Electrochemical oxygen therapy patch as well as preparation method and application thereof

Abstract

The invention provides an electrochemical oxygen therapy patch and a preparation method and application thereof, and belongs to the technical field of medical instruments. The electrochemical oxygen therapy patch comprises a flexible anode metal current collector, a composite ion exchange membrane and a flexible cathode metal current collector which are sequentially stacked, wherein an oxygen evolution reaction occurs on one side of the anode metal current collector, and an oxygen reduction reaction occurs on one side of the cathode metal current collector.

Description

Technical Field

[0001] The present disclosure relates to the technical field of medical devices, and particularly to an electrochemical oxygen therapy patch, a preparation method thereof, and an application thereof. Background Art

[0002] Diabetic foot ulcers are common and serious complications of diabetic patients, often difficult to heal due to poor blood circulation and insufficient oxygen supply. Traditional wound treatment methods include hyperbaric oxygen therapy and local oxygen supply, but both have serious limitations. For example, hyperbaric oxygen therapy needs to be carried out in a professional oxygen chamber, which is expensive, limited in use, and has a risk of oxygen poisoning. Local oxygen therapy relies on oxygen cylinder supply, making it difficult to achieve deep tissue oxygen penetration, restricting patient movement, and possibly leading to dry wound healing, affecting patient comfort. In addition, related technologies have also proposed various solutions including new wound oxygen therapy membranes, chemical oxygen therapy patches, and oxygen therapy devices, but these technologies usually have problems such as being unable to precisely adjust oxygen supply according to different stages of wound healing, poor adaptability, and insufficient portability.

[0003] Therefore, there is an urgent need for a new type of oxygen therapy device in the prior art to provide a flexible, portable, and in-situ oxygen control treatment plan, and at the same time be able to adjust oxygen supply according to the wound healing process to improve the treatment effect and patient comfort. Summary of the Invention

[0004] In view of this, the present disclosure provides an electrochemical oxygen therapy patch, a preparation method thereof, and an application thereof.

[0005] According to an embodiment of one aspect of the present disclosure, there is provided an electrochemical oxygen therapy patch, which includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence; wherein, an oxygen evolution reaction occurs on one side of the anode metal current collector, and an oxygen reduction reaction occurs on one side of the cathode metal current collector.

[0006] According to an embodiment of another aspect of the present disclosure, there is provided a method for manufacturing the above-mentioned electrochemical oxygen therapy patch, including: using a physical pressing process to assemble the flexible anode metal current collector, the composite ion exchange membrane, and the flexible cathode metal current collector to obtain the electrochemical oxygen therapy patch.

[0007] According to an embodiment of another aspect of the present disclosure, there is provided a method for using the electrochemical oxygen therapy patch, including: placing the above-mentioned electrochemical oxygen therapy patch at the wound and turning on the power supply to promote the healing of the above-mentioned wound.

[0008] According to an embodiment of the present disclosure, the flexible anode metal current collector, the composite ion exchange membrane, and the flexible cathode metal current collector stacked in sequence ensure the flexibility of the electrochemically oxygenated therapy patch, enabling the electrochemically oxygenated therapy patch to directly adhere to the wound surface, maximizing the contact between oxygen and the wound surface; the electrochemically oxygenated therapy patch can precisely supply oxygen to the wound by regulating voltage or current, and can precisely adjust the oxygen supply according to different stages of wound healing to promote wound healing; the operation mode is controllable and has strong stability, and can be continuously used for a long time during wound recovery; the size of the electrochemically oxygenated therapy patch can be adjusted according to the actual situation of the wound, and the use process is not restricted by space, improving the convenience and comfort of use; the electrochemically oxygenated therapy patch can utilize the humidity in the environment or the moisture near the wound, without the need for additional electrolyte solution and without using metal electrode plates, with a simple structure and being easy to manufacture and use.

[0009] According to an embodiment of the present disclosure, through a physical pressing process, the flexible anode metal current collector, the composite ion exchange membrane, and the flexible cathode metal current collector are assembled to obtain the electrochemically oxygenated therapy patch. The manufacturing method is simple and the cost is low, which is beneficial to large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Through the following description of the embodiments of the present disclosure with reference to the drawings, the above and other objects, features, and advantages of the present disclosure will become clearer. In the drawings:

[0011] Figure 1 It is a scanning electron microscope photo of the electrochemically oxygenated therapy patch provided in Embodiment 2 of the present disclosure;

[0012] Figure 2 It is a flexible detection photo of the electrochemically oxygenated therapy patch provided in Embodiment 2 of the present disclosure;

