A ball type main electrode plate structure for hydrogen production by electrolysis of water and a preparation method thereof

Abstract

The application relates to the technical field of hydrogen production by electrolysis of water, in particular to a ball type main electrode plate structure for hydrogen production by electrolysis of water and a preparation method thereof, which comprises metal balls with surface electroplating treatment, a main electrode plate with a plurality of ball grooves opened on two sides, and a bipolar frame with flow-through holes opened on the top and / or the bottom, the metal balls are a plurality of and respectively flowably laid in the ball grooves, and the metal balls can be discharged or filled through the flow-through holes. The application fills the metal balls with catalytic activity in the ball grooves of the main electrode plate, can greatly improve the contact area between the components, reduce the contact resistance of the internal components of the small chamber, improve the effective catalytic area, promote the flow of the electrolyte in the chamber, greatly improve the electrolysis current density, reduce the energy consumption of hydrogen production by electrolysis of water, simplify the manufacturing process, reduce the manufacturing cost, and after long-time work, the metal balls are discharged and refilled through the flow-through holes, thereby reducing the maintenance cost.

Description

TECHNICAL FIELD

[0001] The application relates to a water electrolysis hydrogen production technology field, in particular to a ball type main electrode plate structure for water electrolysis hydrogen production and a preparation method. BACKGROUND

[0002] At present, among various hydrogen production methods, hydrogen produced by water electrolysis is the highest in purity and is favored, so water electrolysis hydrogen production using an electrolytic tank is considered as the main development direction of future hydrogen production. However, in a typical electrolytic tank structure, the electrolytic tank is usually composed of a tank body, a diaphragm, electrodes (cathode and anode), an electrode plate, a metal mesh and the like. The electrolytic tank is usually connected with multiple electrodes in series and forms independent small chambers. In an independent small chamber of the electrolytic tank, the electrode plate is arranged on both sides of the metal mesh, and the electrode plate is used for conducting electrons, so that the electrolytic current density on the electrode plate is more uniform, the contact resistance between the electrode plate and the metal mesh is reduced, the current density is increased, the hydrogen production energy consumption is reduced, the electrode plate is arranged at both ends of a complete small chamber structure, a cavity for electrolyte flow of the cathode region and the anode region is formed, the cathode electrolyte and the anode electrolyte are separated, the content of hydrogen in oxygen and the content of oxygen in hydrogen are reduced to a certain extent, and the safety of electrolysis operation is ensured.

[0003] Especially in the pressure filtration type electrolytic tank electrolysis chamber, the main electrode plate in the interior is selected to have a main electrode plate with a papillary structure (concave-convex structure) arranged on the surface. The papillary structure enables the electrode plates on both sides of the diaphragm to be in contact with each other through the top end, and forms a cavity and a circulation channel for the electrolyte in the small chamber. Although the number of papillary structures on the papillary type electrode plate and the depth of the papillary structures can be changed to strengthen the heat and mass transfer in the electrolytic tank, balance the liquid concentration and reduce the probability of formation of large bubbles, the number of papillary structures is not the more the better. The increase in the number of papillary structures directly leads to an increase in the stamping cost, and also has an adverse effect on the mechanical strength of the main electrode plate. As for the depth of the papillary structure, the increase in the depth of the papillary structure increases the spacing of the electrolytic tank chamber, so that the overall structure is not compact enough, the resistance of the small chamber is increased, and the tonnage requirement of the stamping machine for manufacturing the papillary structure with large depth is higher, and the cost is higher. Moreover, in the process of long-time discharge of the electrolytic tank, the papillary part on the main electrode plate is easy to be electrochemically corroded at the contact point with the metal mesh, so that the papillary part or even the main electrode plate is broken down, liquid leakage between the small chambers is caused, and if the electrolytic tank body is not disassembled in time and the whole main electrode plate is replaced, the damage of the diaphragm caused by the insufficient number or uneven distribution of the papillary structures leads to the direct contact between the electrodes on both sides, causes a short circuit, reduces the voltage of the small chamber, reduces the gas purity, and thus increases the maintenance cost of the equipment.

[0004] Based on this, the application provides a ball type main electrode plate structure for water electrolysis hydrogen production and a preparation method. SUMMARY

[0005] The application aims to provide a ball type main electrode plate structure for electrolysis of water to produce hydrogen and a preparation method.

