An electrode device, a manufacturing method and applications

Abstract

This application relates to an electrode device, its fabrication method, and its application. The electrode device includes: a conductive current collector, which is a metal square tube structure; a detachable wall body, obtained by cutting one side of the metal square tube structure, wherein the detachable wall body has multiple holes, and the inner wall of the holes is coated with conductive adhesive; a tubular electrode, matching the number of holes, inserted into the holes, wherein the tubular electrode has multiple pores; and a sealing layer, covering the connection between the holes and the tubular electrode and the distal end of the tubular electrode; after the detachable wall body is inserted into the tubular electrode and covered by the sealing layer, it is re-fixed to the conductive current collector by welding. This method effectively integrates the tubular electrode in a highly ordered and rational manner, greatly improving electrochemical conversion efficiency, and is simple in design, easy to operate, and readily scalable.

Description

Technical Field

[0001] This application mainly relates to the field of electrochemical reaction technology, and in particular to an electrode device, its preparation method and application. Background Technology

[0002] Electrochemical reactions at the gas-liquid-solid three-phase interface are highly complex, making the optimized design and construction of the electrode, as a core component of the electrochemical reaction process, extremely important. In existing technologies, porous self-supporting tubular structures represent a novel and ideal electrode configuration for the efficient electrocatalysis of gas-phase reactants. Compared to conventional electrode configurations, porous self-supporting tubular electrode structures significantly enhance the electrochemical reaction kinetics at the electrode interface, optimize mass and charge transfer, and make the electrochemical reaction system suitable for high-efficiency, large-scale electrochemical conversion processes. Furthermore, porous self-supporting tubular electrodes are suitable for large-scale, low-cost, and high-efficiency fabrication, possess a single component, and have a robust and reliable structure, making them suitable for long-term, stable operation of electrochemical conversion processes. Therefore, electrochemical reaction systems constructed based on porous self-supporting tubular electrodes are more readily able to meet the needs of engineering scale-up and industrial production.

[0003] However, existing methods for fabricating and assembling porous self-supporting tubular electrodes are still at the laboratory scale and cannot meet the needs of large-scale production applications. The key to the large-scale engineering application of porous self-supporting tubular electrodes lies in how to fabricate and assemble them into ultra-large area, compact, and practical electrode systems. Summary of the Invention

[0004] One objective of this application is to provide an electrode device, a fabrication method, and an application, thereby addressing the problems of complex assembly schemes and inability to meet the needs of large-scale production applications in the prior art.

[0005] According to one aspect of this application, an electrode device is provided, the electrode device comprising: The conductive current collector has a metal square tube structure; The detachable wall is obtained by cutting one side of the metal square tube structure. The detachable wall has multiple holes, the inner wall of the holes is coated with conductive adhesive, the wall thickness of the detachable wall is 1mm to 10mm, and the drilling depth of the holes is the same as the wall thickness. A tubular electrode, matching the number of holes, is inserted into the holes, and the tubular electrode has multiple pores distributed on it; A sealing layer covers the connection between the hole and the tubular electrode, as well as the distal end of the tubular electrode; After the detachable wall is inserted into the tubular electrode and covered by the sealing layer, it is re-fixed to the conductive current collector by welding.

[0006] Optionally, the conductive current collector includes an inlet located on the end side, through which gaseous reactants are introduced into the conductive current collector and diffused into the electrolyte via multiple pores on the tubular electrode.

[0007] Optionally, the length of the metal square tube structure is 2cm to 60cm, and the inner side length of the cross-section of the metal square tube structure is 1mm to 20mm, and the outer side length is 2mm to 40mm.

[0008] Optionally, the inner diameter of the hole is 0.1mm to 5mm, the holes are arranged in an array, the distance between adjacent holes in the same row is 0.2mm to 5mm, and the distance between adjacent rows is 0.2mm to 5mm.

[0009] Optionally, the diameter of the tubular electrode matches the diameter of the pores, the outer diameter of the tubular electrode is 0.1 mm to 5 mm, the thickness is 100 nm to 300 μm, and the pore diameter is 10 nm to 10 μm.

[0010] Optionally, the tubular electrode is composed of any one or more of conductive metals, metal oxides, metal nitrides, carbon, and metal carbides.