[0013] Figure 3 It is a photo of the oxygen production and transdermal effect of the electrochemically oxygenated therapy patch provided in Embodiment 2 of the present disclosure;

[0014] Figure 4 It is a graph of the oxygen production rate regulation result of the electrochemically oxygenated therapy patch provided in Embodiment 2 of the present disclosure;

[0015] Figure 5 It is a graph of the impedance test results of the electrochemically oxygenated therapy patches provided in Embodiment 1 and Comparative Example 1 of the present disclosure;

[0016] Figure 6 It is a graph of the oxygen production stability test results of the electrochemically oxygenated therapy patches provided in Embodiment 2 and Embodiment 5 of the present disclosure;

[0017] Figure 7 It is a photo of the rabbit wound test of the electrochemically oxygenated therapy patch provided in Embodiment 2 of the present disclosure and the oxygenated therapy patch provided by the control group;

[0018] Figure 8 The enlarged views of the rabbit wounds in the patch group and the control group after 5 days of treatment, with a magnification of 100 times; and

[0019] Figure 9 The enlarged views of the rabbit wounds in the patch group and the control group after 5 days of treatment, with a magnification of 400 times. Detailed implementation manners

[0020] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are merely exemplary and are not intended to limit the scope of the present disclosure. In the following detailed description, for the sake of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, obviously, one or more embodiments can also be implemented without these specific details. In addition, in the following description, descriptions of well-known structures and technologies are omitted to avoid unnecessarily confusing the concepts of the present disclosure.

[0021] The terms used herein are merely for describing specific embodiments and are not intended to limit the present disclosure. The term "including" used herein indicates the presence of features, steps, operations, but does not exclude the presence or addition of one or more other features.

[0022] In the case of using expressions such as "at least one of A, B, and C, etc.", generally, it should be interpreted according to the meaning that those skilled in the art usually understand this expression (for example, "a system having at least one of A, B, and C" should include, but is not limited to, a system having only A, only B, only C, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.). In the case of using expressions such as "at least one of A, B, or C, etc.", generally, it should be interpreted according to the meaning that those skilled in the art usually understand this expression (for example, "a system having at least one of A, B, or C" should include, but is not limited to, a system having only A, only B, only C, having A and B, having A and C, having B and C, and / or having A, B, and C, etc.).

[0023] In the process of implementing the concept of the present disclosure, it is found that an electrochemical oxygen therapy patch can be used to directly adhere to the wound surface, accurately supply oxygen to the wound, and can accurately regulate the oxygen supply rate according to the wound recovery situation to assist in wound treatment.

[0024] Specifically, according to an embodiment of one aspect of the present disclosure, an electrochemical oxygen therapy patch is provided. The electrochemical oxygen therapy patch includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence; wherein, an oxygen evolution reaction occurs on one side of the anode metal current collector, and an oxygen reduction reaction occurs on one side of the cathode metal current collector.

[0025] According to an embodiment of the present disclosure, the flexible anode metal current collector, the composite ion exchange membrane, and the flexible cathode metal current collector stacked in sequence ensure the flexibility of the electrochemically oxygenated therapy patch, enabling the electrochemically oxygenated therapy patch to be directly attached to the wound surface, maximizing the contact between oxygen and the wound surface; the electrochemically oxygenated therapy patch can accurately supply oxygen to the wound by regulating voltage or current, and can precisely adjust the oxygen supply according to different stages of wound healing, promoting wound healing; the operation mode is controllable and has strong stability, and can be continuously used for a long time during wound recovery; the size of the electrochemically oxygenated therapy patch can be regulated according to the actual situation of the wound, and the use process is not restricted by space, improving the convenience and comfort of use; the electrochemically oxygenated therapy patch can utilize the humidity in the environment or the moisture near the wound, without the need for additional electrolyte solution and without using metal electrode plates, with a simple structure and being easy to manufacture and use.

[0026] According to an embodiment of the present disclosure, the composite ion exchange membrane is loaded with an oxygen evolution catalyst on the side close to the anode metal current collector, so that an oxygen evolution reaction occurs on the side of the anode metal current collector; the composite ion exchange membrane is loaded with an oxygen reduction catalyst on the side close to the cathode metal current collector, so that an oxygen reduction reaction occurs on the side of the cathode metal current collector.

[0027] According to an embodiment of the present disclosure, the flexible anode metal current collector and the flexible cathode metal current collector are each independently selected from at least one of metal fiber cloth, metal mesh, foam metal, and metal foil.

