Supercapacitor, wound dressing using supercapacitor, and preparation method

Abstract

The present invention discloses a supercapacitor, a wound dressing using a supercapacitor, and a preparation method. The supercapacitor and wound dressing using a supercapacitor include a gel electrolyte (gel diaphragm) and a gel electrode (gel dressing), wherein the gel electrolyte and gel electrode are assembled to form a supercapacitor; the gel dressing serves as a wound dressing and is separated from the supercapacitor by a gel diaphragm, together forming the wound dressing using a supercapacitor. The present invention uses a supercapacitor as an energy storage and energy supply device to provide the electrical energy required for electrical stimulation to the wound dressing, allowing the wound dressing to release more active substances under the action of the electric field, thereby accelerating the cell proliferation rate and improving the wound healing ability. At the same time, the integrated structural design improves its portability, wearability, and practicality. The present invention combines the respective advantages of biomedical and flexible electronic technologies to effectively alleviate the compatibility issues of portable flexible electronic technologies.

Description

Technical Field

[0001] The present invention mainly relates to the field of biomedical materials technology, and also to the field of energy storage technology, and specifically to a supercapacitor and a preparation method thereof, as well as a wound dressing using a supercapacitor and a preparation method thereof. Background Art

[0002] The healing of skin wounds, especially chronic wounds, is often accompanied by a lengthy treatment process. Currently, wound treatments are mostly based on technologies such as compression bandage therapy, wound dressing therapy, hyperbaric oxygen therapy, negative pressure therapy, and ultrasound therapy. Hydrogel wound dressings, among others, are widely used in wound dressing therapy due to their excellent water absorption, moisturizing, breathability, antibacterial properties, and flexibility. They protect the affected area, prevent wound infection, and promote wound healing (Application Publication Numbers: CN113209361 A, CN114344558 A). However, most of these methods do not involve the regulation of cellular behavior and suffer from high treatment costs, poor therapeutic efficacy, and prolonged wound healing times, resulting in long-term physical and mental suffering for patients.

[0003] With the development of modern biomedicine and medical technology, electrical stimulation therapy, as a novel treatment method, has attracted widespread attention due to its ability to mimic the physiological mechanisms of endogenous electric fields in the body, effectively promoting the healing of skin wounds (Application Publication No.: CN113786282A). Electrical stimulation therapy can act on different stages of wound healing (Wang L, et al. Enhanced cell proliferation by electrical stimulation based on electroactive regenerated bacterial cellulose hydrogels. CarbohydratePolymers 2020, 249: 116829). The proliferation stage is a key stage in wound healing. During this stage, fibroblasts, the primary mesenchymal cells in connective tissue, synthesize collagen fibers to form granulation tissue. Together with new capillaries, they fill the defective wound tissue and form an epithelialized edge around the wound. Furthermore, the newly formed capillaries provide sufficient oxygen and nutrients for the proliferation process, thereby promoting skin regeneration. Electrical stimulation therapy can promote the proliferation and migration of fibroblasts during this phase, effectively promoting wound healing, reducing healing time, and alleviating pain (Application Publication Numbers: CN113262105A, CN107929805A). Therefore, electrical stimulation therapy, as a safe, effective, simple, and low-cost method for healing skin wounds, has garnered widespread attention in treating various types of acute and chronic skin wounds.

[0004] At present, electrical stimulation therapy mainly shortens the healing time by applying an electric field to the wound site using an electroactive scaffold as a medium. As the most common electroactive scaffold, electroactive hydrogel wound dressings can form a physical barrier that isolates the wound from the external environment during the wound healing process, preventing microorganisms from invading the wound and reducing the risk of infection. On the other hand, hydrogel wound dressings containing electroactive substances cover the wound area and contact the underlying skin, establishing a circuit to electrically stimulate the wound area, thereby accelerating fibroblast proliferation, producing collagen, increasing blood flow, and promoting granulation tissue growth, thereby enhancing the wound healing effect (Mao L, et al. Biodegradable and electroactive regenerated bacterial cellulose / MXene (Ti3C2Tx) composite hydrogel as wound dressing for accelerating skin wound healing under electrical stimulation. Advanced Healthcare Materials 2020, 9(19): 2000872). In addition, the electroactive hydrogel wound dressing can completely cover the wound during the wound healing process, has conductivity similar to human tissue and good biocompatibility, and accelerates wound healing (application publication numbers: CN113730647 A, CN113499470 A).

