figure 2 It is the test result of the self-healing performance of the electrode patch obtained in Example 1;

[0024] Figure 3 It is the test result of the temperature reduction performance of the electrode patch obtained in Example 1. Specific Embodiments

[0025] The present invention provides a preparation method of an electrode patch with self-cooling and self-healing functions, which includes the following steps:

[0026] (1) Mix polydimethylsiloxane, water-soluble particles and a curing agent, and successively carry out curing and dissolution to obtain a porous polydimethylsiloxane skeleton;

[0027] (2) Mix the porous polydimethylsiloxane skeleton, the hydrogel precursor solution and the micro-nano particles and then cure to obtain the electrode patch.

[0028] In the present invention, the water-soluble particles are preferably sucrose, sodium chloride, potassium chloride or sodium bicarbonate; the particle size of the water-soluble particles is preferably 200 nm to 800 μm, more preferably 600 nm to 600 μm; the curing agent is preferably Dow Corning DC-184 curing agent; the mass ratio of polydimethylsiloxane, water-soluble particles and the curing agent is preferably 1:2 to 12:9 to 11, more preferably 1:3 to 11:10 to 10.5.

[0029] In step (1) of the present invention, the curing temperature is preferably 50 to 70 °C, more preferably 60 to 65 °C; the curing time is preferably 0.5 to 2 h, more preferably 1 to 1.5 h; the reagent used for dissolution is preferably water; the dissolution temperature is preferably 70 to 90 °C, more preferably 80 to 85 °C; the dissolution time is preferably 4 to 6 h, more preferably 4.5 to 5.5 h.

[0030] In step (1) of the present invention, after the dissolution is completed, the obtained product is dried; the drying temperature is preferably 70 to 90 °C, more preferably 80 to 85 °C; the drying time is preferably 30 to 50 min, more preferably 40 to 45 min.

[0031] In step (1) of the present invention, the pore size and density of the porous polydimethylsiloxane framework can be controlled by the size and mass of the incorporated water-soluble particulate matter.

[0032] In step (2) of the present invention, the mixing preferably includes the following steps: mixing the hydrogel precursor solution and the micro-nano particles to obtain a mixed solution; then immersing the porous polydimethylsiloxane framework in the mixed solution.

[0033] In the present invention, the hydrogel precursor solution is preferably an aqueous solution of a hydrogel precursor; the mass concentration of the hydrogel precursor solution is preferably 2-8%, more preferably 3-6%; the hydrogel precursor in the hydrogel precursor solution is preferably polyvinyl alcohol or sodium alginate; the micro-nano particles are preferably silicon dioxide, polytetrafluoroethylene or barium sulfate; the mass of the micro-nano particles is preferably 10-50% of the mass of the hydrogel precursor solution, more preferably 20-40% of the mass of the hydrogel precursor solution; the immersion time is preferably 30-50 min, more preferably 35-45 min.

[0034] In step (2) of the present invention, the curing is preferably carried out in an ionic crosslinking agent; the ionic crosslinking agent is preferably an aqueous solution of sodium borate or an aqueous solution of calcium chloride; the mass concentration of the ionic crosslinking agent is preferably 2-8%, more preferably 5-7%; the addition of the ionic crosslinking agent can endow the electrode patch with electrical conductivity, enabling it to measure physiological electrical signals.

[0035] In step (2) of the present invention, the curing temperature is preferably room temperature; the curing time is preferably 0.5-2 h, more preferably 1-1.5 h.

[0036] In step (2) of the present invention, after the curing is completed, the obtained product is successively washed and dried; the number of washing times is preferably 2-4 times, more preferably 3 times; the specific steps of air drying are to use a hair dryer to dry the moisture on the surface of the product obtained by washing at room temperature; the air drying time is preferably 30-50 min, more preferably 40-45 min; in the present invention, air drying can avoid water loss of the gel.

[0037] In step (2) of the present invention, by controlling the pore size and density of the porous polydimethylsiloxane framework and the dosage of the micro-nano particles, controllable adjustment of the visible light reflectivity and infrared emissivity of the electrode patch can be achieved.