[0006] To solve the above technical problems, the application provides a ball type main electrode plate structure for electrolysis of water to produce hydrogen, which comprises metal balls with surface electroplated, a main electrode plate with a plurality of ball grooves opened on two sides, and a bipolar frame with flow-through holes opened on the top and / or bottom, wherein the main electrode plate and the bipolar frame are annular, the main electrode plate is arranged in the bipolar frame coaxially, the metal balls are arranged in the ball grooves in a flowable manner, the metal balls can be discharged or filled through the flow-through holes, the flow-through holes are provided with plugs for sealing, and the bipolar frame is further provided with two exhaust ports and two liquid inlets on the top and bottom respectively.

[0007] Preferably, the ball grooves are square or semicircular in shape.

[0008] Preferably, the ball grooves are arranged in a horizontal and vertical double direction.

[0009] Preferably, the ball grooves are arranged in a vertical direction, the outer periphery of the main electrode plate is provided with an annular groove in communication with the ball grooves on the vertical outer side, and the annular groove is in communication with the flow-through hole.

[0010] Preferably, the metal balls are solid in structure, and the surface thereof is knurled.

[0011] Preferably, one or more through holes are opened on the metal ball, and any one of the through holes passes through the center of the metal ball.

[0012] In another aspect, the application further provides a preparation method of the ball type main electrode plate structure for electrolysis of water to produce hydrogen.

[0013] S1, initial forming of metal balls

[0014] Stainless steel or nickel alloy material is selected as the material for making the metal balls, the material is cut into small pieces on a high-speed upsetting machine, then is pressed into spherical shape in a forging die, and is coarsely ground by a ball mill.

[0015] S2, electroplating of metal balls

[0016] Place a metal mesh at the bottom of the electroplating tank, evenly lay the processed metal balls on the metal mesh after pretreatment, then inject the electrolyte of the metal to be plated, and finally connect the metal mesh to the negative electrode of the power supply for electroplating. The uniformity and thickness of the plating layer are controlled by the applied current and electroplating time.

[0017] S3, processing of main electrode plate

[0018] According to the diameter and number of metal balls, process ball grooves on the double-sided surface of the main electrode plate in a longitudinal or longitudinal and transverse manner. After the ball grooves are processed, the main electrode plate is electroplated with nickel.

[0019] When only longitudinal ball grooves are processed, an annular groove is processed on the outer periphery of the main electrode plate, which communicates with the flow-through hole on the bipolar frame. The annular groove communicates with the ball grooves on the outer side of each longitudinal direction.

[0020] S4, processing of bipolar frame

[0021] Two exhaust ports and two liquid inlets are respectively processed on the top and bottom of the bipolar frame, and a flow-through hole with an inner diameter larger than the diameter of the metal ball is processed on the top and / or bottom of the bipolar frame. A plurality of metal balls are discharged or filled through the flow-through hole.

[0022] S5, assembly of ball type main electrode plate structure

[0023] Weld the bipolar frame and the main electrode plate together. When assembling the metal balls, control the main electrode plate to be horizontal, and evenly spread the metal balls into the ball grooves on one side. Check whether the plug at the flow-through hole meets the sealing requirements, ensure that there is no blockage of metal balls near the flow-through hole, and the metal balls can flow out smoothly from the flow-through hole.

[0024] Then tightly attach the metal mesh to the metal balls, assemble the diaphragm to the outside of the metal mesh and seal it with the bipolar frame through the sealing gasket, and then repeat the above operation to spread the metal balls to the ball grooves on the other side. After the assembly of the metal mesh and the diaphragm is completed, the assembled ball type main electrode plate structure is used for electrolytic water hydrogen production, and multiple stages are connected in series according to the actual electrolytic water hydrogen production.

[0025] Preferably, the S1 selects the processing or non-processing of through holes according to the diameter of the metal balls:

[0026] When no through hole is processed, the surface of the solid structure metal ball is knurled to increase the surface roughness; when one or more through holes are processed, any one of the through holes passes through the center of the ball, promoting the flow of electrolyte and forming a turbulent flow.