[0028] According to an embodiment of the present disclosure, the materials of the flexible anode metal current collector and the flexible cathode metal current collector are each independently selected from at least one of titanium, platinum, gold, nickel, and stainless steel.

[0029] Preferably, the flexible anode metal current collector and the flexible cathode metal current collector can be titanium mesh or titanium fiber cloth.

[0030] According to an embodiment of the present disclosure, the oxygen evolution catalyst can include at least one of ruthenium-based catalysts, iridium-based catalysts, cobalt-based catalysts, nickel-based catalysts, manganese-based catalysts, iron-based catalysts, and molybdenum-based catalysts.

[0031] According to an embodiment of the present disclosure, the oxygen reduction catalyst can include at least one of platinum-based catalysts, cobalt-based catalysts, iron-based catalysts, nickel-based catalysts, manganese-based catalysts, copper-based catalysts, and doped carbon-based catalysts.

[0032] According to an embodiment of the present disclosure, the composite ion exchange membrane is loaded with a hydrophilic material on the side close to the anode metal current collector.

[0033] According to an embodiment of the present disclosure, the composite ion exchange membrane is loaded with a hydrophilic material on the side close to the cathode metal current collector.

[0034] In one embodiment of the present disclosure, the composite ion exchange membrane may be loaded with a hydrophilic material only on the side close to the anode metal current collector.

[0035] In another embodiment of the present disclosure, the composite ion exchange membrane may be loaded with a hydrophilic material only on the side close to the cathode metal current collector.

[0036] In still another embodiment of the present disclosure, the composite ion exchange membrane may be loaded with hydrophilic materials on the side close to the cathode metal current collector and on the side close to the cathode metal current collector, respectively. At this time, the hydrophilic materials loaded on the side close to the cathode metal current collector and on the side close to the cathode metal current collector may be the same or different.

[0037] According to the embodiments of the present disclosure, the hydrophilic material and the catalyst may form a catalytic layer. The hydrophilic material may include at least one of polyvinyl alcohol and polyethylene glycol. Among them, polyvinyl alcohol has a large number of hydroxyl groups, good hydrophilicity, and can effectively improve the hydrophilicity of the catalytic layers on both sides of the composite ion exchange membrane; at the same time, it has good film-forming properties, can enhance the structural stability of the catalytic layer; in addition, it can improve the microstructure of the catalytic layer and enhance its water management ability. The chain segments in polyethylene glycol are rich in ether bonds, can form hydrogen bonds with water molecules, and have good hydrophilicity; it can increase the adsorption and retention ability of the catalytic layer for water; in addition, the flexible chain segments can improve the flexibility of the catalytic layer and reduce structural damage caused by wet-dry cycling.

[0038] According to the embodiments of the present disclosure, on the side close to the anode metal current collector, the mass of the hydrophilic material is 0.1% - 5% of the mass of the oxygen evolution catalyst. Exemplarily, the mass of the hydrophilic material can be 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% of the mass of the oxygen evolution catalyst or any range between any two of the above.

[0039] According to the embodiments of the present disclosure, on the side close to the cathode metal current collector, the mass of the hydrophilic material is 0.1% - 5% of the mass of the oxygen reduction catalyst. Exemplarily, the mass of the hydrophilic material can be 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% of the mass of the oxygen reduction catalyst or any range between any two of the above. According to the embodiments of the present disclosure, the ion exchange membrane may be a proton exchange membrane.

[0040] According to the embodiments of the present disclosure, the proton exchange membrane is at least one of fluorosulfonic acid group polymer proton membranes or polybenzimidazole proton membranes.

[0041] According to embodiments of the present disclosure, the proton exchange membrane may be at least one of NR212, N115, N117, N1110, and Fumapem AM-40.

[0042] According to embodiments of the present disclosure, the ion exchange membrane, such as the proton exchange membrane, may be infiltrated with water or an aqueous solution to more favorably generate oxygen persistently.

[0043] According to embodiments of the present disclosure, the thicknesses of the flexible anode metal current collector and the flexible cathode metal current collector may both be 0.1 - 0.5 mm, preferably 0.15 - 0.20 mm.

[0044] According to embodiments of the present disclosure, the thicknesses of the flexible anode metal current collector and the flexible cathode metal current collector may be the same or different. Specifically, the flexible anode metal current collector may be in the range of 0.1 mm, 0.12 mm, 0.15 mm, 0.17 mm, 0.18 mm, 0.20 mm, 0.22 mm, 0.23 mm, 0.25 mm, 0.3 mm, 0.4 mm, 0.5 mm or any range between any two of them, and the flexible cathode metal current collector may be in the range of 0.1 mm, 0.12 mm, 0.15 mm, 0.17 mm, 0.18 mm, 0.20 mm, 0.22 mm, 0.23 mm, 0.25 mm, 0.3 mm, 0.4 mm, 0.5 mm or any range between any two of them.