[0011] Optionally, the coverage of the conductive adhesive can be adjusted by adjusting the coating parameters, wherein the coverage is 20% to 50%.

[0012] Optionally, the area of ​​the electrode device is determined by the number and diameter of the tubular electrodes and the exposed length after insertion into the hole.

[0013] According to another aspect of this application, a method for fabricating an electrode device is also provided, the method comprising: A detachable wall is obtained by cutting one side of the conductive current collector, and multiple holes are provided on the detachable wall. The conductive current collector is a metal square tube structure, the wall thickness of the detachable wall is 1mm to 10mm, and the drilling depth of the holes is the same as the wall thickness. Heat the conductive adhesive, apply the adhesive to the outside of the hole, and then blow air to cover the inner wall of the hole with the adhesive. After the conductive adhesive has cured, the tubular electrode is inserted into the hole, wherein the number of the tubular electrode matches the number of the holes and is distributed with multiple pores; A sealing layer is used to seal the connection between the hole and the tubular electrode, as well as the distal end of the tubular electrode. The detachable wall is welded back onto the cut conductive current collector to complete the device fabrication.

[0014] Optionally, the heating conductive adhesive, after being applied to the outside of the hole and then blown with air, includes: The removable wall is installed below the adhesive application device; The three-dimensional coordinates of the hole are obtained through a visual recognition device; Gas is introduced into the coating tank and the purging device respectively, and the conductive adhesive is heated to a preset temperature; Set the glue dispensing time of the glue coating device and the air dispensing time of the blowing device; A batch gluing command is set, and the gluing device and the blowing device are controlled by the controller to execute the batch gluing command, thereby completing the gluing and blowing of the outside of the hole.

[0015] Optionally, the batch adhesive application instruction is executed, and the following steps are repeated until adhesive is applied to all holes: The conductive adhesive is applied to the outer opening of the target hole, and air is blown into the target hole to extend the conductive adhesive to the inner wall of the target hole.

[0016] According to another aspect of this application, an application of the aforementioned electrode device in an electrochemical reaction is also provided, wherein the electrode device is installed in the electrochemical reaction apparatus.

[0017] Optionally, the electrochemical reaction device includes a chamber and a diaphragm, the chamber including an anode chamber and a cathode chamber respectively containing electrolyte, and the diaphragm is used to isolate the anode chamber and the cathode chamber.

[0018] Compared with existing technologies, the electrode device of this application includes: a conductive current collector, which is a metal square tube structure; a detachable wall body, obtained by cutting one side of the metal square tube structure, wherein the detachable wall body has multiple holes, the inner wall of the holes is coated with conductive adhesive, the wall thickness of the detachable wall body is 1mm to 10mm, and the drilling depth of the holes is the same as the wall thickness; a tubular electrode, matching the number of holes, inserted into the holes, wherein the tubular electrode has multiple pores distributed on it; and a sealing layer, covering the connection between the holes and the tubular electrode and the distal end of the tubular electrode; after the detachable wall body is inserted into the tubular electrode and covered by the sealing layer, it is re-fixed to the conductive current collector by welding. This effectively integrates the tubular electrodes in a highly ordered and rational manner, greatly improving the electrochemical conversion efficiency, and is simple in design, easy to operate, and easy to scale up. Attached Figure Description

[0019] To make the above-mentioned objectives, features and advantages of this application more apparent and understandable, the specific embodiments of this application will be described in detail below with reference to the accompanying drawings, wherein: Figure 1 This diagram illustrates a schematic representation of an electrode device structure according to one aspect of this application. Figure 2This diagram illustrates a process flow chart of an electrode device fabrication method provided according to another aspect of this application.

[0020] The same or similar reference numerals in the accompanying drawings represent the same or similar parts. Detailed Implementation

[0021] To make the above-mentioned objectives, features and advantages of this application more apparent and understandable, the specific embodiments of this application will be described in detail below with reference to the accompanying drawings.

[0022] Many specific details are set forth in the following description in order to provide a full understanding of this application. However, this application may also be implemented in other ways different from those described herein, and therefore this application is not limited to the specific embodiments disclosed below.