[0027] Preferably, the pre-treatment in S2 includes sequentially immersing the metal balls in anhydrous ethanol and acetic acid solution for 15 minutes each, assisted by stirring or ultrasonic vibration, to remove grease, metal residues and oxide film on the surface of the metal balls, and finally drying treatment;

[0028] The metal plating electrolyte is prepared by mixing ammonium chloride and nickel chloride hexahydrate, the deposition current is set to -0.25 Acm-2, the deposition time is 15 min, and after deposition, the product is taken out, washed with ultrapure water and dried.

[0029] Preferably, the processing method of the flow-through hole in S4 is adjusted according to the thickness of the bipolar frame:

[0030] When the thickness of the bipolar frame is greater than twice the diameter of the metal ball, a flow-through hole is bored in the center of the top and / or bottom of the bipolar frame, the depth of the flow-through hole extends to the outermost metal ball of the main plate that can be contacted, and the metal ball can be smoothly discharged from the flow-through hole, the flow-through hole has a stepped hole structure, an internal thread is processed in the stepped hole, a plug is processed with the large hole diameter size of the stepped hole, and the flow-through hole is sealed by the plug;

[0031] When the thickness of the bipolar frame is between one time and two times the diameter of the metal ball, a groove-shaped flow-through hole with a size greater than the diameter of the metal ball is processed on the inner surface of the top and / or bottom of the bipolar frame, the metal ball can be smoothly discharged from the groove-shaped flow-through hole, a plug with the same size as the groove-shaped flow-through hole structure is processed, the plug is combined with a gasket and placed in the groove-shaped flow-through hole, and the bipolar frame is fastened by bolts on both sides to achieve a sealing effect.

[0032] The beneficial effects of the present application are:

[0033] 1. The ball type main plate structure for electrolysis of water to produce hydrogen can solve the defects of high power consumption and high device maintenance cost in the prior art, by filling the main plate ball groove with metal balls with catalytic activity, the contact area between components can be greatly improved, the contact resistance of the internal components of the cell can be reduced, the effective catalytic area can be improved, the flow of electrolyte in the chamber can be promoted, the electrolysis current density is greatly improved, the energy consumption of electrolysis of water to produce hydrogen is reduced, and the preparation method of the ball type main plate structure for electrolysis of water to produce hydrogen simplifies the manufacturing process, reduces the manufacturing cost, and after a long time of work, the metal balls are discharged or refilled through the flow-through hole, which facilitates the maintenance and repair work of the device, and further reduces the maintenance cost of the equipment.

[0034] Specifically, this invention features a design with electroplated metal balls on both sides of the main electrode plate. This design not only enhances the catalytic water decomposition capability during water electrolysis for hydrogen production, but also promotes electrolyte flow and turbulence as the electrolyte flows from the surface and grooves of the metal balls, thus improving the product gas evolution capability. Furthermore, during maintenance, the metal balls in the grooves of the main electrode plate can be quickly removed by removing the plugs and allowed to flow along the grooves to the flow holes for discharge, improving maintenance efficiency and facilitating replacement. If corrosion or material fatigue occurs in the metal balls after prolonged use, only the balls need to be discharged from the flow holes and replaced with new ones. This invention allows operators to discharge or refill the metal balls on both sides of the main electrode plate from the flow holes at the bottom and / or top without completely disassembling the electrolytic cell, without removing the main electrode plate or bipolar frame. This reduces maintenance time and costs, and solves the problem in the prior art where the main electrode plate with a protruding structure requires removal from the bipolar frame during maintenance, and the entire main electrode plate needs to be replaced if problems occur, increasing maintenance time and costs.

[0035] Furthermore, this invention can adapt to electrode meshes of different specifications by adjusting the diameter of the assembled metal balls, making it widely applicable and highly flexible. It solves the problem in the prior art where the nipple structure is formed by stamping with a press, and once the processing is completed, the depth of the nipple cannot be changed, making it difficult to adapt to electrodes of different specifications. Moreover, through the design of the metal balls, it can solve the problem in the prior art where the entire main electrode plate needs to be replaced after the nipple part is corroded. Only the plug needs to be removed to drain and refill the new metal balls from the flow hole, without replacing the main electrode plate, which greatly improves maintenance efficiency and reduces maintenance costs.