[0045] According to embodiments of the present disclosure, the thickness of the ion exchange membrane may be 50 μm - 250 μm, preferably 100 μm - 200 μm. Specifically, the thickness of the ion exchange membrane may be in the range of 50 μm, 80 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, 220 μm, 250 μm or any range between any two of them.

[0046] According to embodiments of another aspect of the present disclosure, there is provided a method for manufacturing the above-mentioned electrochemical oxygen therapy patch, including: using a physical pressing process to assemble the flexible anode metal current collector, the composite ion exchange membrane, and the flexible cathode metal current collector to obtain the electrochemical oxygen therapy patch.

[0047] According to embodiments of the present disclosure, by using a physical pressing process to assemble the flexible anode metal current collector, the composite ion exchange membrane, and the flexible cathode metal current collector to obtain the electrochemical oxygen therapy patch, the manufacturing method is simple and the cost is low, which is beneficial to large-scale production.

[0048] According to an embodiment of the present disclosure, the composite ion exchange membrane may include an ion exchange membrane with an oxygen evolution catalyst and an oxygen reduction catalyst respectively loaded on both sides. The oxygen evolution catalyst and the oxygen reduction catalyst can be respectively loaded on both sides of the ion exchange membrane by at least one of screen printing, spraying, magnetron sputtering, roll coating, and chemical vapor deposition (CVD).

[0049] According to an embodiment of the present disclosure, the temperature of the physical pressing process is 20~250°C, the pressure is 5~40 MPa, and the pressing time is 5~180 min. Optionally, the temperature of the physical pressing process can be 80~250°C.

[0050] Exemplarily, the temperature of the physical pressing process can be in the range between any two of 20°C, 30°C, 50°C, 170°C, 80°C, 100°C, 120°C, 130°C, 150°C, 170°C, 180°C, 200°C, 220°C, 230°C, 250°C or above, and can be selected as 80°C; the pressure can be 5 MPa, 10 MPa, 15 MPa, 20 MPa, 25 MPa, 30 MPa, 35 MPa, 40 MPa, etc.; the pressing time can be in the range between any two of 5 min, 6 min, 8 min, 10 min, 15 min, 20 min, 30 min, 50 min, 80 min, 100 min, 120 min, 150 min, 180 min or above.

[0051] According to an embodiment of the present disclosure, the preferred physical pressing process conditions can not only ensure the stability of the assembled electrochemically oxygenated therapy patch (good mechanical properties), but also ensure its function of providing oxygen.

[0052] According to an embodiment of the present disclosure, before assembling the flexible anode metal current collector, the composite ion exchange membrane and the flexible cathode metal current collector, it may further include: roughening the flexible anode metal current collector and the flexible cathode metal current collector.

[0053] According to an embodiment of another aspect of the present disclosure, a method for using an electrochemically oxygenated therapy patch is provided, including: placing the above-mentioned electrochemically oxygenated therapy patch at the wound and turning on the power supply to promote wound healing.

[0054] According to an embodiment of the present disclosure, a hydrophilic breathable cotton or medical gauze is arranged between the wound and the electrochemically oxygenated therapy patch.

[0055] According to an embodiment of the present disclosure, after turning on the power supply, the current density of the electrochemically oxygenated therapy patch can be 10~500 A / m 2 . Exemplarily, the current density of the electrochemically oxygenated therapy patch can be 10 A / m 2 、20 A / m 2 、30 A / m2 , 40 A / m 2 , 50 A / m 2 , 60 A / m 2 , 70 A / m 2 , 80 A / m 2 , 90 A / m 2 , 100 A / m 2 , 200 A / m 2 , 250 A / m 2 , 300 A / m 2 , 350 A / m 2 , 400 A / m 2 , 450 A / m 2 , 500 A / m 2 or the range between any two of the above.

[0056] According to an embodiment of the present disclosure, the flexible anode metal current collector on the anode side is disposed closer to the wound than the flexible cathode metal current collector on the cathode side.

[0057] The electrochemically oxygenated therapy patch provided by the embodiments of the present disclosure can be used for the treatment of diabetic foot ulcers to provide a flexible, portable, and in-situ oxygen-controlled treatment solution, and at the same time can adjust the oxygen supply according to the wound healing process, improving the treatment effect and patient comfort.

