Electrode plate of electrolysis device, and electrolysis device using same

Abstract

An electrode plate of an electrolysis device, and an electrolysis device using same. The electrolysis device is connected to a direct-current power source, and an electrolyte is injected into the electrolysis device, so as to convert electrical energy into chemical energy. The electrode plate comprises a silicon-based electrode plate made of doped conductive silicon, wherein the silicon-based electrode plate is electrically connected to the direct-current power source, and at least one surface of the silicon-based electrode plate is provided with a flow channel, such that the electrolyte is inputted into the electrolysis device by means of the silicon-based electrode plate, an electrochemical reaction occurs, and a reaction product is outputted. On the basis of maintaining good mechanical supporting and sealing functions, the material and process costs of the electrode plate of the electrolysis device are reduced, the mass transfer rate is improved, the operating voltage of the electrochemical reaction is reduced, and the energy conversion efficiency of the electrochemical reaction is improved.

Description

Electrolytic device and electrolytic device using the same

[0001] This application claims priority from a Chinese patent application filed with the Patent Office of the State Intellectual Property Office of China on August 12, 2023, with application number 2023110128956 and invention name “A plate of an electrolytic device and an electrolytic device using the same”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] The invention belongs to the field of electrolysis, and in particular relates to a pole plate of an electrolysis device. The invention also relates to an electrolysis device using the pole plate. Background Art

[0003] An electrolyzer converts electrical energy into chemical energy. Typical electrolyzers include water electrolysis for hydrogen production. Producing hydrogen through water electrolysis is not only a mature technology but also offers zero carbon emissions, making it a green and sustainable development path. Currently, water electrolysis for hydrogen production has become one of the most important components of hydrogen energy development.

[0004] Specifically, the electrode plate is one of the important key components of the electrolysis device (especially the water electrolysis hydrogen production device), and mainly serves multiple functions such as mechanical support of the main structure of the electrolysis device, sealing the main body, current conduction and distribution, transmission and distribution of reactants and products, transmission and distribution of heat and coolant (if any), etc.

[0005] However, since the electrolysis device, especially the anode side, works in a high temperature and high potential environment, the chemical stability of the material is very high. Most of the current electrolysis device plates are made of metal plates (titanium, nickel, stainless steel and other metal materials), which have poor durability in the electrochemical working environment. In order to improve durability, it is necessary to use expensive and difficult-to-process metal materials, and at the same time, it is necessary to set a precious metal protective coating on the surface of the anode plate, which is expensive and has a cumbersome processing process. In addition, the existing electrolysis device plates are usually made by mechanical processing, and the flow channel structure size processing accuracy on the plate is poor, which will significantly affect the mass transfer rate of the reactants and products in the electrolysis device. At the same time, the surface structure of the plate is simple and the area is relatively small, which affects the reaction rate per unit area in the electrolysis device. At present, no research reports have been found on the use of non-metallic materials as electrode plates in the field of pure electrolytic hydrogen production.

[0006] To this end, this application is based on the follow-up research on electrolysis devices and the knowledge accumulated by the inventor team in silicon-based materials, hoping to seek technical solutions to solve the above technical problems.

[0007] Summary of the Invention

[0008] In view of this, the purpose of the present invention is to propose an electrolytic device electrode plate and an electrolytic device using the same, which significantly reduces the material cost of the electrolytic device electrode plate while maintaining good mechanical support and sealing functions, while reducing the overpotential of the electrochemical reaction to generate reaction products, and increasing the electrolytic reaction rate per unit area in the electrolytic device, thereby effectively reducing the operating voltage at the same electrochemical reaction rate, and ultimately significantly increasing the energy conversion efficiency of the electrochemical reaction.

[0009] The technical solution adopted in the present invention is as follows:

[0010] A plate for an electrolysis device, which is connected to a direct current power supply and injected with an electrolyte to convert electrical energy into chemical energy; the plate is characterized in that it comprises a silicon-based plate made of a doped conductive silicon material; wherein the silicon-based plate is electrically connected to the direct current power supply and has at least one surface provided with a flow channel, so that the electrolyte is input into the electrolysis device through the silicon-based plate, an electrochemical reaction occurs, and a reaction product is output.

[0011] Preferably, the resistivity of the silicon-based plate is not greater than 0.1 ohm-cm, preferably 1-30 milliohm-cm; and / or the silicon-based plate is made of single crystal silicon or polycrystalline silicon material, preferably single crystal silicon material; and / or the thickness of the silicon-based plate is in the range of 0.1-10 mm, preferably 0.2-5 mm.

[0012] It should be noted that the silicon-based plate made of crystalline silicon material (including single crystal silicon or polycrystalline silicon) in the present application has better thermal conductivity than metal, so that it can better conduct and distribute the heat generated in the electrochemical reaction of the electrolysis device used by the silicon-based plate provided by the present application; at the same time, the electrolysis device used by the silicon-based plate provided by the present application has better temperature uniformity, reducing the impact of temperature unevenness on the performance and life of the electrolysis device; in addition, the silicon-based plate can not only produce a fine flow channel structure, but also accurately control the consistency of the silicon-based plate in the flow field structure and surface morphology. In subsequent applications, multiple electrolysis units made based on silicon-based plates will be stacked to obtain a multi-layer electrolysis device. The performance of each electrolysis unit in the multi-layer electrolysis device is more consistent, which is more conducive to the application demand of increasing the number of electrolysis units in the multi-layer electrolysis device, and can further improve the performance and life of the multi-layer electrolysis device.

[0013] Preferably, the flow channel includes a channel structure consisting of staggered grooves and ridges, wherein the width of the groove is 0.2-5 mm, preferably 0.5-1 mm; the width of the ridge is 0.1-10 mm, preferably 0.2-0.4 mm; the height of the ridge is 0.1-5 mm, preferably 0.12-0.5 mm; and / or the flow channel includes porous pores or a velvet structure, the pore size of the porous pores or the characteristic size of the velvet structure is 0.1 μm-1000 μm, preferably 0.3 μm-10 μm.