[0036] 2. When the diameter of the metal ball of the present invention is less than 1 mm, in order to ensure its own metal strength, through holes can be omitted. Knurling is performed on the surface of the solid metal ball to increase the surface roughness, which can further promote the flow of electrolyte and the formation of turbulence, thereby improving the product gas evolution ability. When the diameter of the metal ball is greater than 1 mm, one or more through holes can be opened on the metal ball. Any one of the through holes passes through the center of the metal ball. Through the design of the through holes, the electrolyte not only passes through the surface of the metal ball, but also passes through the interior of the metal ball, which greatly promotes the flow of electrolyte and the formation of turbulence, thereby improving the product gas evolution ability.

[0037] 3. The design of the longitudinal or transverse bidirectional ball grooves of the present invention facilitates the uniform distribution and smooth flow of metal balls, which can all be collected at the flow hole for discharge, or facilitate the refilling of metal balls from the flow hole to replace damaged metal balls, thereby reducing maintenance costs and improving the service life of the main electrode plate and the electrolytic cell. Attached Figure Description

[0038] In order to more clearly illustrate the technical solutions of the present application, the drawings needed to be used in the embodiments or prior art description will be briefly introduced as follows. Obviously, the drawings in the following description are only some embodiments of the present application, and all other drawings obtained by those skilled in the art without creative efforts based on the drawings belong to the protection scope of the present application.

[0039] Figure 1 is the schematic diagram of the alkaline electrolytic cell structure applied to ultra-short electrode distance of the ball type main electrode plate structure for electrolyzing water to produce hydrogen according to embodiment 1 of the present application;

[0040] Figure 2 is the schematic diagram of the bipolar frame structure according to embodiment 1 of the present application;

[0041] Figure 3 is the schematic diagram of the ball groove of the main electrode plate according to embodiment 1 of the present application;

[0042] Figure 4 is the schematic diagram of the solid structure of the metal ball and the structure of different through holes according to embodiment 1 of the present application;

[0043] In the figure: 1-metal ball, 2-main electrode plate, 3-bipolar frame, 4-plug, 5-electrode net, 6-separator, 7-sealing gasket, 11-through hole, 21-ball groove, 31-flowing hole, 32-exhaust port, 33-liquid inlet, 211-longitudinally distributed ball groove, 212-transversely and longitudinally distributed ball groove. DETAILED DESCRIPTION

[0044] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the present application specification. Obviously, the described embodiments are only some embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present application.

[0045] Embodiment 1

[0046] As Figures 1-4As shown, a ball type main electrode plate structure for hydrogen production by electrolysis of water comprises metal balls 1 with surface electroplated, main electrode plate 2 with a plurality of ball grooves 21 opened on both sides, and bipolar frame 3 with flow-through holes 31 opened on the top and bottom, main electrode plate 2 and bipolar frame 3 are annular, main electrode plate 2 is placed in bipolar frame 3 and coaxially arranged, metal balls 1 are a plurality of and respectively flowably laid in ball grooves 21, metal balls 1 can be discharged or filled through flow-through holes 31, flow-through holes 31 are provided with plugs 4 for sealing, and bipolar frame 3 is further provided with two exhaust ports 32 and two liquid inlets 33 on the top and bottom respectively. Of course, in other embodiments, flow-through holes can be opened only on the top or bottom of bipolar frame 3 according to actual needs.

[0047] The ball type main electrode plate structure for hydrogen production by electrolysis of water can solve the defects of high power consumption and high device maintenance cost in the prior art, by filling metal balls with catalytic activity in the main electrode plate ball groove, the contact area between components can be greatly improved, the contact resistance of the internal components of the small chamber can be reduced, the effective catalytic area can be improved, the flow of electrolyte in the chamber can be promoted, the electrolysis current density is greatly improved, the energy consumption of hydrogen production by electrolysis of water is reduced, the manufacturing process is simplified, the manufacturing cost is reduced, after a long time of work, the metal balls are discharged or refilled through the flow-through hole, which is convenient for the maintenance work of the device, and further reduces the maintenance cost of the equipment;