[0023] As indicated in this application and claims, unless the context clearly indicates otherwise, the words "a," "an," "an," and / or "the" are not specifically singular and may include plural forms. Generally speaking, the terms "comprising" and "including" only indicate the inclusion of explicitly identified steps and elements, which do not constitute an exclusive list, and the method or apparatus may also include other steps or elements.

[0024] Figure 1 This diagram illustrates a schematic structure of an electrode device according to one aspect of this application, the electrode device comprising: The conductive current collector 100 has a metal square tube structure; a detachable wall 101 is obtained by cutting one side of the metal square tube structure, and the detachable wall 101 has multiple holes 102, the inner wall of the holes 102 is coated with conductive adhesive; a tubular electrode 103 is matched with the number of holes 102 and is inserted into the holes 102, and the tubular electrode 103 has multiple pores distributed on it; a sealing layer 104 covers the connection between the holes 102 and the tubular electrode 103 and the distal end of the tubular electrode 103; after the detachable wall 101 is inserted into the tubular electrode 103 and covered by the sealing layer 104, it is re-fixed to the conductive current collector 100 by welding.

[0025] The conductive current collector 100 adopts a metal square tube structure. A side wall of the conductive current collector, from which the electrode is to be inserted, is cut off to form a removable wall 101. Multiple holes 102 arranged in an array are drilled on the surface of this removable wall 101. The metal square tube used is made of one or more conductive materials, including stainless steel, aluminum, copper, and silver.

[0026] Conductive adhesive is sequentially coated on the inner wall of each hole arranged in an array. By using a conductive current collector with a metal square tube structure and cutting one side of the wall for drilling and adhesive application, the repeatability of batch drilling and the accuracy of adhesive application are greatly improved, with virtually no missed coating or misalignment of adhesive application position.

[0027] A tubular electrode 103 of a certain length, matching the diameter of the hole, is inserted into the hole 102 whose inner wall is coated with conductive adhesive. The tubular electrode 103 has multiple pores distributed on it, making it a porous self-supporting tubular electrode. The diameter of the electrode tube is as close as possible to the size of the current collector hole to ensure good contact and conductivity between the electrode and the current collector after insertion.

[0028] The tubular electrode 103 is composed of any one or more of conductive metals, metal oxides, metal nitrides, carbon, and metal carbides. The outer diameter of the tubular electrode is 0.1–5 mm, the wall thickness is 100 nm–300 μm, and the pore size on the inner and outer surfaces and wall is 10 nm–10 μm. This tubular electrode can be formed in a single process to a length of several kilometers, and can be laser-cut into electrodes of various lengths to meet application requirements, assembling them into electrode devices of various sizes.

[0029] After the conductive adhesive has cured, a sealing layer 104 is used to seal the connection between the hole 102 and the tubular electrode 103, as well as the far end of the tubular electrode 103 (i.e. the other end away from the hole 102). When sealing, epoxy resin can be applied to form a sealing layer 104 to isolate air and electrolyte, and prevent corrosion of the metal conduit of the conductive current collector or even short circuit.

[0030] The detachable wall 101, after being coated with adhesive, inserted with electrodes, and sealed with adhesive, is welded to the conductive current collector. The cut wall is then assembled into a whole by welding to ensure conductivity, thus completing the fabrication of a large-area electrode device.

[0031] In one embodiment of this application, the conductive current collector 100 includes an inlet located at the end side, through which gaseous reactants are introduced into the conductive current collector and diffused into the electrolyte via multiple pores on the tubular electrode.

[0032] An inlet 200 for the gaseous reactant is provided at one end of the conductive current collector 100, and the other end is sealed with epoxy resin. The distal end of the tubular electrode 103 is also sealed with epoxy resin, allowing the gaseous reactant to flow through the conductive current collector 100 and then into the narrower tubular electrode 103. This tubular electrode 103 is a porous, self-supporting tubular electrode with a porous array of micron- or nano-sized pores (gas pores) on its electrode wall. (Continue to refer to...) Figure 1300 represents the pores on the surface of the tubular electrode and the gas-solid-liquid three-phase reaction interface; the gaseous reactants diffuse out from the pores on the electrode wall under the drive of internal gas pressure, and interact strongly with the catalytic active sites and electrolyte solution, thereby achieving process intensification and a significant improvement in electrode reaction kinetics.