[0005] Although electrical stimulation therapy has received a certain amount of attention and application in the wound repair process, in actual clinical applications, it usually requires an external large power supply device to provide an appropriate electric field and continuous power supply, which limits the patient's treatment scenario. At the same time, these electroactive wound dressings only serve as carriers during the electrical stimulation process and do not provide growth factors or active substances. The way they promote wound healing is mostly passive promotion and cannot actively induce cell proliferation. Therefore, the existing technology lacks a wound dressing that can be connected to an external power supply for continuous electrical stimulation and can also be charged with the help of an external power supply and then discharged to perform electrical stimulation. Summary of the Invention

[0006] The first object of the present invention is to provide a supercapacitor, which is a sandwich-type, all-gel supercapacitor that is convenient for combining with a wound dressing to achieve self-power supply. The supercapacitor includes a gel electrolyte and gel electrodes attached to both sides of the gel electrolyte.

[0007] The second object of the present invention is to provide a method for preparing the above-mentioned full-gel supercapacitor, which can produce a full-gel supercapacitor that meets the requirements. To achieve this object, the technical solution adopted by the present invention is:

[0008] A method for preparing a supercapacitor comprises the following steps:

[0009] (1) 0.3-1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0-0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a. Solution a was then poured into a mold to prepare a gel electrolyte by a freeze-thaw method.

[0010] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) to the solution a obtained in step (1) to obtain solution b, and then pour the solution b into a mold to prepare a gel electrode by freeze-thaw method;

[0011] (3) Two gel electrodes are respectively covered on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the two sides of the sandwich-type supercapacitor are assembled with conductive materials such as carbon cloth, metal sputtering film, graphene or nanocarbon prepared on a flexible substrate, metal foil, metal foil, etc. as current collectors to obtain a full-gel supercapacitor.

[0012] A third object of the present invention is to provide a wound dressing that is self-powered and can be used in electrical stimulation wound healing treatments. To achieve this object, the present invention employs the following technical solutions:

[0013] A wound dressing comprises a supercapacitor, a gel membrane, and a gel dressing. The supercapacitor and gel dressing are attached to both sides of the gel membrane. The supercapacitor and gel dressing are connected via a conductive material such as carbon cloth, metal sputtering film, graphene or nanocarbon prepared on a flexible substrate, metal sheet, or metal foil to achieve current collection and transmission. The wound dressing can utilize the supercapacitor provided in the first object of the present invention or the supercapacitor prepared in the second object.

[0014] A fourth object of the present invention is to provide a method for preparing the above-mentioned wound dressing, which is achieved by the following steps:

[0015] (1) 0.3-1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0-0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a. Solution a was then poured into a mold to prepare a gel membrane by freeze-thaw method.

[0016] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) to the solution a obtained in step (1) to obtain a solution b, and then pour the solution b into a mold to prepare a gel dressing by freeze-thaw method;

[0017] (3) The supercapacitor and the gel dressing are attached to both sides of the gel diaphragm and connected through conductive materials such as carbon cloth, metal sputtering film, graphene or nanocarbon prepared on a flexible substrate, metal sheet, metal foil, etc. to prepare a wound dressing.

[0018] Furthermore, the supercapacitor can be made by pressing two gel dressings onto either side of a gel membrane, with the gel dressing serving as the electrode material and the gel membrane serving as the electrolyte material. The electrode and electrolyte materials can be prepared simultaneously during the preparation of the gel membrane and gel dressing, simplifying the overall wound dressing preparation process.