[0058] According to an embodiment of the present disclosure, when the ion exchange membrane is a proton exchange membrane, the anodic reaction is:

[0059]

[0060] The cathodic reaction is:

[0061]

[0062] The following lists a plurality of specific embodiments to illustrate the technical solutions of the present disclosure in detail. It should be noted that the specific embodiments below are only for illustration and do not limit the present disclosure.

[0063] Example 1

[0064] This embodiment provides an electrochemically oxygenated therapy patch, which includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence. Among them, the flexible anode metal current collector and the flexible cathode metal current collector are selected from nickel foam with a thickness of 0.1 mm; the composite ion exchange membrane is loaded with an oxygen evolution catalyst and a hydrophilic material polyvinyl alcohol on the side close to the anode metal current collector, and the mass of the hydrophilic material is 2% of the mass of the oxygen evolution catalyst; the composite ion exchange membrane is loaded with an oxygen reduction catalyst The hydrophilic material is polyvinyl alcohol, and the mass of the hydrophilic material is 2% of the mass of the oxygen reduction catalyst; the ion exchange membrane is NR212 membrane.

[0065] The electrochemical oxygen therapy patch provided in this embodiment is fabricated by the following method:

[0066] (1) Prepare a proton exchange membrane with a size of 10 cm × 10 cm; by means of spraying method, an oxygen evolution catalyst is loaded on one side of the ion exchange membrane, and an oxygen reduction catalyst is loaded on the other side to obtain a composite ion exchange membrane.

[0067] (2) Prepare two flexible metal current collectors that match the size of the above-mentioned cut composite ion exchange membrane.

[0068] (3) Place the composite ion exchange membrane between the two flexible metal current collectors, and assemble the three into a whole through a physical pressing process to obtain an electrochemical oxygen therapy patch. Among them, the temperature of the physical pressing is 80 °C, the pressure is 5 MPa, and the time is 15 min.

[0069] Example 2

[0070] This embodiment provides an electrochemical oxygen therapy patch, which includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence. Among them, the flexible anode metal current collector and the flexible cathode metal current collector are selected from titanium fiber cloth, and the thickness is 0.1 mm; the composite ion exchange membrane loads an oxygen evolution catalyst on the side close to the anode metal current collector and a hydrophilic material polyvinyl alcohol, and the mass of the hydrophilic material is 2% of the mass of the oxygen evolution catalyst; the composite ion exchange membrane loads an oxygen reduction catalyst on the side close to the cathode metal current collector and a hydrophilic material polyvinyl alcohol, and the mass of the hydrophilic material is 2% of the mass of the oxygen reduction catalyst; the ion exchange membrane is NR212 membrane with a thickness of 50 μm.

[0071] The manufacturing method of the electrochemical oxygen therapy patch provided in this embodiment refers to Example 1 and will not be elaborated here.

[0072] The above-mentioned electrochemical oxygen therapy patch is detected by scanning electron microscope, and the scanning electron microscope photos are as Figure 1 shown. It can be seen from Figure 1 that in the electrochemical oxygen therapy patch provided in this embodiment, the interface between the titanium fiber cloth and the composite ion exchange membrane is well combined.

[0073] The above-mentioned electrochemical oxygen therapy patch is subjected to a flexibility test, and the flexibility test photos are as Figure 2 shown. It can be seen from Figure 2 that the electrochemical oxygen therapy patch provided in this embodiment has good flexibility and adaptability to the curvature of the wound shape.

[0074] The oxygen generation and transdermal effect of the above-mentioned electrochemically oxygenated therapy patch was tested, and the oxygen generation and transdermal effect diagram is as follows Figure 3 shown. Figure 3 Among them, the black curve is the dissolved oxygen amount of only using a moist medical gauze, the red curve is the dissolved oxygen amount of using a moist medical gauze and porcine epidermal tissue, the blue curve is the dissolved oxygen amount of the electrochemically oxygenated therapy patch passing through the moist medical gauze, and the green curve is the dissolved oxygen amount of the electrochemically oxygenated therapy patch passing through the moist medical gauze and porcine epidermal tissue. It can be seen from Figure 3 this that the above-mentioned electrochemically oxygenated therapy patch can treat the wound area through the medical gauze and porcine epidermal tissue.

[0075] The connection voltage of the above-mentioned electrochemically oxygenated therapy patch was regulated to conduct oxygen generation rate regulation, and the oxygen generation rate regulation detection is as follows Figure 4 shown. It can be seen from Figure 4 this that the oxygen generation rate and the voltage are approximately linearly related, and the oxygen generation rate of the electrochemically oxygenated therapy patch can be regulated by changing the voltage.