[0033] In one embodiment of this application, the length of the metal square tube structure is 2cm to 60cm, the inner side length of the cross-section of the metal square tube structure is 1mm to 20mm, the outer side length is 2mm to 40mm, and the wall thickness is 1mm to 10mm. The drilling depth of the hole is the same as the wall thickness.

[0034] The length of a metal square tube structure refers to the overall longitudinal dimension of the square tube. Square tubes with lengths ranging from 2cm to 60cm are selected for ease of processing, reduced splicing requirements, and improved overall stability. The outer side length of the cross-section is the side length of the outer contour of the square tube's cross-section, the inner side length is the side length of the cross-section of the internal cavity of the square tube, and the wall thickness is the thickness of the tube wall. The thickness of the detachable wall section cut along the axial direction (length direction) is the same as the tube wall thickness.

[0035] The drilling depth is the same as the wall thickness of the conductive current collector metal conduit, so that the hole only penetrates the pipe wall and does not enter the internal cavity, thus maintaining the internal seal and preventing leakage or corrosion.

[0036] In one embodiment of this application, the inner diameter of the hole 102 is 0.1mm to 5mm, the holes are arranged in an array, the distance between adjacent holes in the same row is 0.2mm to 5mm, and the distance between adjacent rows is 0.2mm to 5mm.

[0037] For example, the conductive current collector is 190 mm long, with an outer side length of 13 mm, an inner side length of 9 mm, and a wall thickness of 2 mm. 270 holes are drilled 10 mm from one end of the conductive current collector wall, arranged in three rows of 90 holes each. Each hole is a circle with a diameter of 0.6 mm, and the distance between the centers of adjacent holes is 0.5 mm, as is the distance between adjacent rows.

[0038] In one embodiment of this application, the diameter of the tubular electrode matches the diameter of the pore, the outer diameter of the tubular electrode is 0.1 mm to 5 mm, the thickness is 100 nm to 300 μm, and the pore diameter is 10 nm to 10 μm.

[0039] The electrode tube diameter should be matched with the size of the current collector hole, ideally being the same, to ensure good contact and conductivity between the electrode and the current collector after insertion. If the outer diameter of the electrode is less than 0.1 mm, it is prone to bending or breakage; if it is greater than 5 mm, it is unsuitable for micro-hole applications, as fluid flow is obstructed, affecting processing efficiency and quality. A thickness within the range of 100 nm to 300 μm balances the electrode's mechanical strength and fluid permeability. If the thickness is less than 100 nm, the electrode is easily damaged; if it is greater than 300 μm, it increases the electrode weight, affecting accuracy and increasing processing difficulty. The pore diameter of 10 nm to 10 μm is matched to the electrode tube diameter to ensure precise insertion of the electrode into the hole. If the pore diameter is too small (e.g., less than 10 nm), processing is difficult and costly; if the pore diameter is too large (e.g., greater than 10 μm), it cannot effectively adapt to the electrode tube diameter, leading to inaccurate processing.

[0040] As shown in Table 1, several sample examples illustrate the material, length, outer side length, inner side length, as well as the drilling diameter, number of drilling rows, number of holes per row, and total number of holes of the conductive current collector.

[0041] Table 1

[0042] In one embodiment of this application, the coverage of the conductive adhesive is adjusted by adjusting the coating parameters, and the coverage is 20% to 50%.

[0043] A detachable wall with an array of drilled holes is fixed below an adhesive applicator. A certain amount of conductive adhesive is applied to the outer opening of one hole using the applicator. Then, a blowing device is used to blow the adhesive into the hole, using airflow to spread the conductive adhesive onto the inner wall of the hole. The amount of adhesive applied is controlled by adjusting the adhesive dispensing time of the applicator, and the airflow rate is controlled by adjusting the air dispensing time of the blowing device. By adjusting the adhesive application parameters (application amount and airflow rate), the coverage rate of the conductive adhesive on the inner wall of the hole is adjusted to 20%~50%. A coverage rate of at least 20% ensures the formation of a continuous conductive path, while a rate of at least 50% avoids adhesive overflow and cost waste.

[0044] In one embodiment of this application, the area of ​​the electrode device is determined by the number and diameter of the tubular electrodes, as well as the exposed length after insertion into the hole. Here, the construction of a large-area electrode device can be controlled by the arrangement of a porous self-supporting tubular electrode array and the length of the tubular electrodes.