[0019] The beneficial effects of the present invention are:

[0020] The present invention is based on the combination of a full-gel supercapacitor and a full-gel dressing to form an integrated structure, which is applied to the electrical stimulation wound healing treatment plan; the special integrated structure integrates the gel power supply equipment and the wound dressing, which can be used in the electrical stimulation process under a conventional external power supply, and can also be charged so that the patient can continue to receive electrical stimulation while carrying it, broadening the use scenarios of electrical stimulation therapy; since the supercapacitor and wound dressing are both in a full-gel state, they have excellent antibacterial properties, good biocompatibility and mechanical properties when used, and can accelerate the release of active substances under the action of the electric field, effectively improving the wound healing rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a schematic diagram of the wound dressing structure using a supercapacitor in this application. In the figure: 1 is the gel electrolyte (gel diaphragm); 2 is the gel electrode (gel dressing).

[0022] Figure 2 Schematic diagram of charging a wound dressing using a supercapacitor for this application;

[0023] In the figure: 1 is a sandwich-type supercapacitor consisting of a gel electrode and a gel electrolyte; 2 is a gel diaphragm used as a diaphragm; 3 is a gel dressing used as a wound dressing; and 4 is a carbon cloth.

[0024] Figure 3 Schematic diagram of discharge of wound dressing using supercapacitor for this application;

[0025] In the figure: 1 is a sandwich-type supercapacitor consisting of a gel electrode and a gel electrolyte; 2 is a gel diaphragm used as a diaphragm; 3 is a gel dressing used as a wound dressing; and 4 is a carbon cloth.

[0026] Figure 4 This is the cyclic voltammetry test diagram of the supercapacitor in this application.

[0027] Figure 5 This is a diagram of the constant current charge and discharge test of the supercapacitor in this application.

[0028] Figure 6 This is the electrochemical impedance spectroscopy test diagram of the supercapacitor in this application.

[0029] Figure 7 This is a cycle test diagram of the supercapacitor used in this application.

[0030] Figure 8 A bar graph showing the cytotoxicity optical density and cell proliferation rate of the wound dressing using supercapacitors for this application.

[0031] Figure 9 This is a discharge test diagram of the supercapacitor used in this application, which is charged by an external power supply and then replaces the power supply to provide the electric field required for electrical stimulation treatment for the wound dressing.

[0032] Figure 10 Figure 1 shows a wound healing test in mice using a supercapacitor wound dressing for this application.

[0033] Figure 11 Pathological analysis of tissue sections after wound healing in mice treated with supercapacitor wound dressing for this application.

[0034] Figure 12 This is a discharge voltage test diagram of a wound dressing using a supercapacitor for this application. DETAILED DESCRIPTION

[0035] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is described in detail below with reference to the accompanying drawings and embodiments. It is necessary to point out that the following embodiments are only intended to explain and illustrate the present invention, rather than to represent all embodiments. Based on the embodiments of the present invention, some non-essential improvements and adjustments made by those skilled in the art based on the above-mentioned invention content still fall within the scope of protection of the present invention.

[0036] like Figures 1 to 3 As shown, a supercapacitor includes a gel electrolyte and gel electrodes attached to both sides of the gel electrolyte; the supercapacitor is a sandwich type and is in a full gel state.

[0037] A method for preparing a supercapacitor comprises the following steps:

[0038] (1) 0.3-1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0-0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a. Solution a was then poured into a mold and a gel electrolyte was prepared by a freeze-thaw method. The sodium hyaluronate (HA) solution was prepared by dissolving 0-15 mg of sodium hyaluronate (HA) in 10 mL of deionized water. The freeze-thaw method preparation conditions were: freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours.

[0039] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to the solution a obtained in step (1) to obtain solution b; then pour solution b into a mold and prepare a gel electrode by freeze-thaw method; wherein the preparation conditions of the freeze-thaw method are: freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours.

[0040] (3) Two gel electrodes are respectively covered on both sides of a gel electrolyte and pressed into shape to obtain a sandwich supercapacitor. On this basis, the two sides of the sandwich supercapacitor are assembled with carbon cloth, metal sputtering film, graphene or nanocarbon prepared on a flexible substrate, metal sheet, metal foil and other conductive materials as current collectors. The carbon cloth is adhered to the opposite sides of the edge of the sandwich supercapacitor using the inherent viscosity of the supercapacitor material, and finally a full gel supercapacitor is obtained.