[0014] Preferably, the channel structure is produced by an alkaline corrosion process or an electrochemical corrosion process; the porous pore structure or velvet structure is produced by a liquid phase method or a gas phase method; wherein preferably, the liquid phase method specifically includes selective corrosion, electrochemical corrosion, catalytic corrosion and other processes; the gas phase method includes plasma etching and other processes; these processes are all well-known processes, and various required channel structures, porous pore structures or velvet structures can be produced according to actual application requirements. While realizing the input of the electrolyte into the electrolysis device, the mass transfer rate of the reaction raw materials and reaction products in the electrochemical reaction and / or the reaction rate on the surface of the silicon-based plate are increased by increasing the effective contact area between the catalyst and the electrolyte on the silicon-based plate.

[0015] Preferably, a catalyst for promoting electrochemical reaction is coated on at least a portion of the flow channel; the catalyst is a metal-based catalyst or a non-metal-based catalyst, preferably an iridium-based catalyst, a platinum-based catalyst, a nickel catalyst or a nickel alloy catalyst.

[0016] Preferably, the area ratio of the flow channel is in the range of 1.2-5, preferably 1.5-3, and more preferably 1.7-2. The area ratio involved in the whole application refers to the ratio of the sum of the surface area of ​​the flow channel exposed to the electrolyte (that is, the area of ​​the corresponding plate in contact with the electrolyte, that is, the effective reaction area of ​​the plate) and the area occupied by the surface of the flow channel in the electrolytic cell. Among them, the "sum of the surface area of ​​the flow channel exposed to the electrolyte" and "the area occupied by the surface of the flow channel in the electrolytic cell" involved in this application can be obtained by scanning the plate with a known scanning electron microscope (SEM) to obtain an SEM image. The surface area of ​​the flow channel exposed to the electrolyte and the area occupied by the surface of the flow channel in the electrolytic cell can be measured respectively by scanning with an electron microscope, thereby obtaining the area ratio of the flow channel.

[0017] Preferably, the polar plate is a bipolar plate; wherein,

[0018] The silicon-based plates are respectively provided with at least an electrolyte connection port, an anode product outlet and a cathode product outlet;

[0019] One surface of the silicon-based plate is provided with an anode flow channel connected to the anode product outlet, and the other surface is provided with a cathode flow channel connected to the cathode product outlet;

[0020] The electrolyte communication port is in communication with the anode flow channel and / or the cathode flow channel.

[0021] Preferably, the plate is a bipolar plate, and the bipolar plate comprises at least a first silicon-based plate and a second silicon-based plate stacked together, wherein:

[0022] Each silicon-based plate is provided with at least an electrolyte connection port, an anode product outlet, a cathode product outlet and a coolant connection port;

[0023] The outer surface of the first silicon-based plate is provided with an anode flow channel connected to the anode product outlet, and the second silicon-based plate is provided with a cathode flow channel connected to the cathode product outlet;

[0024] The electrolyte communication port is in communication with the anode flow channel and / or the cathode flow channel;

[0025] At the same time, a cooling liquid flow channel connected to the cooling liquid communication port is formed between the first silicon base plate and the second silicon base plate.

[0026] Preferably, the electrode plate serves as an end anode plate or an end cathode plate; the end anode plate or the end cathode plate comprises a silicon-based electrode plate made of a doped conductive silicon material, wherein:

[0027] The silicon-based plate is provided with an electrolyte connection port, an anode product outlet or a cathode product outlet;

[0028] One surface of the silicon-based plate is provided with an anode flow channel connected to the anode product outlet or a cathode flow channel connected to the cathode product outlet;

[0029] The electrolyte communication port is communicated with the anode flow channel or the cathode flow channel.

[0030] Preferably, the electrode plate serves as an end anode plate or an end cathode plate; the end anode plate or the end cathode plate comprises at least a first silicon-based electrode plate and a second silicon-based electrode plate stacked as one, each silicon-based electrode plate being made of doped conductive silicon material, wherein:

[0031] Each silicon-based plate is provided with at least an electrolyte connection port, an anode product outlet or a cathode product outlet and a coolant connection port;

[0032] The outer surface of the first silicon-based plate or the second silicon-based plate is provided with an anode flow channel connected to the anode product outlet or a cathode flow channel connected to the cathode product outlet;

[0033] The electrolyte communication port is in communication with the anode flow channel or the cathode flow channel;

[0034] At the same time, a cooling liquid flow channel connected to the cooling liquid communication port is formed between the first silicon base plate and the second silicon base plate.

[0035] Preferably, an electrolysis device is connected to a DC power supply and injected with electrolyte to convert electrical energy into chemical energy, and the electrode plates of the electrolysis device are the electrode plates described above.

[0036] Preferably, the electrolyte is pure water or an alkaline aqueous solution or an acidic aqueous solution, and water is electrolyzed to generate hydrogen and oxygen through an electrochemical reaction.

[0037] Preferably, it includes an anode current collecting plate connected to the positive electrode of a DC power supply, a cathode current collecting plate connected to the negative electrode of a DC power supply, an end anode plate electrically connected to the anode current collecting plate, and an end plate cathode plate electrically connected to the cathode current collecting plate; a diaphragm or a proton exchange membrane or one or more electrolysis units connected in series and / or in parallel is provided between the end anode plate and the end plate cathode plate; the single electrolysis unit includes a bipolar plate and a diaphragm or proton exchange membrane located on both sides of the bipolar plate.

[0038] Preferably, the electrolysis device is made into a standard product, and is assembled into the required electrolysis device module by connecting the DC power supply in series and / or in parallel. When the power supply of the DC power supply is insufficient for all the electrolysis devices to operate, some of the electrolysis devices are selectively stopped, so that the remaining electrolysis devices can perform electrolysis normally.