[0045] The number of holes can be adjusted by changing the length and size of the conductive current collector, thus adjusting the number of inserted tubular electrodes, and simultaneously adjusting the length of the tubular electrodes. Using the number of tubular electrodes (n), the exposed length (L) after insertion into the holes, and the electrode diameter (R), the area (S) of the final assembled electrode device can be controlled: S = n × πR × L. Therefore, the electrode area can be expanded from 1 square centimeter to over 50,000 square centimeters, surpassing the area of ​​flat plate electrodes below 1,000 square centimeters in existing technologies.

[0046] As shown in Table 2, several sample examples illustrate the electrode composition, electrode diameter, electrode length, electrode exposed length, and area of ​​the assembled electrode device of the tubular electrode.

[0047] Table 2

[0048] The conductive current collector adopts a square tube structure, and the side wall of the current collector where the electrode is to be inserted through a hole can be cut off, which facilitates the drilling of the hole array and ensures consistency in the drilling direction and parameters. Simultaneously, the consistency of the hole direction and parameters and the light transmittance on the wall of the square tube current collector improve the accuracy of subsequent automatic coating of conductive adhesive and insertion of the porous self-supporting tubular electrode, simplifying the process. The light transmittance of the holes allows for direct visual observation of the amount of adhesive applied, eliminating the need for probes and control plates. After completing the adhesive coating, electrode insertion, and sealing steps, the wall is welded to the square tube current collector. This effectively integrates the porous self-supporting tubular electrode in a highly ordered and rational manner, greatly improving the electrochemical conversion efficiency.

[0049] Figure 2 The diagram illustrates a fabrication method for an electrode device according to another aspect of this application, comprising steps S11 to S15. This method for fabricating the electrode device is applicable to the assembly and large-scale application of various porous self-supporting tubular electrodes, and has broad industrial prospects and value.

[0050] Step S11: Cut one side of the conductive current collector to obtain a detachable wall, and set multiple holes in the detachable wall, wherein the conductive current collector is a metal square tube structure.

[0051] A side wall of the conductive current collector with the electrode to be inserted through a hole is cut off to create a removable wall. Multiple holes arranged in an array are drilled on the surface of this removable wall. The metal conduit of the conductive current collector is made of one or more conductive materials, such as stainless steel, aluminum, copper, or silver. The current collector has a length of 2cm to 60cm, an inner side length of 1mm to 20mm, an outer side length of 2mm to 40mm, and a wall thickness of 1mm to 10mm. The inner diameter of the holes is 0.1mm to 5mm, the distance between two adjacent holes in the same row is 0.2mm to 5mm, and the distance between two adjacent rows of holes is 0.2mm to 5mm.

[0052] In a specific embodiment, the conductive current collector has a length of 190 mm, an outer side length of 13 mm, an inner side length of 9 mm, and a wall thickness of 2 mm. 270 holes are drilled 10 mm from one end of the conductive current collector wall, arranged in three rows of 90 holes each. Each hole is a circle with a diameter of 0.6 mm. The distance between the centers of adjacent holes is 0.5 mm, and the distance between adjacent rows is 0.5 mm. The drilling depth is the same as the wall thickness of the metal conduit of the conductive current collector.

[0053] Step S12: Heat the conductive adhesive, apply the adhesive to the outside of the hole, and then blow air to cover the inner wall of the hole with the adhesive.

[0054] An automated adhesive applicator is used to sequentially apply a certain amount of conductive adhesive to the outer opening of each hole on a removable wall. The automated adhesive applicator includes a controller, a vision recognition device, an adhesive applicator, a blowing device, an auxiliary lighting device, and a temperature control device. After the conductive adhesive is applied, the blowing device blows the adhesive into the hole, using airflow to spread the conductive adhesive onto the inner wall of the hole.

[0055] In one embodiment of this application, in step S12, the detachable wall is installed below the adhesive applicator; the three-dimensional coordinates of the hole are obtained through a visual recognition device; gas is injected into the adhesive applicator and the blowing device respectively, and the conductive adhesive is heated to a preset temperature; the adhesive dispensing time of the adhesive applicator and the air dispensing time of the blowing device are set; a batch adhesive applicator command is set, and the adhesive applicator and the blowing device are controlled by the controller to execute the batch adhesive applicator command to complete the adhesive application and air blowing on the outside of the hole.