[0041] like Figures 1 to 3 As shown, a wound dressing includes a supercapacitor prepared by the above method, a gel diaphragm and a gel dressing, wherein the supercapacitor and the gel dressing are attached to both sides of the gel diaphragm, and the supercapacitor and the gel dressing are connected by conductive materials such as carbon cloth, metal sputtering film, graphene or nanocarbon prepared on a flexible substrate, metal sheet, metal foil, etc.

[0042] A method for preparing a wound dressing comprises the following steps:

[0043] (1) 0.3-1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0-0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a. Solution a was then poured into a mold to prepare a gel membrane by a freeze-thaw method. The freeze-thaw method was prepared under the following conditions: freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours. The sodium hyaluronate (HA) solution was prepared by dissolving 0-15 mg of sodium hyaluronate (HA) in 10 mL of deionized water.

[0044] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT):PSS) and 20 μL of polyethylene glycol (PEG) to the solution a obtained in step (1) to obtain a solution b; then pour the solution b into a mold and prepare a gel dressing by a freeze-thaw method; wherein the preparation conditions of the freeze-thaw method are: freezing at -18°C for 12 hours and then placing at 25°C for 12 hours;

[0045] (3) The supercapacitor and the gel dressing are attached to both sides of the gel diaphragm and connected through conductive materials such as carbon cloth, metal sputtering film, graphene or nanocarbon prepared on a flexible substrate, metal sheet, metal foil, etc. to prepare a wound dressing. The supercapacitor can be a supercapacitor of the above structure or a supercapacitor prepared; wherein, since the preparation steps (1) and (2) of the prepared supercapacitor are the same as the steps (1) and (2) in the wound dressing preparation method, the electrode material and the electrolyte material can be prepared simultaneously during the wound dressing preparation process, thereby simplifying the entire wound dressing preparation process; in this way, the supercapacitor can be prepared by covering two pieces of gel dressing on both sides of a gel diaphragm respectively and then pressing and forming them, the gel dressing is used as the electrode material, and the gel diaphragm is used as the electrolyte material.

[0046] Since the preparation processes for the gel diaphragm and gel electrolyte, as well as the gel dressing and gel electrode, are identical, the gel diaphragm and gel dressing can be prepared simultaneously with the preparation of the gel electrolyte and gel electrode. The following examples illustrate this simultaneous preparation process. Of course, to achieve optimal performance for both the gel dressing and the supercapacitor independently, the supercapacitor can be prepared independently.

[0047] Example 1

[0048] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0049] (1) 0.7 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0.1 wt% sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a, where the sodium hyaluronate (HA) solution was prepared by dissolving 10 mg of sodium hyaluronate (HA) in 10 mL of deionized water. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by a freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0050] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0051] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0052] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1) and connected by carbon cloth to prepare a wound dressing. Its structure is as follows Figures 1 to 3 shown.

[0053] Example 2

[0054] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0055] (1) 0.3 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0.1 wt% sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a, where the sodium hyaluronate (HA) solution was prepared by dissolving 10 mg of sodium hyaluronate (HA) in 10 mL of deionized water. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by a freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0056] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0057] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0058] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1), and connected by carbon cloth to prepare a wound dressing.

[0059] Example 3

[0060] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0061] (1) 0.5 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0.1 wt% sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a, where the sodium hyaluronate (HA) solution was prepared by dissolving 10 mg of sodium hyaluronate (HA) in 10 mL of deionized water. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by a freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0062] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0063] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0064] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1), and connected by carbon cloth to prepare a wound dressing.

[0065] Example 4

[0066] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0067] (1) 1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0.1 wt% sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a, where the sodium hyaluronate (HA) solution was prepared by dissolving 10 mg of sodium hyaluronate (HA) in 10 mL of deionized water. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by a freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0068] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0069] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0070] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1), and connected by carbon cloth to prepare a wound dressing.

[0071] Example 5

[0072] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0073] (1) 0.7 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of deionized water. The resulting solution was called solution a. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0074] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0075] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0076] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1), and connected by carbon cloth to prepare a wound dressing.