[0048] Specifically, the metal balls laid on both sides of the main electrode plate are designed by electroplating treatment, which not only improves the ability of catalytic decomposition of water during electrolysis of water to produce hydrogen, but also can flow the metal balls in the ball groove of the main electrode plate to the flow-through hole for discharge by quickly removing the plug during maintenance, which improves the maintenance efficiency of convenient maintenance and replacement, and if the metal balls corrode and the material is fatigued after a long time of use, only the new metal balls need to be discharged from the flow-through hole and filled, the electrolytic cell can be discharged or refilled with metal balls on both sides of the main electrode plate from the flow-through hole at the bottom and / or top without disassembling the main electrode plate or bipolar frame, which solves the problem that the main electrode plate with papillary structure in the prior art needs to be disassembled with the bipolar frame during maintenance, and the entire main electrode plate needs to be replaced when problems occur, which increases the maintenance time and maintenance cost; and when the electrolyte flows from the surface of the metal balls and the ball groove during electrolysis of water to produce hydrogen, the electrolyte flow and turbulent flow are promoted, and the product gas precipitation capacity is improved.

[0049] In addition, the present application can be adapted to different specifications of electrode mesh by adjusting the diameter of the assembled metal balls, has a wide application range and high flexibility, and solves the problem in the prior art that the papilla structure is formed by punching by a punching machine, and once the processing is completed, the depth of the papilla cannot be changed and cannot be well adapted to different specifications of electrodes.

[0050] Specifically, the shape of the ball groove 21 is square or semicircular, the inside of the ball groove 21 can be finished according to actual needs, and simple polishing can be performed if necessary to reduce the roughness of the surface of the ball groove 21, avoid blockage or serious wear on the surface of the metal ball during subsequent filling of the metal ball, and uniformly distribute and smoothly flow the metal balls densely laid on the ball groove 21. The material of the main electrode plate can be selected from stainless steel or nickel alloy. After the ball groove 21 is processed, the whole main electrode plate should be electroplated with nickel, and the nickel plating layer should completely cover the whole main electrode plate.

[0051] Specifically, the plurality of ball grooves 21 are longitudinally or longitudinally and transversely distributed, which can realize the uniform flow of the metal balls in the ball grooves to flow out or re-fill into the flow-through hole. Here, when only longitudinally distributed ball grooves are processed, an annular groove communicating with each longitudinal outer ball groove 21 is provided on the outer periphery of the main electrode plate 2, and the annular groove communicates with the flow-through hole 31 to realize the purpose that the metal balls assembled in each longitudinal ball groove can be collected to flow out at the flow-through hole. In the embodiment, as shown in Figure 3 , the processing schematic diagram of the longitudinally distributed ball groove 211 and the longitudinally and transversely distributed ball groove 212, one of the longitudinally and transversely distributed ball grooves 212 is filled with metal balls. Of course, the main electrode plate is preferably processed into a longitudinally and transversely distributed ball groove structure.

[0052] Specifically, as shown in Figure 4 , when the diameter of the metal ball 1 is less than 1 mm, in order to ensure the metal strength itself, a through hole can not be processed, and knurling can be performed on the surface of the solid structure metal ball to increase the surface roughness, which can further promote the flow and turbulence of the electrolyte and improve the product gas precipitation capacity;

[0053] When the diameter is greater than 1 mm, one or more through holes 11 can be provided on the metal ball 1, and any through hole 11 passes through the center of the metal ball 1. Specifically, it can be a through hole, a cross-shaped hole, or three through holes for strengthening mass transfer under the premise of meeting the mechanical strength of the metal ball. Here, through the design of the through hole, the electrolyte not only passes through the surface of the metal ball, but also passes through the inside of the metal ball, greatly promoting the flow and turbulence of the electrolyte and improving the product gas precipitation capacity.

[0054] In another aspect, the present application also provides a preparation method of a ball-type main electrode plate structure for hydrogen production by water electrolysis, the ball-type main electrode plate structure for hydrogen production by water electrolysis is prepared, and the preparation method comprises the following steps:

[0055] S1, initial forming of metal balls

[0056] Stainless steel or nickel alloy material is selected as the material for manufacturing the metal balls 1, the material is cut into small pieces on a high-speed upsetting machine, and then is pressed into a spherical shape in a forging die, and then is coarsely ground by a ball mill;

[0057] Specifically, when stainless steel material is selected, the metal strength of the metal balls can be increased by quenching after coarse grinding;