[0039] Working principle and advantages of the present invention: Before the conception of the present invention was proposed, the applicant discovered that in order to achieve good mechanical support and excellent current conduction, heat conduction and heat distribution, reactant and product distribution and other functions, the prior art generally believed that metal plates (especially carbon steel or titanium plates with a thickness of 2-5 mm are usually preferred) are used as the plates of the water electrolysis device; the applicant surprisingly found that when silicon wafers are used to make electrodes of silicon-based electrolysis devices, while maintaining good mechanical support and sealing functions, due to the abundant silicon material resources and the mature silicon wafer processing technology, the material and process costs of the electrolysis device plates are significantly reduced. It should be noted that the present application proposes to connect the silicon-based plates to a DC power supply and to form the required precision flow channels on the silicon-based plates to form a precise and reliable flow field distribution, thereby improving the mass transfer rate of reactants and products in the electrolysis device, thereby reducing the overpotential of the electrolysis reaction; and the rich surface morphology is formed on the silicon-based plates with flow fields, which can effectively increase the contact area between the electrolyte and the plates, thereby reducing the overpotential of the electrochemical reaction. Because the present invention can reduce the overpotential of electrochemical reactions at multiple levels, it effectively reduces the operating voltage of the electrochemical reaction, ultimately significantly increasing the energy conversion efficiency of the electrochemical reaction. Furthermore, compared to metal-based electrodes in the prior art, the present invention can significantly improve the uniformity of the operating temperature of the electrochemical reaction and the consistency between the units within an electrolysis device composed of multiple electrochemical reaction units, thereby improving the electrolytic performance and lifespan of the electrolysis device. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] FIG1 is a schematic diagram of the bipolar plate structure in Example 1 according to a specific embodiment of the present invention;

[0041] FIG2 is a schematic diagram of the structure of the end anode plate in Example 2 of a specific embodiment of the present invention;

[0042] FIG3 is a schematic diagram of the structure of the end cathode plate in Example 3 of the specific embodiment of the present invention;

[0043] FIG4 is a schematic diagram of the bipolar plate structure in Example 4 of the specific embodiment of the present invention;

[0044] FIG5 is a schematic diagram of the structure of the end anode plate in Example 5 according to a specific embodiment of the present invention;

[0045] FIG6 is a schematic diagram of the structure of the end cathode plate in Example 6 of the specific embodiment of the present invention;

[0046] FIG7 is a schematic diagram of the bipolar plate structure in Example 7 of a specific embodiment of the present invention;

[0047] FIG8 is a schematic diagram of the bipolar plate structure in Example 9 of the specific embodiment of the present invention;

[0048] FIG9 is a schematic diagram of the bipolar plate structure in Example 10 according to a specific embodiment of the present invention;

[0049] FIG10 is a schematic diagram of the plate installation structure of the electrolysis device in Example 14 according to a specific embodiment of the present invention;

[0050] FIG11 is a schematic diagram of the installation structure of the electrolysis device in Example 14 according to a specific embodiment of the present invention;

[0051] FIG12 is a schematic diagram of the electrode plate installation structure in the electrolysis device in Example 15 according to a specific embodiment of the present invention;

[0052] FIG13 is a schematic diagram of the installation structure of the electrolysis device in Example 16 according to a specific embodiment of the present invention;

[0053] FIG14 is a SEM photograph of a suede structure 13 on a silicon-based plate in Example 7 according to a specific embodiment of the present invention;

[0054] FIG. 15 is another SEM photograph of the textured structure 13 on the silicon-based plate in Example 7 according to a specific embodiment of the present invention. DETAILED DESCRIPTION

[0055] An embodiment of the present invention discloses a plate of an electrolysis device, which is connected to a direct current power supply and injected with electrolyte to convert electrical energy into chemical energy; the plate includes a silicon-based plate made of doped conductive silicon material; wherein the silicon-based plate is electrically connected to the direct current power supply and has at least one surface provided with a flow channel (the flow channel is used to transport and distribute the electrolyte or reaction products), so that the electrolyte is input into the electrolysis device through the flow channel on the silicon-based plate to generate an electrochemical reaction and output the reaction product.

[0056] Preferably, in this embodiment, the resistivity of the silicon-based plate is not greater than 0.1 ohm-cm, preferably 1-30 milliohm-cm, more preferably 1-10 milliohm-cm, further preferably 1-5 milliohm-cm, and further preferably 1-3 milliohm-cm; and / or preferably, in this embodiment, the silicon-based plate is made of crystalline silicon (in terms of crystal type: may include single crystal silicon or polycrystalline silicon, etc.; in terms of doping type: may include N-type doped crystalline silicon or P-type doped crystalline silicon) or amorphous silicon material (including metallic silicon), preferably made of single crystal silicon material, more preferably amorphous silicon with a crystal orientation of non- <111> Crystal orientation, specifically <100> Crystal orientation or <110> Crystal orientation or other <111> The crystal orientation has a clear angle, and the most preferred <100> crystal orientation;

[0057] And / or preferably, in this embodiment, the thickness of the silicon-based plate is in the range of 0.1-10 mm, preferably 0.2-5 mm, and more preferably 0.5-2 mm; and / or preferably, in this embodiment, the shape of the silicon-based plate can be square, circular, or other required shapes, and this application does not make any specific implementation restrictions on this. The substrate of the silicon-based plate used in this application can be a silicon wafer obtained by cutting, and can be further chemically polished or mechanically polished to improve the surface flatness, which is beneficial for the subsequent process treatment of the silicon wafer; when implementing this application, the thickness and shape of the silicon-based plate can also be selected according to the dynamic development level of silicon wafer cutting processing technology, and this application does not make any special restrictions within a single range;

[0058] Preferably, in this embodiment, the flow channel comprises a channel structure consisting of staggered grooves and ridges, wherein the width of the groove is 0.2-5 mm, preferably 0.5-1 mm; the width of the ridge is 0.1-10 mm, preferably 0.2-0.4 mm; the height of the ridge (i.e., equivalent to the depth of the groove) is 0.1-5 mm, more preferably 0.1-2 mm, further preferably 0.12-0.5 mm, and further preferably 0.15-0.5 mm, and / or preferably ... The channel includes porous pores or a velvet structure. In actual implementation, the porous pores or the velvet structure can be formed separately on the silicon-based plate, or can be further formed on the surface of the silicon-based plate where the channel structure is located after the channel structure is set. Preferably, in this embodiment, the pore size of the porous pores or the characteristic size of the velvet structure is 0.1 microns to 1000 microns, preferably 0.3 microns to 10 microns; in actual application, the electrolysis device can obtain a plate with a fine flow field structure distribution and a high area ratio surface morphology.