[0077] Example 6

[0078] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0079] (1) 0.7 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0.05 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a, where the sodium hyaluronate (HA) solution was prepared by dissolving 5 mg of sodium hyaluronate (HA) in 10 mL of deionized water. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by a freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0080] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0081] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0082] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1), and connected by carbon cloth to prepare a wound dressing.

[0083] Example 7

[0084] The preparation process of the full gel supercapacitor and the preparation process of the wound dressing using the full gel supercapacitor are as follows:

[0085] (1) 0.7 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of a 0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a, where the sodium hyaluronate (HA) solution was prepared by dissolving 15 mg of sodium hyaluronate (HA) in 10 mL of deionized water. Solution a was then poured into a mold and a gel electrolyte (gel separator) was prepared by a freeze-thaw method (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0086] (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) (molecular weight 200, as a secondary dopant) to solution a prepared in step (1) to obtain solution b. Then pour solution b into a mold and prepare a gel electrode (gel dressing) by freeze-thawing (freezing at -18 °C for 12 hours and then placing at 25 °C for 12 hours).

[0087] (3) Two gel electrodes were placed on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, the sandwich-type supercapacitor was assembled with carbon cloth as a current collector on both sides to obtain a full gel supercapacitor with an area of 1 cm × 1 cm;

[0088] (4) The supercapacitor prepared in step (3) and the gel dressing prepared in step (2) are attached to both sides of the gel diaphragm prepared in step (1), and connected by carbon cloth to prepare a wound dressing.

[0089] Test example:

[0090] The electrochemical performance test of the sandwich supercapacitor prepared in step (3) of Example 1 of the present application is carried out, comprising the following steps:

[0091] (1) The electrochemical performance of the sandwich-type supercapacitor prepared in Example 1 was tested by cyclic voltammetry (CV), constant current charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) using an electrochemical workstation (CHI 660E).

[0092] (2) Furthermore, in step (1), the test conditions of cyclic voltammetry are: in the potential range of 0-0.8 V, 10-50 mV·s -1 The electrochemical performance of the sandwich-type supercapacitor prepared in Example 1 was tested at different scan rates.

[0093] (3) Furthermore, in step (1), the constant current charge and discharge test conditions are: in the potential range of 0-0.8 V, 0.05-0.5 mA·cm-2 The electrochemical performance of the sandwich-type supercapacitor prepared in Example 1 was tested at a current density of .

[0094] (4) Furthermore, in step (1), the test conditions of electrochemical impedance spectroscopy are: -2 -10 5 Hz, the electrochemical performance of the sandwich-type supercapacitor prepared in Example 1 was tested.

[0095] (5) The cycling performance of the sandwich-type supercapacitor prepared in Example 1 was tested using a LAND (CT2001A) instrument.

[0096] (6) Furthermore, in step (1), the cycle test conditions are: at a current density of 5 mA·cm -2 The long cycle performance of the sandwich-type supercapacitor prepared in Example 1 was tested.

[0097] (7) The electrochemical performance test results of the sandwich supercapacitor prepared in Example 1 of the present application can be obtained by Figure 4-7 As shown, the sandwich-type supercapacitor has good charge and discharge behavior and excellent long cycle characteristics, which can meet the needs of repeated charge and discharge of electrical stimulation wound dressings.

[0098] The gel dressing prepared in step (2) of Example 1 of the present application was used as a wound dressing to perform a cytotoxicity test, comprising the following steps:

[0099] (1) The gel dressing prepared in Example 1 was used as a wound dressing to perform a cytotoxicity test using the CCK-8 method.

