An electrolytic water tubular electrode, an electrolytic water device comprising the same, and uses thereof

Abstract

The present invention belongs to the technical field of electrolyzed water, and particularly relates to an electrolyzed water tubular electrode, an electrolyzed water device comprising the same, and uses thereof. The tubular electrode (10) includes an ion exchange membrane (2), a coaxial hollow inner layer tube (1) and a hollow outer layer tube (3); wherein, the space between the inner layer tube (1) and the outer layer tube (3) is filled with the ion exchange membrane (2); the inner layer tube (1) is an electrolyzed water anode tube, and the outer layer tube (3) is an electrolyzed water cathode tube; or the inner layer tube (1) is an electrolyzed water cathode tube, and the outer layer tube (3) is an electrolyzed water anode tube; the inner layer tube (1) and the outer layer tube (3) are conductive tubes with breathable and water-permeable tube walls. The present invention designs an electrolyzed water device comprising the electrolyzed water tubular electrode, which is convenient to install. A plurality of electrolyzed water tubular electrodes can be arranged side by side therein, and the electrolysis efficiency is high. The diameter of hydrogen gas bubbles in the hydrogen-rich water generated by electrolysis is mainly distributed below 350 nm, and the hydrogen content in the hydrogen-rich water is up to 2.5 ppm at most.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrolyzed water, and particularly relates to an electrolyzed water tubular electrode, an electrolyzed water device comprising the same, and uses thereof. Background Art

[0002] Hydrogen is the smallest and simplest molecule in nature and plays a very important role in life. Hydrogen can neutralize some of the more oxidizing reactive oxygen species in the body. When an aqueous solution rich in micron- or nano-sized hydrogen bubbles enters daily life, a large number of studies have shown that hydrogen-rich water can regulate the activity of oxidative metabolism and has physiological effects such as anti-fatigue, anti-cancer, and anti-inflammatory. Therefore, hydrogen-rich water can not only be used as a new type of drinking water resource, but also is an ideal antioxidant, and can even provide effective help for the prevention and treatment of chronic diseases.

[0003] Therefore, the market application of hydrogen-rich water is gradually expanding, especially for portable hydrogen-rich cups. However, the following problems currently exist:

[0004] 1. The electrolyzed water electrodes in hydrogen-rich cups mostly adopt a stacked sheet structure. Such a structure has a small contact area with the water body and occupies a large space, is not suitable for the free combination and use of multi-electrode structures, has low electrolyzed water efficiency, and the hydrogen concentration in the prepared hydrogen-rich water is not high.

[0005] 2. The hydrogen bubbles generated by existing electrolyzed water electrodes are mostly micron-sized. Micron-sized hydrogen bubbles have low solubility in water and cannot exist stably. If nano-sized hydrogen bubbles can be generated, the hydrogen concentration dissolved in water will increase significantly, and nano-sized hydrogen bubbles can exist stably in water for a long time.

[0006] 3. In addition, the existing sheet-like electrolyzed water electrodes are not suitable for the free combination of multi-electrode structures and are only suitable for use in small devices such as hydrogen-rich cups, and cannot meet the needs of places such as daily life, industry, and agriculture that require a large amount of hydrogen-rich water.

[0007] In order to solve the above problems, the present invention is proposed. Summary of the Invention

[0008] In a first aspect of the present invention, there is provided an electrolyzed water tubular electrode 10, the tubular electrode 10 comprising an ion exchange membrane 2, a coaxial hollow inner tube 1 and a hollow outer tube 3;

[0009] Wherein, the space between the inner tube 1 and the outer tube 3 is filled with the ion exchange membrane 2;

[0010] The inner tube 1 is an electrolyzed water anode tube, and the outer tube 3 is an electrolyzed water cathode tube; or the inner tube 1 is an electrolyzed water cathode tube, and the outer tube 3 is an electrolyzed water anode tube;

[0011] The ion exchange membrane 2 includes a proton exchange membrane or an anion exchange membrane;

[0012] The inner layer tube 1 and the outer layer tube 3 are conductive tubes with breathable and water-permeable tube walls.

[0013] The ion exchange membrane 2 is basically airtight and water-impermeable. When in use, it will be slightly water-permeable and wetted.

[0014] Preferably, the hollow inner layer tube and the hollow outer layer tube are porous conductive tubes, including porous metal tubes or porous carbon tubes.

[0015] Preferably, the tube wall of the inner layer tube 1 has a plurality of first gas production holes 1-1, and the tube wall of the outer layer tube 3 has a plurality of second gas production holes 3-1.

[0016] Preferably, the tubular electrode 10 further includes a hollow insulating breathable support tube arranged coaxially with and inside the inner layer tube 1. The purpose is to discharge the gas generated by electrolyzing water.

[0017] Preferably, the tube wall of the support tube has a plurality of ventilation holes.

[0018] Preferably, one end of the tubular electrode is sealed by an insulating layer, the inner layer tube 1 or the outer layer tube 3.

[0019] In this article, breathable means that as long as it is a material or structure that can achieve the breathable function, for example, the material has microscopic or macroscopic through holes for breathing and water permeation.

[0020] Preferably, the electrolyzed water anode tube is a tubular structure made of any suitable existing material that can be used as an anode in electrolyzing water.