[0059] Preferably, in this embodiment, the channel structure is manufactured by an alkaline etching process or an electrochemical etching process. During implementation, the alkaline etching process can adopt any well-known alkaline etching process or any well-known electrochemical etching process. Further preferably, in this embodiment, it is recommended to use a strong alkaline solution for etching or electrochemical etching for the silicon-based plate made of N-type doped crystalline silicon, and it is recommended to use an electrochemical process for etching for the silicon-based plate made of P-type doped crystalline silicon. Preferably, in this embodiment, the strong alkaline solution can be an organic or inorganic strong alkaline aqueous solution, and the mass concentration of the strong alkaline solution is recommended to be in the range of 10%-50%, preferably a KOH aqueous solution with a mass concentration of 25-35% is used; the etching temperature is 50-120°C, preferably, the etching temperature of the alkaline etching process is 70-85°C; of course, in other embodiments, other methods can also be used to process and manufacture the channel structure required by this embodiment; preferably, in this embodiment, the porous pore structure or velvet structure is manufactured by a liquid phase method or a gas phase method; wherein the liquid phase method includes processes such as selective etching, electrochemical etching, and catalytic etching; the gas phase method includes processes such as plasma etching. In specific implementation, any known silicon wafer texturing process (selective etching in the liquid phase method) can be used to texturize the surface of the silicon-based plate, or any known process (such as vapor deposition) can be used to produce a porous silicon layer (that is, a porous pore structure). Due to the texturing process, the area ratio of the silicon-based plate is increased, and the electrochemical reaction rate per unit area of ​​the plate surface in the electrolysis device is increased, which is not only beneficial to the performance of the electrolysis device, but also reduces the cost of the electrolysis device; and after the porous silicon layer is made on the silicon-based plate, the corresponding surface of the silicon-based plate is formed with a porous pore structure for fluid circulation, which can not only significantly increase the area ratio of the plate, but also is beneficial to the transport flow efficiency of the electrolyte and reaction products (mainly in gaseous form) in the plate flow channel, thereby increasing the electrochemical reaction rate per unit area of ​​the electrolysis device. At the same time, the porous pore structure can also reduce the hydrophobicity and air affinity of the plate, thereby reducing the formation of large bubbles in the flow channel (including the exchange between the reaction raw materials and reaction products in the flow channel, if any), thereby further increasing the electrochemical reaction rate and energy conversion efficiency of the electrolysis device to which it is applied;

[0060] Preferably, in this embodiment, a catalyst for promoting the electrochemical reaction is coated on at least part of the flow channel (specifically, it can be: at least part of the channel structure or at least part of the porous pores or at least part of the velvet structure); the catalyst is a metal-based catalyst or a non-metal-based catalyst, wherein preferably, in this embodiment, the metal-based catalyst includes a noble metal-based catalyst and a non-noble metal-based catalyst, the noble metal-based catalyst is selected from any one or more of Ir, Pt, Pd, Au, Ag, the non-noble metal-based catalyst is selected from any one or more of Fe, Co, Ni, Al, the non-metal-based catalyst is selected from carbon, Materials or carbon composite materials, etc.; It has been confirmed by experiments in this application that in the application of alkaline electrolysis devices, the silicon-based plates are matched with precious metal catalysts, such as Ir and Al alloys, and non-precious metal nickel-based catalysts (that is, catalysts containing nickel Ni components, including nickel catalysts or nickel alloy catalysts). The nickel catalyst can specifically adopt pure electroplated nickel, and the nickel alloy catalyst can adopt high-activity nickel alloy catalysts, such as: Raney nickel, activated nickel sulfide, Ni-Mo alloy or activated NiAl, etc. In actual implementation, the appropriate catalyst is selected according to the specific requirements of cost and / or performance, and this embodiment does not make the sole limitation on this. It has been confirmed by experiments that when the plate provided in the embodiment of the present application is provided with a catalyst layer, in specific applications, a diffusion layer may no longer be provided for the diaphragm or proton exchange membrane, further saving structural costs.

[0061] When implementing this application, any known method can be used to coat the catalyst, and this application does not impose any special restrictions on it. For example, spraying, printing, electroplating, PVD and the like can be used. Specifically, when the catalyst is directly coated on the channel structure, it is recommended to preferably use electroplating, PVD or other integrated deposition coating methods. When the catalyst is coated on a porous structure, it is recommended to preferably use physical coating methods such as spraying and printing.

[0062] Preferably, in this embodiment, the area ratio of the flow channels ranges from 1.2 to 5, more preferably from 1.7 to 2. In practical applications, this can significantly reduce the overpotential required for the electrochemical reaction to occur in the electrolysis device, while increasing the reaction rate per unit area. It should be noted that coating the flow channels in this embodiment with a catalyst can further increase the catalyst's activity, thereby further reducing the overpotential required for the electrochemical reaction and increasing the reaction rate per unit area in the electrolysis device.

[0063] It should be noted that the present application can manufacture different bipolar plates, end anode plates or end cathode plates according to the electrode plate scheme provided in the above embodiment and the specific requirements of the electrolysis device, and this embodiment does not impose the sole limitation on this.