[0100] (2) Furthermore, in step (1), DMEM complete medium containing NIH3T3 cells (7,500 cells / well) was cultured in a 96-well plate at 37°C in a 5% CO2 incubator for 24 hours. Then, 10 μL of the sterile gel dressing extract prepared in Example 1 of different concentrations was added to each well of the above 96-well plate, and then the 96-well plate was cultured at 37°C in a 5% CO2 incubator for 24, 48 and 72 hours, respectively. After that, 10 μL of CCK-8 reagent was added to each well, and then the plate was cultured in a CO2 incubator at 37°C for another 2 hours. Subsequently, the absorbance (OD) of the 96-well plate was measured at 450 nm using a microplate reader, and the relative cell proliferation rate was calculated according to the following formula. Among them, the blank control group was not inoculated with NIH3T3 cells; the negative control group was only inoculated with NIH3T3 cells in the 96-well plate and then DMEM complete medium was added. Cell proliferation rate (%) = (optical density of experimental group - optical density of blank group) / (optical density of negative group - optical density of blank group) × 100.

[0101] (3) The cytotoxicity test results of the gel dressing prepared in Example 1 of the present application as a wound dressing are as follows: Figure 8 As shown in the results, the absorbance was around 1.0, and the relative cell proliferation rate was higher than 91%, indicating that the wound dressing had no cytotoxicity to NIH3T3 cells.

[0102] In Example 1 of the present application, the gel dressing prepared in step (2) was used as a wound dressing to perform wound healing and pathological analysis tests on a full-thickness skin defect model in mice, the steps comprising:

[0103] (1) Normal clean-grade female Kunming mice (20 ± 5 g) (experimental animal use license number SYXK Zhe2021-0043) were adaptively fed for 5 days and anesthetized with 7 mg / mL sodium pentobarbital, with the volume depending on the mouse body weight (0.1 mL / 10 g). After anesthesia, the back of the mouse was completely depilated and cleaned with alcohol, and then a full-thickness rectangular wound (area 0.8 cm × 0.8 cm) was formed on the back of each mouse. After modeling, mice were treated with corresponding wounds according to the groups: the wounds of the blank control group were covered with gauze only; the wounds of the negative control group were covered with the gel dressing prepared in Example 1 as a wound dressing, and then covered and fixed with gauze; the wounds of the experimental group were covered with the gel dressing prepared in Example 1 as a wound dressing and subjected to electrical stimulation therapy; the electrical stimulation test method of the experimental group was as follows: the gel dressing prepared in Example 1 was used as a wound dressing, copper foil or carbon cloth was fixed at both ends, and electrical stimulation therapy was applied to the wound site for a certain period of time every two days, wherein the electrical stimulation therapy was divided into two stages: in the first stage, an external DC power supply was connected to the wound dressing at a rate of 0.1 mA·cm -2 The current density was 0.8 mA·cm, and the electrical stimulation treatment was carried out for 20 minutes. At the same time, the external DC power supply could also stimulate the supercapacitor with a current density of 0.8 mA·cm -2 Therefore, after the external power supply is removed, the supercapacitor can replace the external DC power supply in the second stage of electrical stimulation therapy and continue to provide the same electric field for the wound dressing for electrical stimulation therapy, which lasts for about 5 minutes. The schematic diagram of supercapacitor charging and discharging is shown in Figure 9 In practical applications, the supercapacitor can be charged regularly according to treatment requirements. During treatment, the supercapacitor acts as a portable power supply, directly and continuously powering the gel dressing, allowing patients to receive electrical stimulation wound healing treatment anytime and anywhere without the need for an external power supply. The supercapacitor and gel dressing prepared in Example 1 can be removed and replaced multiple times depending on the treatment effect.

[0104] (2) The start of the experiment was marked as day 0. On days 0, 2, 3, 4, 6, 7, 8, 10, 12, 14, and 16, the wound area was photographed with a digital camera, and the wound size was measured respectively. The modeling time was recorded as day 0 (no treatment), and then the three groups of mice were given corresponding treatment methods every 2 days. On days 3, 7, and 16, one mouse in each group was killed and the wound tissue was collected.

[0105] (3) Pathological analysis of wound tissue by hematoxylin-eosin staining. Tissue from the wound area in step (1) was collected on days 3, 7, and 16. Sections were sliced according to histological analysis methods, and the wound tissue was pathologically analyzed by hematoxylin-eosin staining.