[0058] Or, when nickel alloy material is selected, such as Raney nickel material, for example, commonly used W-type Raney nickel, generally 1:1 nickel-aluminum alloy is used, after the metal balls are obtained by cold upsetting, quenching and fine grinding are not needed, in order to ensure the overall structure and mechanical strength of the Raney nickel metal balls in the subsequent use process, without processing through holes, and after being assembled into an electrolytic cell, the aluminum in the alloy is removed by using high-concentration alkali solution (30wt.% NaOH or KOH), finally, the nickel skeleton type metal balls with three-dimensional interconnected porous structure are obtained, which can greatly strengthen the effect of catalytic decomposition of water by the metal balls, and the electrolyte can flow through the porous structure, thereby improving the product gas precipitation capacity;

[0059] S2, electroplating of metal balls

[0060] The metal balls 1 are uniformly laid on a metal mesh placed at the bottom of an electroplating tank after pretreatment, and then an electrolyte to be plated is injected, and finally the metal mesh is connected to the negative electrode of a power supply for electroplating, wherein the uniformity and thickness of the plating layer are controlled by the applied current and electroplating time;

[0061] The pretreatment comprises sequentially immersing the metal balls 1 in anhydrous ethanol and acetic acid solution for 15 minutes respectively, and is assisted by stirring or ultrasonic oscillation, etc., to quickly remove oil, metal residues and oxide film on the surface of the metal balls 1, and finally drying treatment is performed;

[0062] The metal plating electrolyte is prepared by mixing ammonium chloride and nickel chloride hexahydrate, the deposition current of the electroplating is set to -0.25Acm -2 , the deposition time is 15 minutes, and after the deposition is completed, the metal balls are taken out, washed with ultrapure water and dried;

[0063] S3, processing of main electrode plate

[0064] According to the diameter and number of the metal balls 1, the ball grooves 21 are processed on the double-sided surface of the main electrode plate 2 in a longitudinal or transverse longitudinal manner. After the ball grooves 21 are processed, the main electrode plate 2 is subjected to nickel plating treatment.

[0065] When the ball grooves 21 are processed only in the longitudinal direction, an annular groove is processed on the outer periphery of the main electrode plate 2, which is in communication with the flow-through hole 31 on the bipolar frame 3, and the annular groove is in communication with the ball grooves 21 on the longitudinal outer side.

[0066] S4, processing of the bipolar frame

[0067] Two exhaust ports 32 and two liquid inlets 33 are respectively processed on the top and bottom of the bipolar frame 3, and a flow-through hole 31 with an inner diameter larger than the diameter of the metal ball 1 is processed on the top and / or bottom of the bipolar frame 3, and a plurality of metal balls 1 can be discharged or filled through the flow-through hole 31; during the operation of the electrolytic cell, the electrolyte is introduced through the liquid inlet 33, and the hydrogen and oxygen generated after electrolysis are discharged from the two exhaust ports 32, respectively.

[0068] S5, assembly of the ball type main electrode plate structure

[0069] The bipolar frame 3 is welded with the main electrode plate 2, the main electrode plate is controlled to be horizontal during the assembly of the metal balls 1, and the metal balls 1 are uniformly spread into the ball grooves 21 on one side, the plug 4 at the flow-through hole 31 is checked to see if it meets the sealing requirements, and it is ensured that there is no blockage of metal balls 1 near the flow-through hole 31, and the metal balls 1 can flow out smoothly from the flow-through hole 31.

[0070] Then the electrode mesh 5 is tightly attached to the metal balls 1, and the diaphragm 6 is assembled to the outside of the electrode mesh 5 and sealed with the bipolar frame 3 through the sealing gasket 7, and the above operation is repeated to spread the metal balls 1 to the ball grooves 21 on the other side, and after the assembly of the electrode mesh 5 and the diaphragm 6 is completed, the assembled ball type main electrode plate structure is used for electrolytic water hydrogen production, and the actual electrolytic water hydrogen production is carried out in multiple stages in series.

[0071] Specifically, according to the diameter of the metal balls 1, the through holes 11 are processed or not processed: when the through holes are not processed, the surface of the solid metal balls 1 is knurled to increase the surface roughness; when one or more through holes 11 are processed, any one of the through holes 11 passes through the center of the ball, which promotes the flow of electrolyte and forms a turbulent flow.