[0076] Example 3

[0077] In this example, the design of the electrochemically oxygenated therapy patch and the manufacturing method of the electrochemically oxygenated therapy patch refer to Example 2. The difference is that the oxygen evolution catalyst is an iridium ruthenium composite catalyst; the oxygen reduction catalyst is a cobalt oxide catalyst.

[0078] Example 4

[0079] In this example, the design of the electrochemically oxygenated therapy patch and the manufacturing method of the electrochemically oxygenated therapy patch refer to Example 2. The difference is that the temperature of the physical pressing process is 20°C, the pressure is 8 MPa, and the time is 1 h.

[0080] Examples 5 to 11

[0081] For Examples 5 to 11, the design of the electrochemically oxygenated therapy patch and the manufacturing method of the electrochemically oxygenated therapy patch refer to Example 2. The difference lies in that in Example 5, the composite ion exchange membrane is not loaded with the hydrophilic material polyvinyl alcohol on both the side close to the anode metal current collector and the side close to the cathode metal current collector; in Examples 6 to 9, the composite ion exchange membrane is loaded with the hydrophilic material polyvinyl alcohol on both the side close to the anode metal current collector and the side close to the cathode metal current collector. Among them, in Example 6, the mass of the hydrophilic material on both sides of the composite ion exchange membrane is 0.05% of the mass of the oxygen evolution catalyst; in Example 7, the mass of the hydrophilic material on both sides of the composite ion exchange membrane is 0.1% of the mass of the oxygen evolution catalyst; in Example 8, the mass of the hydrophilic material on both sides of the composite ion exchange membrane is 1% of the mass of the oxygen evolution catalyst; in Example 9, the mass of the hydrophilic material on both sides of the composite ion exchange membrane is 3% of the mass of the oxygen evolution catalyst; in Example 10, the mass of the hydrophilic material on both sides of the composite ion exchange membrane is 5% of the mass of the oxygen evolution catalyst; in Example 11, the mass of the hydrophilic material on both sides of the composite ion exchange membrane is 6% of the mass of the oxygen evolution catalyst.

[0082] Example 12

[0083] This example provides an electrochemically oxygenated therapy patch, which includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence. Among them, the flexible anode metal current collector and the flexible cathode metal current collector are selected from platinum meshes with a thickness of 0.3 mm; the composite ion exchange membrane is loaded with an oxygen evolution catalyst and the hydrophilic material polyvinyl alcohol on the side close to the anode metal current collector, and the mass of the hydrophilic material is 3% of the mass of the oxygen evolution catalyst; the composite ion exchange membrane is loaded with an oxygen reduction catalyst and the hydrophilic material polyvinyl alcohol on the side close to the cathode metal current collector, and the mass of the hydrophilic material is 3% of the mass of the oxygen reduction catalyst; the ion exchange membrane is a polybenzimidazole-based ion exchange membrane with a thickness of 180 μm.

[0084] The manufacturing method of the electrochemically oxygenated therapy patch provided in this example refers to Example 1, with the difference that the temperature of the physical pressing process is 200 °C, the pressure is 35 MPa, and the time is 1 h.

[0085] Example 13

[0086] This example provides an electrochemically oxygenated therapy patch, which includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence. Among them, the flexible anode metal current collector and the flexible cathode metal current collector are selected from stainless steel foils with a thickness of 0.4 mm; the composite ion exchange membrane is loaded with an oxygen evolution catalyst The hydrophilic material is polyvinyl alcohol, and the mass of the hydrophilic material is 1% of the mass of the oxygen evolution catalyst; the composite ion exchange membrane is loaded with an oxygen reduction catalyst on the side close to the cathode metal current collector. ; the ion exchange membrane is Fumapem AM-40 with a thickness of 120 μm.

[0087] The manufacturing method of the electrochemical oxygen therapy patch provided in this example refers to Example 1, except that the temperature of the physical pressing process is 150 °C, the pressure is 25 MPa, and the time is 2 h.

[0088] Example 14

[0089] This example provides an electrochemical oxygen therapy patch, which includes a flexible anode metal current collector, a composite ion exchange membrane, and a flexible cathode metal current collector stacked in sequence. Among them, the flexible anode metal current collector and the flexible cathode metal current collector are selected from titanium fiber cloth with a thickness of 0.2 mm; the composite ion exchange membrane is loaded with an oxygen evolution catalyst on the side close to the anode metal current collector. and the hydrophilic material polyvinyl alcohol, and the mass of the hydrophilic material is 5% of the mass of the oxygen evolution catalyst; the composite ion exchange membrane is loaded with an oxygen reduction catalyst on the side close to the cathode metal current collector. and the hydrophilic material polyvinyl alcohol, and the mass of the hydrophilic material is 5% of the mass of the oxygen evolution catalyst; the ion exchange membrane is NR212 with a thickness of 200 μm.