[0056] Using a visual recognition device with auxiliary lighting, the controller accurately identifies holes on the removable wall and converts them into three-dimensional spatial coordinates. Based on the set adhesive application parameters, a batch adhesive application command is set, and the controller instructs the adhesive application device and the blowing device to complete the adhesive application operation on the specified coordinates. Specifically, when executing the batch adhesive application command, the following steps are repeated until all holes are coated: the conductive adhesive is applied to the outer opening of the target hole, and air is blown into the target hole to extend the conductive adhesive to the inner wall of the target hole.

[0057] In one specific embodiment of this application, a detachable wall with an array of drilled holes is fixed below the adhesive application device. A visual recognition device, aided by auxiliary lighting, is used by the controller to accurately identify the holes on the wall and convert them into three-dimensional spatial coordinates. The air inlet is opened to fill the adhesive application tank and the blowing device with air. Simultaneously, a temperature control device heats the conductive adhesive to 80°C. The adhesive application time of the adhesive application device is set to 100ms, and the air release time of the blowing device is set to 150ms. A batch adhesive application command is then set. A certain amount of conductive adhesive is applied to the outer opening of the holes using the adhesive application device. The adhesive application head of the adhesive application device is then blown into the holes by the blowing device, using airflow to spread the conductive adhesive onto the inner wall surface of the holes. The controller instructs the adhesive application device and the blowing device to complete the batch adhesive application operation at the specified coordinates.

[0058] The method of using square tube current collectors and cutting one side of the wall for drilling and adhesive application greatly improves the repeatability of batch drilling and the accuracy of adhesive application, virtually eliminating issues such as missed coating or misaligned adhesive application. The cut wall is then welded together to ensure conductivity.

[0059] Step S13: After the conductive adhesive has cured, insert the tubular electrode into the hole, wherein the number of the tubular electrode matches the number of the holes and multiple pores are distributed thereon.

[0060] A porous, self-supporting tubular electrode of a certain length, matching the pore size, is inserted into the current collector array pores coated with conductive adhesive on the inner wall. The electrode tube diameter is as close as possible to the size of the current collector pores to ensure good contact conductivity between the electrode and the current collector after insertion. The porous, self-supporting tubular electrode is composed of one or more conductive metals, metal oxides, metal nitrides, metal carbides, carbon, etc. The outer diameter of the electrode tube is 0.1 mm to 5 mm, the wall thickness is 100 nm to 300 μm, and the pore size on the inner and outer surfaces and the tube wall is 10 nm to 10 μm. The porous, self-supporting tubular electrode can be formed in a single process to a length of several kilometers. Depending on the application scale, it can be laser-cut into electrodes of various lengths and assembled into electrode devices of various sizes.

[0061] Step S14: Seal the connection between the hole and the tubular electrode and the distal end of the tubular electrode using a sealing layer.

[0062] After the conductive adhesive has cured, apply epoxy resin to the connection between the hole and the porous self-supporting tubular electrode, as well as to the other end of the porous self-supporting tubular electrode, to seal it, so as to isolate air and electrolyte and prevent corrosion of the metal conduit of the conductive current collector or even short circuit.

[0063] Step S15: Weld the detachable wall back onto the cut conductive current collector to complete the device fabrication.

[0064] After one side of the conductive current collector is cut, the cut conductive current collector is obtained. The wall that has been coated with glue, inserted with electrodes and sealed with glue is then welded back onto the cut conductive current collector, thus completing the fabrication of a large-area electrode device.

[0065] In one specific embodiment of this application, an Ag porous self-supporting tubular electrode is inserted into the holes of a current collector array coated with conductive adhesive on its inner wall. The electrode tube has a diameter of 0.5 mm, a length of 110 mm, and an exposed length of 100 mm after insertion into the hole. After the conductive adhesive cures, epoxy resin is applied to the connection between the current collector array holes and the porous self-supporting tubular electrode, as well as to the other end of the porous self-supporting tubular electrode, for sealing to isolate air and electrolyte and prevent corrosion of the current collector metal conduit or even short circuit. The wall after adhesive coating, electrode insertion, and sealing is welded to the square tube current collector, completing the fabrication of the large-area electrode device. According to the formula S=n×πR×L, the electrode area is 424 square centimeters.