[0072] Specifically, the processing method of the flow hole 31 is adjusted according to the thickness of the bipolar frame 3: when the thickness of the bipolar frame 3 is greater than twice the diameter of the metal ball 1, a bore hole of the flow hole 31 is bored in the center of the top and / or bottom of the bipolar frame, the depth of the flow hole 31 extends to the outermost metal ball 1 on the main pole plate 2, and the metal ball 1 can be smoothly discharged from the flow hole 31, the flow hole 31 has a stepped hole structure, a thread is processed in the stepped hole, and a plug 4 is processed with the large hole diameter size of the stepped hole, the flow hole is sealed by the plug 4;

[0073] When the thickness of the bipolar frame 3 is between one time and two times the diameter of the metal ball 1, a recessed flow hole 31 with a size greater than the diameter of the metal ball 1 is processed on the inner surface of the top and / or bottom of the bipolar frame 3, the metal ball 1 can be smoothly discharged from the recessed flow hole 31, and a plug 4 with the same structure as the recessed flow hole 31 is processed, is combined with a gasket, and is placed in the recessed flow hole 31, and is fastened by bolts on both sides of the bipolar frame 3 to achieve a sealing effect. The flow hole 31 in the embodiment has a stepped hole structure, as shown in Figure 1

[0074] The above disclosure is only one preferred embodiment of the present application, and of course cannot limit the scope of the present application, so equivalent changes made according to the claims of the present application are still within the scope of the present application.​

Claims

1. A ball-type main electrode plate structure for hydrogen production by electrolysis of water, characterized by, The application relates to a ball-type main electrode plate structure, which comprises metal balls (1) plated on surfaces, a main electrode plate (2) provided with a plurality of ball grooves (21) on two sides, and a bipolar frame (3) provided with flow-through holes (31) on a top and / or a bottom, The main electrode plate (2) and the bipolar frame (3) are annular, the main electrode plate (2) is arranged coaxially in the bipolar frame (3), the metal balls (1) are arranged in the ball grooves (21) in a flowing mode, the metal balls (1) are discharged or filled through the flow-through holes (31), the flow-through holes (31) are provided with plugs (4) for sealing, and the bipolar frame (3) is further provided with two exhaust ports (32) and two liquid inlets (33) on the top and the bottom respectively.

2. A ball-type main electrode plate structure for hydrogen production by electrolysis of water according to claim 1, characterized in that, The ball grooves (21) are square or semicircular in shape.

3. A ball type main electrode plate structure for hydrogen production by electrolysis of water according to claim 1, wherein The ball grooves (21) are arranged in a horizontal and vertical double direction.

4. A ball-type main electrode plate structure for hydrogen production by electrolysis of water according to claim 1, characterized in that, The ball grooves (21) are arranged in a vertical direction, and an annular groove is arranged on the outer periphery of the main electrode plate (2) and is communicated with the ball grooves (21) on the vertical outer side, and the annular groove is communicated with the flow-through holes (31).

5. A ball type main electrode plate structure for hydrogen production by electrolysis of water according to claim 1, wherein The metal balls (1) are solid in structure, and the surfaces of the metal balls (1) are knurled.

6. A ball-type main electrode plate structure for hydrogen production by electrolysis of water according to claim 1, characterized in that, One or more through holes (11) are arranged on the metal balls (1), and any one of the through holes (11) penetrates the ball center of the metal ball (1).