[0064] Preferably, this embodiment proposes an electrolysis device, which is connected to a DC power supply and injected with electrolyte to convert electrical energy into chemical energy, wherein the electrode plates of the electrolysis device adopt the above-mentioned electrode plates.

[0065] Preferably, in this embodiment, the electrolyte is pure water or an alkaline aqueous solution or an acidic aqueous solution, and water is electrolyzed to generate hydrogen and oxygen through an electrochemical reaction; of course, a suitable electrolyte can also be selected according to actual needs to prepare the desired reaction products.

[0066] Preferably, in this embodiment, the electrolysis device includes an anode end plate connected to the positive pole of a DC power supply, a cathode end plate connected to the negative pole of a DC power supply, an end anode plate electrically connected to the anode end plate, and an end plate cathode plate electrically connected to the cathode end plate; a diaphragm or a proton exchange membrane or one or more electrolysis units connected in series and / or in parallel is provided between the end anode plate and the end plate cathode plate; a single electrolysis unit includes a bipolar plate and a diaphragm or proton exchange membrane located on both sides of the bipolar plate.

[0067] It should also be noted that the present application can also apply the electrode plate structure provided in this embodiment to various types of electrolysis devices according to actual needs, including but not limited to: alkaline electrolysis devices (also known as alkaline electrolysis cells), PEM (abbreviation of "Proton Exchange Membrane" in English, corresponding to the Chinese meaning of proton exchange membrane) electrolysis devices (also known as PEM electrolysis cells), and of course, it can also be applied to other types of electrolysis devices with similar needs. These are all conventional application choices that can be made by those skilled in the art according to the scope of the present application, and the embodiments of the present application will no longer list them one by one.

[0068] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0069] Example 1: Please refer to FIG1 , a plate of a water electrolysis device, the plate is a bipolar plate, including a silicon-based plate 10 made of doped conductive silicon material; wherein,

[0070] The silicon-based plate 10 is provided with an electrolyte connection port, an anode product outlet and a cathode product outlet respectively;

[0071] The lower surface of the silicon-based plate 10 is provided with an anode flow channel 11 connected to the anode product outlet, and the upper surface thereof is provided with a cathode flow channel 12 connected to the cathode product outlet;

[0072] The electrolyte connection port is connected to the anode flow channel 11; in other embodiments, as a less preferred embodiment, it can also be selected to be connected to the cathode flow channel 12, or it can be selected to be connected to both the anode flow channel 11 and the cathode flow channel 12 at the same time.

[0073] In the actual production of this embodiment, a 1.5 mm thick, round-shaped, N-type doped single crystal silicon ( <100> A silicon wafer made of a silicon substrate 10 (with a crystal orientation) is used as a substrate of the silicon-based plate 10, and the resistivity is 2.5 milliohm centimeters;

[0074] A 30% KOH aqueous solution was used to selectively etch both surfaces of the silicon wafer to obtain silicon-based plates with channel structures on the upper and lower surfaces, respectively. The channel structure on the upper surface of the silicon-based plate 10 served as the cathode flow channel 12, and the channel structure on the lower surface of the silicon-based plate 10 served as the anode flow channel 11.

[0075] In a specific implementation, the channel structure of the cathode flow channel 12 and the channel structure of the anode flow channel 11 can be set to the same or different sizes; and the channel structure in the same electrode flow channel (for example, the anode flow channel 11 and the cathode flow channel 12) can also be arranged in an alternating pattern of coarse and fine channel units, which can achieve better fluid transport efficiency, thereby increasing the efficiency of the electrochemical reaction and reducing the power consumption of driving the flow of reactants and products in the electrolysis device;

[0076] Among them, in this embodiment, the groove 11a of the channel structure serving as the anode flow channel 11 has a width of 0.8 mm, a depth of 0.2 mm, and a width of the ridge 11b of 0.4 mm. The channel structure serving as the cathode flow channel 12 is the same as the channel structure serving as the anode flow channel 11, and its groove 12a has a width of 0.8 mm, a depth of 0.15 mm, and a width of the ridge 12b of 0.4 mm. The electrolyte connection port, the anode product outlet, and the cathode product outlet are respectively manufactured on the silicon wafer by laser processing or other processes. These two steps can be performed in any order according to actual needs.

[0077] It should be noted that in order to achieve the connection effect between the electrolyte connection port, the anode product outlet and the cathode product outlet and their corresponding flow channels, those skilled in the art will know that it is necessary to make a guide structure at a suitable position on the periphery of the silicon wafer to introduce the electrolyte, the anode product and the cathode product into and out of the electrolysis device from the electrode flow field respectively. Specifically, preferably, the guide structure can be completed together with the channel structure, which will not be explained in detail in this embodiment.

[0078] This embodiment uses a single silicon wafer as the substrate for the silicon-based plate 10. When used in a PEM water electrolysis device, no thin film coating is required on the silicon-based plate. After prolonged electrolysis and hydrogen production, no changes in the plate's electrical, mechanical, or chemical properties were observed. This embodiment achieves cooling by directly connecting the electrolyte to the anode flow channel. Therefore, it is recommended that the electrolyte flow rate be set higher, consuming greater electrolyte drive power.

[0079] Example 2: Please refer to FIG2 , a plate of an electrolysis device, the plate serving as an end anode plate; the end anode plate comprises a silicon-based plate 20 made of doped conductive silicon material, wherein:

[0080] The silicon-based plate 20 is provided with an electrolyte connection port and an anode product outlet;

[0081] The lower surface of the silicon-based plate 20 is provided with an anode flow channel 21 connected to the anode product outlet;

[0082] The electrolyte communication port is communicated with the anode flow channel 21;

[0083] The remaining implementation plans of this Example 2 are the same as those of Example 1.