[0090] The manufacturing method of the electrochemical oxygen therapy patch provided in this example refers to Example 1, except that the temperature of the physical pressing process is 150 °C, the pressure is 25 MPa, and the time is 2 h.

[0091] Comparative Example 1

[0092] This comparative example provides an electrochemical oxygen therapy patch, which is different from Example 2 in that the flexible anode metal current collector and the flexible cathode metal current collector in Example 2 are replaced with carbon cloth. Other designs of the electrochemical oxygen therapy patch and the manufacturing method of the electrochemical oxygen therapy patch refer to Example 2.

[0093] Comparative Example 2

[0094] In this comparative example, the design of the electrochemical oxygen therapy patch and the manufacturing method of the electrochemical oxygen therapy patch refer to Example 2. The difference is that the pretreated composite ion exchange membrane and two roughened flexible metal current collectors are assembled by the adhesive method, and the adhesive used is conductive copper paste.

[0095] Comparative Example 3

[0096] In this comparative example, the design of the electrochemically oxygenated therapy patch and the manufacturing method of the electrochemically oxygenated therapy patch refer to Example 2. The difference is that in this comparative example, the composite ion exchange membrane is not loaded with a catalyst on either the side close to the anode metal current collector or the side close to the cathode metal current collector.

[0097] The alternating current impedance spectroscopy (EIS) was used to test the impedance of the electrochemically oxygenated therapy patches provided in Example 2 and Comparative Example 1 above. The test results are as Figure 5 shown. By comparing the impedance of the electrochemically oxygenated therapy patch before and after running for 24 hours, it can be clearly seen that after running for 24 hours, the electrochemically oxygenated therapy patch provided in Example 2 is still superior to the initial state of the electrochemically oxygenated therapy patch provided in Comparative Example 1, and the impedance value of the electrochemically oxygenated therapy patch provided in Example 2 does not increase significantly before and after running for 24 hours. However, the impedance value (0.93 Ω) of the electrochemically oxygenated therapy patch provided in Comparative Example 1 is significantly greater than that of Example 2 (0.74 Ω), and the impedance value increases significantly after 24 hours. From Figure 5 this, it can be known that the electrochemically oxygenated therapy patch provided in this example can continuously supply oxygen for a long time, and the oxygen production rate is stable.

[0098] The oxygen production rates of the electrochemically oxygenated therapy patches provided in Examples 1 to 14 and Comparative Examples 1 to 3 were tested, and the test voltage was 1.5 V. The test results are shown in Table 1 in detail. It can be analyzed from Table 1 that the electrochemically oxygenated therapy patches provided in the embodiments of the present disclosure have a higher oxygen production rate.

[0099] The tightness of the electrochemically oxygenated therapy patches provided in Examples 1 to 14 and Comparative Examples 1 to 3 was tested. The rubber tensile test method was used for the test. The length and width of the effective fitting part of the tensile stress sample were 3 * 2.5 cm, and the tensile rate was 500 mm / min. The maximum force value obtained in the experiment was used as the reference standard. The test results are shown in Table 1 in detail.

[0100] Table 1

[0101]

[0102] The oxygen production stability of the electrochemically oxygenated therapy patches provided in Example 2 and Example 5 was tested. Test conditions: constant current 0.2 A, ambient humidity (70 ± 5)%RH. The test results are as Figure 6 shown. From Figure 6 the analysis, it can be known that the electrochemically oxygenated therapy patch provided in Example 5 has a higher catalytic reaction voltage, and real-time water replenishment may be required to keep the voltage around 1.2 V. The electrochemically oxygenated therapy patch provided in Example 2 has a lower catalytic reaction voltage and can be stably around 1.2 V within 100 min, with good stability.