[0106] The gel dressing prepared in Example 1 of the present application was used as a wound dressing to perform wound healing and pathological analysis on a full-thickness skin defect model in mice. The test results are as follows: Figure 10-11 As shown, it can be seen that in the experimental group where the wound was treated with wound dressing under the action of electrical stimulation, after 16 consecutive days of treatment, the wound was almost closed with only a small amount of scar. Pathological analysis showed that a large number of new blood vessels appeared in the wound tissue treated by the experimental group, the hair follicles were evenly and densely distributed, the fibroblasts were densely populated and had a high density, the granulation tissue thickness increased, and the effect on wound repair was obvious.

[0107] The wound dressing prepared in step (4) of Example 1 of the present application was subjected to a discharge test. Specifically, the wound dressing prepared in Example 1 was subjected to a discharge test using an oscilloscope (TDS 3054B). Before wound healing treatment, the supercapacitor portion assembled in Example 1 was charged to provide the electrical energy required for the electrical stimulation treatment process for the wound dressing layer of the gel dressing prepared in Example 1. The gel dressing prepared in Example 1 was subjected to a discharge test using an oscilloscope. Figure 12 As shown in the figure, it can be seen from the discharge curve that the oscilloscope detected a voltage of 100 mV in the wound dressing layer and the discharge lasted for about 40 s, which proves that the wound dressing prepared in Example 1 has achieved the expected design. This unique and simple structure enables patients to undergo electrical stimulation treatment anytime and anywhere, and can cope with the basic operations and on-demand removal requirements required for future clinical practice.

[0108] The wound dressing prepared by the patent of the present invention, in which the gel dressing is used as the wound dressing and the supercapacitor is used as the energy storage and power supply device, can directly provide the wound dressing with the electrical energy required for electrical stimulation, so that the patient does not need to use external large-scale electric field equipment for continuous and long-term electrical stimulation during the treatment process, and can receive electrical stimulation treatment anytime and anywhere; in actual application, the electrical stimulation process of the external electric field can also be combined with the supercapacitor charging process to reduce the action time of the external electric field, and the usage method can be flexibly selected, thereby broadening the use scenarios of electrical stimulation therapy and effectively improving the wound healing effect.

[0109] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a supercapacitor, characterized in that: The steps include: (1) 0.3-1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0-0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a. Solution a was then poured into a mold to prepare a gel electrolyte by a freeze-thaw method. (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) to the solution a obtained in step (1) to obtain solution b; then pour solution b into a mold and prepare a gel electrode by freeze-thaw method; (3) Two gel electrodes are respectively covered on both sides of a gel electrolyte and pressed into shape to obtain a sandwich-type supercapacitor. On this basis, current collectors are set on both sides of the sandwich-type supercapacitor for assembly to obtain a full-gel supercapacitor.

2. A wound dressing, characterized in that: The invention comprises a supercapacitor prepared according to claim 1, a gel diaphragm and a gel dressing, wherein the supercapacitor and the gel dressing are attached to both sides of the gel diaphragm, and the supercapacitor and the gel dressing are connected by a conductive material to realize the collection and transmission of current.

3. A method for preparing the wound dressing according to claim 2, characterized in that: The steps include: (1) 0.3-1.0 g of polyvinyl alcohol (PVA) and 0.1 g of guar gum (GG) were dissolved in 10 mL of 0-0.15 wt % sodium hyaluronate (HA) solution. The resulting solution was referred to as solution a. Solution a was then poured into a mold to prepare a gel membrane by freeze-thaw method. (2) Add 200 μL of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate (PEDOT:PSS) and 20 μL of polyethylene glycol (PEG) to the solution a obtained in step (1) to obtain a solution b, and then pour the solution b into a mold to prepare a gel dressing by freeze-thaw method; (3) The supercapacitor and the gel dressing are attached to both sides of the gel diaphragm and connected through a conductive material to prepare a wound dressing.

4. The method for preparing a wound dressing according to claim 3, wherein: The supercapacitor can also be made by respectively covering two sheets of gel dressing on both sides of a gel diaphragm and then pressing and molding them. The gel dressing is used as an electrode material, and the gel diaphragm is used as an electrolyte material.

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