[0084] Example 3: Please refer to FIG3 , a plate of an electrolysis device, preferably, the plate is used as an end cathode plate; the end cathode plate includes a silicon-based plate 30 made of doped conductive silicon material, wherein:

[0085] The silicon-based plate 30 is provided with an electrolyte connection port and a cathode product outlet;

[0086] The upper surface of the silicon-based plate 30 is provided with a cathode flow channel 31 connected to the cathode product outlet;

[0087] The remaining implementation schemes of this Example 3 are the same as those of Example 1.

[0088] Example 4: As shown in FIG4 , a plate of an electrolysis device is used as a bipolar plate. The bipolar plate includes a first silicon-based plate 41 and a second silicon-based plate 42 stacked together, wherein:

[0089] Each silicon-based plate 41, 42 is provided with an electrolyte connection port, an anode product outlet, a cathode product outlet and a coolant connection port;

[0090] The outer surface of the first silicon-based plate 41 is provided with an anode flow channel 41a connected to the anode product outlet, and the second silicon-based plate 42 is provided with a cathode flow channel 42a connected to the cathode product outlet;

[0091] The electrolyte communication port is connected to the anode flow channel 41a;

[0092] At the same time, a cooling liquid flow channel 43 communicating with the cooling liquid communication port is formed between the first silicon base plate 41 and the second silicon base plate 42;

[0093] The remaining implementation schemes of this embodiment 4 are the same as those of embodiment 1; it should be noted that the coolant connecting port can also be produced by laser technology or other processes. In order to achieve the connection effect between the coolant connecting port and its corresponding coolant flow channel 43, those skilled in the art will know that it is necessary to produce a guide structure at a suitable position on the periphery of the silicon wafer; in this embodiment, the first silicon-based plate 41 and the second silicon-based plate 42 can directly use sealing materials (such as the sealant layer 44 used in this embodiment) to achieve fixed stacking. In other implementation schemes, high-temperature sintering of metal materials can also be performed to achieve a fixed stacking effect.

[0094] The bipolar plate provided in this embodiment is provided with a coolant flow channel 43 (water can be used as the coolant, of course, other suitable coolants can also be used), and the heat generated during the electrochemical reaction is carried away by the coolant flow channel 43; the flow rate of the electrolyte only needs to consider meeting the needs of the electrochemical reaction, so the flow rate of the electrolyte can be set to a lower level, thereby further saving the energy consumed in transporting the electrolyte.

[0095] Example 5: Please refer to FIG5 , a plate of an electrolysis device, the plate serving as an end anode plate; the end anode plate comprises a first silicon-based plate 51 and a second silicon-based plate 52 stacked together, wherein:

[0096] Each silicon-based plate 51, 52 is provided with an electrolyte connection port, an anode product outlet, and a coolant connection port;

[0097] The outer surface of the first silicon-based plate 51 is provided with an anode flow channel 51a connected to the anode product outlet;

[0098] The electrolyte communication port is connected to the anode flow channel 51a;

[0099] At the same time, a cooling liquid flow channel 53 communicating with the cooling liquid communication port is formed between the first silicon base plate 51 and the second silicon base plate 52;

[0100] The remaining implementation plans of this Example 5 are the same as those of Example 4.

[0101] Example 6: Please refer to FIG6 , a plate of an electrolysis device, the plate serving as an end cathode plate; the end cathode plate comprises a first silicon-based plate 61 and a second silicon-based plate 62 stacked together, wherein:

[0102] Each silicon-based plate 61, 62 is provided with an electrolyte connection port, a cathode product outlet, and a coolant connection port;

[0103] The outer surface of the second silicon-based plate 62 is provided with a cathode flow channel 62a connected to the cathode product outlet;

[0104] At the same time, a cooling liquid flow channel 63 communicating with the cooling liquid communication port is formed between the first silicon base plate 61 and the second silicon base plate 62 .

[0105] Example 7: Please refer to Figure 7. The rest of the technical solutions of Example 7 are the same as those of Example 1. The difference is that the upper and lower surfaces of the silicon-based plate 10 with a channel structure are subjected to a velvet process, and a velvet structure 13 is further manufactured on the basis of the channel structure (please further refer to Figures 14 and 15).

[0106] Example 8: The rest of the technical solutions of Example 8 are the same as those of Example 7, except that a porous silicon layer is further manufactured on the suede structure 13 by a vapor phase method.

[0107] Example 9: The rest of the technical solutions of Example 9 are the same as those of Example 7, with the difference being that, as shown in FIG8 , a catalyst layer 14 is further coated on the porous structure 13 , specifically an activated nickel sulfide layer.

[0108] Example 10: The rest of the technical solutions of Example 10 are the same as those of Example 1, with the difference being that, as shown in FIG9 , a porous silicon layer as a porous structure is deposited on two surfaces of the silicon wafer; preferably, in order to facilitate the flow field effect of the porous structure and the mechanical structure stability of the electrode plate, in this embodiment, grooves 71 and 72 are respectively made in advance in the middle areas of the upper and lower surfaces of the silicon wafer (specifically, any known processing technology can be used), and then a porous silicon layer is obtained in the grooves 71 and 72 by a liquid phase method or a gas phase method (not shown in the figure).

[0109] Example 11: The rest of the technical solutions of Example 11 are the same as those of Example 1, except that a catalyst layer is further coated on the channel structure, specifically an activated nickel sulfide layer.

[0110] Example 12: An electrode plate for an electrolytic device, using the end anode plate provided in Example 2, is subjected to a velvet process on the lower surface of a silicon-based electrode plate having a channel structure, and a velvet structure is further produced on the basis of the channel structure, and then a catalyst layer is further coated on the velvet structure, specifically an activated nickel sulfide layer.

[0111] Example 13: An electrode plate of an electrolytic device, using the end cathode plate provided in Example 3, is subjected to a velvet process on the upper surface of a silicon-based electrode plate with a channel structure, and a velvet structure is further produced on the basis of the channel structure, and then a catalyst layer is further coated on the velvet structure, specifically an activated nickel sulfide layer.