[0038] In the present invention, micro-nano particles are fully dispersed in the hydrogel precursor, and the mixture of the hydrogel precursor and the micro-nano particles is completely embedded in the porous polydimethylsiloxane framework without changing the size of the porous polydimethylsiloxane framework; the micro-nano particles have a high visible light reflectivity; the evaporation of water in the hydrogel precursor solution can achieve a cooling effect; the ionic crosslinking agent can cause the mixture to form dynamic chemical bonds for curing and shaping and have a self-healing function; the porous polydimethylsiloxane framework together with the whole mixture of micro-nano particles and hydrogel precursor solution embedded therein has a high visible light reflectivity (which can reduce the absorption of thermal radiation by light) and a high infrared emissivity (which can effectively emit its own blackbody radiation, resulting in radiative cooling). Together with the evaporation of water in the hydrogel precursor solution, the electrode patch has an evaporation-radiation hybrid cooling function. In addition, due to the use of the ionic crosslinking agent for curing, while imparting conductivity, it forms dynamic chemical bonds with the long-chain molecules in the hydrogel precursor, enabling the entire electrode patch to have a self-healing function. Therefore, the electrode patch obtained in the present invention integrates the functions of self-healing and radiative-evaporation hybrid cooling. When using this electrode patch to measure physiological electrical signals, it can significantly bring a cooling effect to the wearer, improve the wearing comfort, and because of its self-healing function, this electrode is not afraid of damage caused by external forces such as pulling and cutting during daily use and has excellent durability.

[0039] The present invention also provides an electrode patch with self-cooling and self-healing functions prepared by the preparation method of the electrode patch with self-cooling and self-healing functions.

[0040] The present invention also provides the application of the electrode patch with self-cooling and self-healing functions in flexible wearable electrodes.

[0041] The technical solutions provided by the present invention will be described in detail below in conjunction with embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0042] Example 1

[0043] Mix 1 g of polydimethylsiloxane, 10 g of sucrose with a particle size of 800 μm, and 10 g of Dow Corning DC-184 curing agent. Immerse the resulting mixture in an oven and cure it at 60 °C for 1 h. Immerse the cured product in water and dissolve it at 80 °C for 4 h to remove sucrose, and then place it in an oven and dry it at 70 °C for 30 min to obtain a porous polydimethylsiloxane framework;

[0044] Mix silica and an aqueous solution of polyvinyl alcohol with a mass concentration of 5%, where the mass ratio of silica to the aqueous solution of polyvinyl alcohol is 0.5:1 to obtain a mixed solution; immerse the obtained porous polydimethylsiloxane skeleton in the mixed solution for 50 min, then take out the porous polydimethylsiloxane skeleton and immerse it in an aqueous solution of sodium borate with a mass concentration of 5% and cure it at room temperature for 1 h. Wash the cured product with water 3 times and then place it in an oven and dry it at 70 °C for 30 min to obtain an electrode patch.

[0045] Example 2

[0046] The difference from Example 1 is that the amount of sucrose used is 5 g. Others are the same as in Example 1.

[0047] Example 3

[0048] The difference from Example 1 is that the amount of sucrose used is 8 g. Others are the same as in Example 1.

[0049] Example 4

[0050] The difference from Example 1 is that the amount of sucrose used is 12 g. Others are the same as in Example 1.

[0051] Example 5

[0052] The difference from Example 1 is that the particle size of sucrose is 700 nm. Others are the same as in Example 1.

[0053] Example 6

[0054] The difference from Example 1 is that the particle size of sucrose is 400 μm. Others are the same as in Example 1.

[0055] Example 7

[0056] The difference from Example 1 is that the mass ratio of silica to the aqueous solution of polyvinyl alcohol is 0.1:1. Others are the same as in Example 1.

[0057] Example 8

[0058] The difference from Example 1 is that the mass ratio of silica to the aqueous solution of polyvinyl alcohol is 0.3:1. Others are the same as in Example 1.

[0059] Example 9

[0060] Mix 1 g of polydimethylsiloxane, 10 g of potassium chloride with a particle size of 200 nm, and 10 g of Dow Corning DC-184 curing agent. Place the obtained mixed product in an oven and cure it at 55 °C for 1.5 h. Immerse the cured product in water and dissolve it at 90 °C for 5 h to remove potassium chloride, and then place it in an oven and dry it at 80 °C for 30 min to obtain a porous polydimethylsiloxane skeleton;

[0061] Mix polytetrafluoroethylene and an aqueous solution of polyvinyl alcohol with a mass concentration of 7%, where the mass ratio of polytetrafluoroethylene to the aqueous solution of polyvinyl alcohol is 0.5:1, to obtain a mixed solution; immerse the obtained porous polydimethylsiloxane skeleton in the mixed solution for 40 min, then take out the porous polydimethylsiloxane skeleton and immerse it in an aqueous solution of calcium chloride with a mass concentration of 6% for curing at room temperature for 1 h, wash the cured product with water 3 times and then place it in an oven to dry at 80 °C for 30 min to obtain an electrode patch.