[0066] The construction of large-area electrode devices can be controlled by the arrangement of porous self-supporting tubular electrode arrays and the electrode length, and the area can reach more than 50,000 square centimeters, which is a qualitative leap compared to the flat electrode area of ​​less than 1,000 square centimeters in the existing technology.

[0067] According to another aspect of this application, an application of the aforementioned electrode device in an electrochemical reaction is also provided, wherein the electrode device is installed in the electrochemical reaction apparatus.

[0068] The electrode device assembled using the aforementioned porous self-supporting tubular electrodes consists of an array of holes drilled into the surface of a current collector metal conduit. Conductive adhesive is automatically and batch-coated onto the inner walls of the array of holes. The porous self-supporting tubular electrodes are then sequentially inserted into and fixed into the holes, thereby installing the resulting large-area porous self-supporting tubular electrode device in an electrochemical reaction apparatus. Due to the porous structure of the tube wall of the porous self-supporting tubular electrode, gaseous reactants enter from the current collector metal conduit and disperse out through the tube wall of the porous self-supporting tubular electrode array, forming an electrochemical reaction at a gas-liquid-solid three-phase interface electrode. This design is simple, easy to operate, and readily scalable.

[0069] Meanwhile, the electrode device was installed in a large-scale electrochemical reaction device and applied to the electrochemical catalytic reaction of gas-phase reactants, realizing high-power operation of the electrochemical catalytic reaction of gas-phase reactants, which is of great significance for the industrial application of porous self-supporting tubular electrodes.

[0070] In one embodiment of this application, the electrochemical reaction device includes a chamber and a diaphragm. The chamber includes an anode chamber and a cathode chamber respectively containing electrolyte. The diaphragm is used to isolate the anode chamber and the cathode chamber.

[0071] The electrochemical reaction device includes an anode chamber and a cathode chamber respectively filled with electrolyte, as well as a diaphragm separating the anode and cathode. It is used for electrochemical catalytic reactions of gaseous reactants such as N2, O2, CO2, CO, CH4, and C2H4. The gaseous reactants enter through one end of a conductive current collector, and the other end is sealed with epoxy resin. The end of the porous self-supporting tubular electrode furthest from the current collector is also sealed with epoxy resin. This allows the gas to flow through the current collector and then into the narrower-diameter porous self-supporting tubular electrode. Driven by internal gas pressure, the gas diffuses out through the micron or nanometer-scale pores on the porous array electrode wall, interacting strongly with the catalytic active sites and the electrolyte solution, thereby achieving process intensification and a significant improvement in electrode reaction kinetics.

[0072] The basic concepts have been described above. Obviously, for those skilled in the art, the above disclosure is merely illustrative and does not constitute a limitation of this application. Although not explicitly stated herein, those skilled in the art may make various modifications, improvements, and corrections to this application. Such modifications, improvements, and corrections are suggested in this application, and therefore remain within the spirit and scope of the exemplary embodiments of this application.

[0073] Furthermore, this application uses specific terms to describe embodiments of the application. For example, "an embodiment," "one embodiment," and / or "some embodiments" refer to a particular feature, structure, or characteristic related to at least one embodiment of the application. Therefore, it should be emphasized and noted that "an embodiment," "one embodiment," or "an alternative embodiment" mentioned twice or more in different locations in this specification do not necessarily refer to the same embodiment. In addition, certain features, structures, or characteristics in one or more embodiments of the application can be appropriately combined.

[0074] In some embodiments, numbers describing the quantity of components and attributes are used. It should be understood that such numbers used in the description of embodiments are modified in some examples with the terms "approximately," "approximately," or "generally." Unless otherwise stated, "approximately," "approximately," or "generally" indicates that the numbers are allowed to vary by ±20%. Accordingly, in some embodiments, the numerical parameters used in the specification and claims are approximate values, which may be changed depending on the characteristics required by individual embodiments. In some embodiments, numerical parameters should take into account specified significant digits and employ a general method of digit reservation. Although the numerical ranges and parameters used to confirm their breadth of scope in some embodiments of this application are approximate values, in specific embodiments, such values ​​are set as precisely as feasible.