[0112] Example 14: An electrolysis device is connected to a DC power supply and injected with electrolyte to convert electrical energy into chemical energy; please refer to Figures 10 and 11, the electrolysis device includes an anode current collecting plate 83a connected to the positive pole of the DC power supply, a cathode current collecting plate 83b connected to the negative pole of the DC power supply, an end anode plate 84 electrically connected to the anode collecting plate 83a, and an end cathode plate 85 electrically connected to the cathode collecting plate 83b; in order to achieve a safe and reliable installation and connection effect, the upper and lower ends of the electrolysis device are further provided with an anode end plate 81 and a cathode end plate 82, respectively, wherein an anode insulating member 81a is provided between the anode end plate 81 and the anode current collecting plate 83a, and a cathode insulating member 82a is provided between the cathode end plate 82 and the cathode current collecting plate 83b to ensure electrical insulation between the anode collecting plate 83a and the cathode collecting plate 83b;

[0113] Among them, the end anode plate 84 of this embodiment adopts the end anode plate provided in Example 2, and the end cathode plate 85 of this embodiment adopts the end cathode plate provided in Example 3; a proton exchange membrane 86 is provided between the end anode plate 84 and the end plate cathode plate 85, and the peripheries of the two are sealed and stacked by a seal 87. In order to further improve working efficiency, an anode diffusion layer 87a and a cathode diffusion layer 87b are further provided on both sides of the proton exchange membrane 86, and an anode catalyst 88a is provided between the anode diffusion layer 87a and the proton exchange membrane 86, and a cathode catalyst 88b is provided between the cathode diffusion layer 87b and the proton exchange membrane 86. Those skilled in the art can combine and apply them according to actual needs;

[0114] Preferably, in this embodiment 14, the electrolyte is pure water, and the water is electrolyzed to generate hydrogen and oxygen through an electrochemical reaction in the electrolysis device, wherein hydrogen is the cathode product and oxygen is the anode product.

[0115] Example 15: Please refer to Figure 12, an electrolysis device, using the end anode plate provided in Example 12 as the end anode plate 91, and the end cathode plate provided in Example 13 as the end cathode plate 92, a diaphragm 93 is arranged between the end anode plate 91 and the end cathode plate 92 (any known diaphragm structure can be used); the electrolyte is a NaOH aqueous solution; and an alkaline electrolysis device is assembled using a known installation method.

[0116] Example 16: The remaining technical solutions of this Example 16 are the same as those of Example 14, as shown in Figure 13. In the electrolysis device provided in this Example 16, an electrolysis unit is provided between the end anode plate 84 and the end plate cathode plate 85; the electrolysis unit includes a bipolar plate 89a (specifically, the bipolar plate provided in Example 1 is used. In other embodiments, the bipolar plate provided in Example 4 can also be used) and a proton exchange membrane 89b located on both sides of the bipolar plate (similarly, a diffusion layer and a catalyst can be further provided on both sides of the proton exchange membrane 89b with reference to Example 14), and a PEM electrolysis device is assembled; in other embodiments, according to actual needs, a diaphragm can be provided on both sides of the bipolar plate; or two or more electrolysis units connected in series and / or in parallel can be provided between the end anode plate and the end plate cathode plate; wherein, when adjacent electrolysis units are connected in series and / or in parallel, a diaphragm or a proton exchange membrane can be shared.

[0117] It should also be noted that in subsequent applications, the electrolysis device provided in Example 16 can be made into a standard product. By connecting a DC power supply in series and / or in parallel, and connecting an electrolyte and cathode generated gas and anode generated gas, various specifications of electrolysis device modules can be assembled. Different electrolysis device systems can be freely and flexibly assembled according to the size of the connected DC power supply. More preferably, when the power supply is insufficient for all electrolysis devices to operate, some electrolysis devices can be selectively stopped so that the remaining electrolysis devices can perform electrolysis normally. It should be noted that "normal electrolysis operation" here means that these remaining electrolysis devices perform electrolysis at the optimal operating point state, wherein the optimal operating point state means that the electrolysis device operates under the optimal operating current density and optimal operating voltage conditions adapted to achieve the highest energy conversion efficiency as the working goal; thereby ensuring that the entire electrolysis device module system produces hydrogen at the highest rate. This electrolysis device system can perform electrolysis at maximum efficiency when powered by intermittent photovoltaic and wind power systems.

[0118] In order to verify the technical effects achieved by this application, the applicant conducted the following tests on Examples 15 and 16:

[0119] The DC power supply voltage is 1.75V per electrolysis unit. The operating temperature range of the electrolysis device is 60-80°C. The operating voltage range of the electrolysis device is 1.5V-2.4V per electrolysis unit.

[0120] The produced hydrogen flow rate was then tested according to the GB / T 19774-2005 standard. The test results are as follows:

[0121] The hydrogen flow rate output in Example 15 is 0.09 Nm 3 / h, the corresponding energy conversion efficiency is: 84.6%;

[0122] The hydrogen flow rate output in Example 16 is 0.2 Nm 3 / h, and the corresponding energy conversion efficiency is: 84.6%.

[0123] It should be particularly pointed out that under the DC power supply voltage condition of 1.75V / each electrolysis unit, the electrolysis device provided in the embodiment of the present application obtains an energy conversion efficiency of 84.6%, which is sufficiently amazing for the field of electrolysis and represents outstanding progress.

[0124] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and range of equivalents of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

[0125] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. An electrode plate of an electrolysis device, wherein the electrolysis device is connected to a DC power supply and injected with an electrolyte to convert electrical energy into chemical energy; characterized in that: The electrode plate includes a silicon-based electrode plate made of doped conductive silicon material; wherein the silicon-based electrode plate is electrically connected to a DC power source, and at least one surface thereof is provided with a flow channel, so that the electrolyte is input into the electrolysis device through the silicon-based electrode plate, an electrochemical reaction occurs, and a reaction product is output.