[0062] Example 10

[0063] Mix 1 g of polydimethylsiloxane, 10 g of sodium chloride with a particle size of 100 nm, and 10 g of Dow Corning DC-184 curing agent, place the obtained mixed product in an oven to cure at 65 °C for 1.5 h, immerse the cured product in water to dissolve at 75 °C for 5.5 h to remove sodium chloride, and then place it in an oven to dry at 80 °C for 30 min to obtain a porous polydimethylsiloxane skeleton;

[0064] Mix barium sulfate and an aqueous solution of sodium alginate with a mass concentration of 5%, where the mass ratio of barium sulfate to the aqueous solution of sodium alginate is 0.5:1, to obtain a mixed solution; immerse the obtained porous polydimethylsiloxane skeleton in the mixed solution for 35 min, then take out the porous polydimethylsiloxane skeleton and immerse it in an aqueous solution of calcium chloride with a mass concentration of 8% for curing at room temperature for 30 min, wash the cured product with water 3 times and then place it in an oven to dry at 80 °C for 30 min to obtain an electrode patch.

[0065] Test the self-healing performance of the electrode patch obtained in Example 1. The test method and results are as follows:

[0066] Test method: Determine the tensile strength of the electrode patch obtained in Example 1 at a tensile rate of 0-260%, which is recorded as the test result of the electrode before self-healing. After the test, repeat the above steps to test the tensile strength of the electrode patch at a tensile rate of 0-260% again, which is recorded as the test result of the electrode after self-healing. The obtained results are as Figure 2 shown.

[0067] From Figure 2 it can be seen that the electrode patch obtained by the present invention has excellent self-healing performance, and the tensile strength of the electrode patch after self-healing can still meet the requirements of conventional applications.

[0068] Test the temperature reduction performance of the electrode patch obtained in Example 1. The test method and results are as follows:

[0069] Test method: Place the electrode patch obtained in Example 1 at room temperature, and measure the surface temperature of the electrode patch every 60 s within 0-2400 s, which is recorded as △T. The obtained results are asFigure 3 as shown

[0070] As can be seen from Figure 3 the present invention has excellent cooling performance and can greatly improve the wearing comfort.

[0071] From Examples 1 to 10 and Figures 2 to 3 it can be seen that the electrode patch obtained by the present invention has excellent cooling performance and mechanical properties, and can greatly improve the wearing comfort and durability. Moreover, by controlling the pore size and density of the porous polydimethylsiloxane skeleton and the dosage of micro-nano particles, the visible light reflectivity and infrared emissivity of the electrode patch can be controllably adjusted, and then the cooling performance of the electrode patch can be effectively adjusted.

[0072] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of an electrode patch with self-cooling and self-healing functions, characterized in that It includes the following steps: (1) Mix polydimethylsiloxane, water-soluble particles and a curing agent, and successively cure and dissolve them to obtain a porous polydimethylsiloxane skeleton; (2) Mix the porous polydimethylsiloxane skeleton, a hydrogel precursor solution and micro-nano particles and then cure them to obtain an electrode patch; the mass ratio of the polydimethylsiloxane, water-soluble particles and curing agent is 1:2-12:9-11; In step (2), the curing is carried out in an ionic cross-linking agent; the ionic cross-linking agent is an aqueous solution of sodium borate or an aqueous solution of calcium chloride; the mass concentration of the ionic cross-linking agent is 2-8%.

2. The preparation method of the electrode patch with self-cooling and self-healing functions according to claim 1, wherein, The water-soluble particles are sucrose, sodium chloride, potassium chloride or sodium bicarbonate; the particle size of the water-soluble particles is 200 nm-800 μm.

3. The preparation method of the electrode patch with self-cooling and self-healing according to claim 2, characterized in that In step (1), the temperature of the curing is 50-70 °C, and the time of the curing is 0.5-2 h; the reagent used for dissolution is water, the temperature of the dissolution is 70-90 °C, and the time of the dissolution is 4-6 h.

4. The preparation method of the electrode patch with self-cooling and self-healing functions according to any one of claims 1 to 3, characterized in that, In step (2), the mixing includes the following steps: mix the hydrogel precursor solution and micro-nano particles to obtain a mixed solution; then immerse the porous polydimethylsiloxane skeleton in the mixed solution.

5. The preparation method of the electrode patch with self-cooling and self-healing functions according to claim 4, wherein, The hydrogel precursor solution is an aqueous solution of a hydrogel precursor; the mass concentration of the hydrogel precursor solution is 2-8%; The hydrogel precursor in the hydrogel precursor solution is polyvinyl alcohol or sodium alginate; the micro-nano particles are silicon dioxide, polytetrafluoroethylene or barium sulfate; the mass of the micro-nano particles is 10-50% of the mass of the hydrogel precursor solution.

6. The preparation method of the electrode patch with self-cooling and self-healing functions according to claim 5, characterized in that, In step (2), the time of the curing is 0.5-2 h.

7. An electrode patch with self-cooling and self-healing properties prepared by the preparation method of the electrode patch with self-cooling and self-healing properties according to any one of claims 1-6.

8. Application of the electrode patch with self-cooling and self-healing properties according to claim 7 in a flexible wearable electrode.

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