Claims

1. An electrode device, characterized by, The electrode device includes: The conductive current collector has a metal square tube structure; The detachable wall is obtained by cutting one side of the metal square tube structure. The detachable wall has multiple holes, the inner wall of the holes is coated with conductive adhesive, the wall thickness of the detachable wall is 1mm to 10mm, and the drilling depth of the holes is the same as the wall thickness. A tubular electrode, matching the number of holes, is inserted into the holes, and the tubular electrode has multiple pores distributed on it; A sealing layer covers the connection between the hole and the tubular electrode, as well as the distal end of the tubular electrode; After the detachable wall is inserted into the tubular electrode and covered by the sealing layer, it is re-fixed to the conductive current collector by welding.

2. The electrode device according to claim 1, characterized in that The conductive current collector includes an inlet located at the end. The gaseous reactants are introduced into the conductive current collector through the inlet and diffuse into the electrolyte through multiple pores on the tubular electrode.

3. The electrode device according to claim 1, characterized in that, The length of the metal square tube structure is 2cm to 60cm, and the inner side length of the cross-section of the metal square tube structure is 1mm to 20mm, and the outer side length is 2mm to 40mm.

4. The electrode device according to claim 1, characterized by The inner diameter of the holes is 0.1mm to 5mm, and the holes are arranged in an array. The distance between adjacent holes in the same row is 0.2mm to 5mm, and the distance between adjacent rows is 0.2mm to 5mm.

5. The electrode device according to claim 1, characterized by The diameter of the tubular electrode matches the diameter of the pores. The outer diameter of the tubular electrode is 0.1 mm to 5 mm, the thickness is 100 nm to 300 μm, and the pore diameter is 10 nm to 10 μm.

6. The electrode device according to claim 1, characterized by The tubular electrode is composed of any one or more of conductive metals, metal oxides, metal nitrides, carbon, and metal carbides.

7. The electrode device according to claim 1, characterized by The coverage of the conductive adhesive is adjusted by adjusting the coating parameters, and the coverage is 20% to 50%.

8. The electrode device according to claim 1, characterized by The area of ​​the electrode device is determined by the number and diameter of the tubular electrodes and the exposed length after insertion into the hole.

9. A method of manufacturing an electrode device, characterized by, The preparation method includes: A detachable wall is obtained by cutting one side of the conductive current collector, and multiple holes are provided on the detachable wall. The conductive current collector is a metal square tube structure, the wall thickness of the detachable wall is 1mm to 10mm, and the drilling depth of the holes is the same as the wall thickness. Heat the conductive adhesive, apply the adhesive to the outside of the hole, and then blow air to cover the inner wall of the hole with the adhesive. After the conductive adhesive has cured, the tubular electrode is inserted into the hole, wherein the number of the tubular electrode matches the number of the holes and is distributed with multiple pores; A sealing layer is used to seal the connection between the hole and the tubular electrode, as well as the distal end of the tubular electrode. The detachable wall is welded back onto the cut conductive current collector to complete the device fabrication.

10. The method of claim 9, wherein, The heated conductive adhesive, after being applied to the outside of the hole and then blown with air, includes: The removable wall is installed below the adhesive application device; The three-dimensional coordinates of the hole are obtained through a visual recognition device; Gas is introduced into the coating tank and the purging device respectively, and the conductive adhesive is heated to a preset temperature; Set the glue dispensing time of the glue coating device and the air dispensing time of the blowing device; A batch gluing command is set, and the gluing device and the blowing device are controlled by the controller to execute the batch gluing command, thereby completing the gluing and blowing of the outside of the hole.

11. The method of claim 10, wherein, Execute the batch adhesive application command and repeat the following steps until all holes are coated with adhesive: The conductive adhesive is applied to the outer opening of the target hole, and air is blown into the target hole to extend the conductive adhesive to the inner wall of the target hole.

12. Use of the electrode device according to any one of claims 1 to 8 in an electrochemical reaction, characterized in that, The electrode device is installed in the electrochemical reaction apparatus.

13. Use according to claim 12, characterized in that, The electrochemical reaction device includes a chamber and a diaphragm. The chamber includes an anode chamber and a cathode chamber, which are respectively filled with electrolyte. The diaphragm is used to isolate the anode chamber and the cathode chamber.

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