2. The electrode plate of the electrolysis device according to claim 1, characterized in that: The resistivity of the silicon-based plate is not greater than 0.1 ohm-cm, preferably 1-30 milliohm-cm; and / or the silicon-based plate is made of single crystal silicon or polycrystalline silicon material, preferably single crystal silicon material; and / or the thickness of the silicon-based plate is in the range of 0.1-10 mm, preferably 0.2-5 mm.

3. The electrode plate of the electrolysis device according to claim 1, characterized in that: The flow channel includes a channel structure composed of staggered grooves and ridges, wherein the width of the groove is 0.2-5 mm, preferably 0.5-1 mm; the width of the ridge is 0.1-10 mm, preferably 0.2-0.4 mm; the height of the ridge is 0.1-5 mm, preferably 0.12-0.5 mm; and / or the flow channel includes porous pores or velvet structure, the pore size of the porous pores or the characteristic size of the velvet structure is 0.1 μm-1000 μm, preferably 0.3 μm-10 μm.

4. The electrode plate of the electrolysis device according to claim 3, characterized in that: The channel structure is manufactured by an alkaline corrosion process or an electrochemical corrosion process; the porous pore structure or the velvet structure is manufactured by a liquid phase method or a gas phase method.

5. The electrode plate of the electrolysis device according to claim 1, characterized in that: A catalyst for promoting electrochemical reaction is coated on at least part of the flow channel; the catalyst is a metal-based catalyst or a non-metal-based catalyst, preferably an iridium-based catalyst, a platinum-based catalyst, a nickel catalyst or a nickel alloy catalyst.

6. The electrode plate of the electrolysis device according to claim 1 or 5, characterized in that: The area ratio of the flow channel is in the range of 1.2-5, preferably 1.5-3, and more preferably 1.7-2.

7. The electrode plate according to any one of claims 1 to 6, characterized in that: The polar plate is used as a bipolar plate; wherein, The silicon-based plates are respectively provided with at least an electrolyte connection port, an anode product outlet and a cathode product outlet; One surface of the silicon-based plate is provided with an anode flow channel connected to the anode product outlet, and the other surface is provided with a cathode flow channel connected to the cathode product outlet; The electrolyte communication port is in communication with the anode flow channel and / or the cathode flow channel.

8. The electrode plate according to any one of claims 1 to 6, characterized in that: The plate is a bipolar plate, and the bipolar plate comprises at least a first silicon-based plate and a second silicon-based plate stacked as one, wherein: Each silicon-based plate is respectively provided with at least an electrolyte connection port, an anode product outlet, a cathode product outlet and a coolant connection port; The outer surface of the first silicon-based plate is provided with an anode flow channel connected to the anode product outlet, and the second silicon-based plate is provided with a cathode flow channel connected to the cathode product outlet; The electrolyte communication port is in communication with the anode flow channel and / or the cathode flow channel; At the same time, a cooling liquid flow channel connected to the cooling liquid connecting port is formed between the first silicon-based plate and the second silicon-based plate.

9. The electrode plate according to any one of claims 1 to 6, characterized in that: The electrode plate is used as an end anode plate or an end cathode plate; the end anode plate or the end cathode plate comprises a silicon-based electrode plate made of doped conductive silicon material, wherein: The silicon-based plate is provided with an electrolyte connection port, an anode product outlet or a cathode product outlet; One surface of the silicon-based electrode plate is provided with an anode flow channel connected to the anode product outlet or a cathode flow channel connected to the cathode product outlet; The electrolyte communication port is communicated with the anode flow channel or the cathode flow channel.

10. The electrode plate according to any one of claims 1 to 6, characterized in that: The electrode plate is used as an end anode plate or an end cathode plate; the end anode plate or the end cathode plate comprises at least a first silicon-based electrode plate and a second silicon-based electrode plate stacked as one, each silicon-based electrode plate is made of doped conductive silicon material, wherein: Each silicon-based plate is respectively provided with at least an electrolyte connection port, an anode product outlet or a cathode product outlet and a coolant connection port; The outer surface of the first silicon-based plate or the second silicon-based plate is provided with an anode flow channel connected to the anode product outlet or a cathode flow channel connected to the cathode product outlet; The electrolyte communication port is in communication with the anode flow channel or the cathode flow channel; At the same time, a cooling liquid flow channel connected to the cooling liquid connecting port is formed between the first silicon-based plate and the second silicon-based plate.

11. An electrolysis device, connected to a DC power supply and injected with an electrolyte, converting electrical energy into chemical energy, characterized in that: The electrode plate of the electrolysis device adopts the electrode plate according to any one of claims 1-10.

12. The electrolysis device according to claim 11, characterized in that: The electrolyte is pure water or an alkaline aqueous solution or an acidic aqueous solution, and water is electrolyzed to generate hydrogen and oxygen through an electrochemical reaction.

13. The electrolysis device according to claim 11, characterized in that: It comprises an anode current collecting plate connected to the positive electrode of a DC power supply, a cathode current collecting plate connected to the negative electrode of a DC power supply, an end anode plate electrically connected to the anode current collecting plate, and an end plate cathode plate electrically connected to the cathode current collecting plate; a diaphragm or a proton exchange membrane or one or more electrolytic units connected in series and / or in parallel are arranged between the end anode plate and the end plate cathode plate; the single electrolytic unit comprises a bipolar plate and a diaphragm or a proton exchange membrane located on both sides of the bipolar plate.

14. The electrolysis device according to claim 11, characterized in that: The electrolysis device is made into a standard product, and is assembled into the required electrolysis device module by connecting the DC power supply in series and / or in parallel. When the power supply of the DC power supply is insufficient for all the electrolysis devices to work, some of the electrolysis devices are selectively stopped so that the remaining electrolysis devices can perform electrolysis work normally.

Images