[0103] The rabbit wound repair and healing test was carried out using the electrochemically oxygenated therapy patch (patch group) provided in Example 2 and the control group (clean medical gauze). The damaged skin was the back wound of the rabbit. The treatment method for the experimental group was to first place a clean medical gauze at the rabbit's wound, and then place the electrochemically oxygenated therapy patch on the gauze and fix it. After turning on the power supply, the treatment started. The treatment results are shown in Figures 7 - 9 . Figure 7 are the photos of the rabbit wounds in the patch group and the control group. The blue dotted area is the initial wound area, the black dotted area is the wound area after 5 days of treatment, and the red curve area is the infected area. Figure 8 is the enlarged view of the rabbit wounds in the patch group and the control group after 5 days of treatment, with a magnification of 100 times. Figure 9 is the enlarged view of the rabbit wounds in the patch group and the control group after 5 days of treatment, with a magnification of 400 times. It can be seen from Figure 7 that after 5 days, the healing area of the patch group was about 1.37 cm 2 (more than 70% of the initial wound area), without infection; while the healing area of the control group was much less than 1 cm 2 , and the area of the infected area exceeded 3.5 cm 2 . It can be seen from Figure 8 that the patch group showed significant collagen hyperplasia (blue) and a reduced collagen window, indicating active wound repair; the control group had less collagen hyperplasia and a larger collagen window, representing slow wound repair. It can be seen from Figure 9 that without the use of any antibacterial drugs, the number of inflammatory cells (blue) in the patch group was significantly less than that in the control group, representing effective control of wound infection. In summary, by comparing the wound healing conditions of the patch group and the control group, the wounds treated with the oxygenated therapy patch provided in Example 2 healed normally, while the wounds in the control group had obvious infections and slow healing.

[0104] The specific embodiments described above further illustrate the purpose, technical solutions, and beneficial effects of the present disclosure. It should be understood that the above are only specific embodiments of the present disclosure and are not used to limit the present disclosure. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present disclosure shall be included in the protection scope of the present disclosure.

Claims

1. An electrochemical oxygen therapy patch, characterized in that: The electrochemical oxygen therapy patch comprises a flexible anode metal current collector, a composite ion exchange membrane and a flexible cathode metal current collector which are stacked in sequence; Among them, an oxygen evolution reaction occurs on the anode metal current collector side, and an oxygen reduction reaction occurs on the cathode metal current collector side.

2. The electrochemical oxygen therapy patch according to claim 1, characterized in that: The composite ion exchange membrane is loaded with an oxygen evolution catalyst on a side close to the anode metal current collector, so that an oxygen evolution reaction occurs on the side of the anode metal current collector; The composite ion exchange membrane carries an oxygen reduction catalyst on a side close to the cathode metal current collector, so that an oxygen reduction reaction occurs on the cathode metal current collector side.

3. The electrochemical oxygen therapy patch according to claim 1, characterized in that: The flexible anode metal current collector and the flexible cathode metal current collector are each independently selected from at least one of metal fiber cloth, metal mesh, foam metal, and metal foil; The material of the flexible anode metal current collector and the flexible cathode metal current collector is independently selected from at least one of titanium, platinum, gold, nickel and stainless steel.

4. The electrochemical oxygen therapy patch according to claim 3, characterized in that: The composite ion exchange membrane is loaded with a hydrophilic material on the side close to the anode metal current collector; and / or The composite ion exchange membrane is loaded with a hydrophilic material on a side close to the cathode metal current collector.

5. The electrochemical oxygen therapy patch according to any one of claims 1 to 4, characterized in that: The ion exchange membrane is a proton exchange membrane; The proton exchange membrane is at least one of a fluorosulfonic acid polymer proton membrane and a polybenzimidazole proton membrane.

6. The electrochemical oxygen therapy patch according to any one of claims 1 to 4, characterized in that: The thickness of the flexible anode metal current collector and the flexible cathode metal current collector are both 0.1-0.5 mm; The thickness of the ion exchange membrane is 50 μm to 250 μm.

7. A method for preparing the electrochemical oxygen therapy patch according to any one of claims 1 to 6, characterized in that: The production method comprises: The flexible anode metal current collector, the composite ion exchange membrane and the flexible cathode metal current collector are assembled by a physical pressing process to obtain an electrochemical oxygen therapy patch.

8. The method according to claim 7, characterized in that: The temperature of the physical pressing process is 20-250° C., the pressure is 5-40 MPa, and the pressing time is 5-180 min.

9. A method for using an electrochemical oxygen therapy patch, characterized in that: The method of use includes: The electrochemical oxygen therapy patch according to any one of claims 1 to 6 is placed on the wound and powered on to promote the healing of the wound.

10. The method of use according to claim 9, characterized in that: Disposing water-absorbent and breathable cotton or medical gauze between the wound and the electrochemical oxygen therapy patch; After the power is turned on, the current density of the electrochemical oxygen therapy patch is 10~500A / m 2 .

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