7. A method for producing a ball-type main electrode plate structure for hydrogen production by water electrolysis, the ball-type main electrode plate structure for hydrogen production by water electrolysis according to any one of claims 1 to 6, characterized by, The preparation method comprises the following steps: S1, initial forming of metal balls Stainless steel or nickel alloy material is selected as the material for manufacturing the metal balls (1), the material is cut into small pieces on a high-speed upsetting machine, then the small pieces are pressed into spherical shapes in a forging die, and then the spherical shapes are coarsely ground through a ball mill; S2, electroplating of metal balls A metal mesh is arranged at the bottom of an electroplating tank, the processed metal balls (1) are uniformly laid on the metal mesh after pretreatment, then an electrolyte of a metal to be plated is injected, finally the metal mesh is connected to a negative electrode of a power supply for electroplating, and the uniformity and thickness of a plating layer are controlled by applied current and electroplating time; S3, processing of a main electrode plate According to the diameter and quantity of the metal balls (1), ball grooves (21) are processed on the double sides of the main electrode plate (2) in a vertical or horizontal and vertical direction, the main electrode plate (2) is electroplated with nickel after the ball grooves (21) are processed; When the ball grooves (21) are processed in a vertical direction only, an annular groove is processed on the outer periphery of the main electrode plate (2) and is communicated with the flow-through holes (31) on the bipolar frame (3), and the annular groove is communicated with the ball grooves (21) on the vertical outer side; S4, processing of a bipolar frame Two exhaust ports (32) and two liquid inlets (33) are respectively processed on the top and the bottom of the bipolar frame (3), and flow-through holes (31) with an inner diameter larger than the diameter of the metal balls (1) are processed on the top and / or the bottom of the bipolar frame (3), and the metal balls (1) are discharged or filled through the flow-through holes (31); S5, assembly of a ball-type main electrode plate structure The bipolar frame (3) is welded with the main electrode plate (2) as a whole, the main electrode plate is controlled to be horizontal during assembling the metal ball (1), and the metal ball (1) is evenly laid to the ball groove (21) on one side, the plug (4) at the flow-through hole (31) is checked to see whether it meets the sealing requirement, and it is ensured that there is no blockage of the metal ball (1) near the flow-through hole (31), and the metal ball (1) can flow out of the flow-through hole (31) smoothly; Then the electrode net (5) is tightly attached to the metal ball (1), the diaphragm (6) is assembled to the outside of the electrode net (5) and is sealed with the bipolar frame (3) through the sealing gasket (7), and the metal ball (1) is laid to the ball groove (21) on the other side by repeating the above operation, after the assembly of the electrode net (5) and the diaphragm (6) is completed, the assembled ball type main electrode plate structure is used for electrolytic water hydrogen production, and according to the actual electrolytic water hydrogen production, a multi-stage series connection is carried out.

8. The method of claim 7, wherein the method further comprises the step of: In S1, the through hole (11) is processed or not processed according to the diameter of the metal ball (1): ​ When the through hole is not processed, the surface of the solid structure metal ball (1) is knurled to increase the surface roughness; when one or more through holes (11) are processed, any one of the through holes (11) passes through the center of the ball, promoting the flow of electrolyte and forming a turbulent flow.

9. The method of claim 7, wherein the method further comprises: coating the surface of the main electrode plate with a conductive material. In S2, the pretreatment includes sequentially immersing the metal ball (1) in anhydrous ethanol and acetic acid solution for 15 minutes, assisted by stirring or ultrasonic oscillation, to remove grease, metal residues and oxide film on the surface of the metal ball (1), and finally drying treatment; The plating electrolyte is prepared by mixing ammonium chloride and nickel chloride hexahydrate, and the deposition current is set to -0.25 A cm -2 .

10. The method of claim 7, wherein the method further comprises: In S4, the processing mode of the flow-through hole (31) is adjusted according to the thickness of the bipolar frame (3): When the thickness of the bipolar frame (3) is greater than twice the diameter of the metal ball (1), the flow-through hole (31) is bored at the center of the top and / or bottom of the bipolar frame, the depth of the flow-through hole (31) extends to contact the outermost metal ball (1) on the main electrode plate (2), and the metal ball (1) is smoothly discharged from the flow-through hole (31), the flow-through hole (31) is a stepped hole structure, and internal threads are processed in the stepped hole, and the plug (4) is processed with the large hole diameter size of the stepped hole, and the plug (4) is used to seal the flow-through hole; When the thickness of the bipolar frame (3) is between one time and two times the diameter of the metal ball (1), a groove-shaped flow-through hole (31) with a size greater than the diameter of the metal ball (1) is processed on the inner surface of the top and / or bottom of the bipolar frame (3), the metal ball (1) is smoothly discharged from the groove-shaped flow-through hole (31), a plug (4) with the same structure as the groove-shaped flow-through hole (31) is processed, and the plug (4) is combined with the gasket and placed in the groove-shaped flow-through hole (31), and the bipolar frame (3) is fastened by bolts on both sides to achieve the sealing effect.

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