[0021] Preferably, the inner surface and / or the outer surface of the tubular structure of the electrolyzed water anode tube is coated / grown with an electrolyzed water anode catalyst;

[0022] For example, the surface is coated or grown with non-precious metal catalysts such as oxides, hydroxides, carbides, nitrides, sulfides, selenides, phosphides, borides, etc. of elements such as iron, cobalt, nickel, tungsten, molybdenum, copper; or precious metal catalysts such as platinum, ruthenium, iridium, palladium, rhodium, silver and their oxides for the anodic oxygen evolution reaction; the pipe material is a porous conductive material of metal or carbon-based. Here, porous means that the material has microscopic or macroscopic through holes for breathing and water permeation.

[0023] Preferably, the electrolyzed water cathode tube is a tubular structure made of any suitable existing material that can be used as a cathode in electrolyzing water.

[0024] Preferably, the inner surface and / or outer surface of the tubular structure of the electrolyzed water cathode tube is coated / grown with a cathode catalyst; for example, a non-precious metal catalyst such as an oxide, hydroxide, carbide, nitride, sulfide, selenide, phosphide, boride, etc. of elements such as iron, cobalt, nickel, tungsten, molybdenum, copper, etc.; or a noble metal and its oxide catalyst such as platinum, ruthenium, iridium, palladium, rhodium, silver, etc., for the hydrogen evolution reaction at the cathode; the pipe material is a porous conductive material of metal or carbon-based.

[0025] Preferably, the cathode tube is selected from a titanium tube grown with a platinum nanoarray. The anode tube is selected from titanium tubes, such as a tube body made of a titanium sheet, titanium felt, titanium mesh, or titanium foam.

[0026] In the present invention, when the tube body is made of titanium felt, titanium mesh, or titanium foam, since the titanium felt, titanium mesh, or titanium foam has microscopic pores, it is naturally a conductive tube with breathable and water-permeable walls.

[0027] When the tube body is made of a titanium sheet, the tube wall of the tube body has a number of first gas production holes 1-1 or a number of second gas production holes 3-1, making it a conductive tube with breathable and water-permeable walls.

[0028] Here, the gas production holes are used to make the cathode tube / anode tube breathable and water-permeable with the ion exchange membrane, enabling the reaction of electrolyzed water to produce hydrogen / oxygen gas, so they can be called gas production holes.

[0029] Preferably, a porous array electrode is provided on the cathode tube, and the porous array electrode includes:

[0030] A porous conductive substrate and a primary array structure grown on the porous conductive substrate, and each unit of the primary array structure is at least a part of a spherical or ellipsoidal shape; secondary nanostructures in the form of flakes, cones, or spikes radially growing on the surface of each unit of the primary array structure.

[0031] Preferably, the primary array structure and the secondary nanostructures are selected from platinum, ruthenium, iridium, palladium, rhodium, or silver.

[0032] Preferably, both the primary array structure and the secondary nanostructures are platinum.

[0033] Preferably, the preparation method of the porous array electrode includes the following steps:

[0034] (1) Etch the porous conductive substrate with an acidic solution of a certain mass fraction, and then wash it to obtain a porous conductive substrate with a rough structure on the surface;

[0035] (2) In an electrolyte solution of a certain concentration of chloride, configure a soluble platinum solution of a certain concentration to obtain a mixed solution;

[0036] (3) In the mixed solution obtained in step (2), electro-deposition is carried out using a three-electrode system, where the porous conductive substrate obtained in step (1) serves as the working electrode and the saturated calomel electrode serves as the reference electrode; after electro-depositing for a period of time, take it out, wash it, and dry it to obtain the porous array electrode.

[0037] Preferably, in the porous array electrode:

[0038] When the secondary nanostructure is conical or spiky, its length is denoted as H1, and the overall maximum length of the primary array structure and the secondary nanostructure is denoted as H2, and H1 ≤ 1 / 2H2;

[0039] The length of the flaky, conical, or spiky secondary structure is 50 - 800 nanometers, and the width is 50 - 800 nanometers; the thickness of the flaky secondary structure is 4 - 10 nanometers; the maximum distance between the centers of the tops of adjacent conical or spiky secondary nanostructures is greater than 80 nm.

[0040] Preferably, when the secondary nanostructure is conical or spiky, the average distance between the centers of the tops of adjacent secondary nanostructures is in the range of 80 - 200 nm. When the distance is too large, the size of the generated hydrogen bubbles is too large. When the average distance is 80 - 200 nm, hydrogen bubbles in the nanometer size range can be generated.

[0041] The surface of the porous conductive substrate has a rough structure formed by etching; the porous conductive substrate is selected from titanium foam, titanium mesh, titanium felt, or titanium sheet. When the porous conductive substrate is a titanium sheet, the titanium sheet has a number of first gas production holes 1 - 1 or a number of second gas production holes 3 - 1, making the tube formed thereby a conductive tube with a permeable and water-permeable tube wall.

[0042] Preferably, in the preparation method of the porous array electrode:

[0043] The counter electrode in the three-electrode system is a platinum electrode or graphite paper; step (3) further includes the following steps: in an electrolyte solution of nitrate with a certain concentration, a soluble platinum solution with a certain concentration is configured to obtain a second mixed solution; the electro-deposition first electro-deposits in the mixed solution containing chloride salts obtained in step (2) for a period of time, and then deposits in the second mixed solution for a period of time; the electro-deposition is potentiostatic electro-deposition or galvanostatic electro-deposition, the potentiostatic value is -0.4 to -1 V, and the galvanostatic value is -0.4 to -60 mA / cm 2 .

[0044] Preferably, the acidic solution in step (1) is oxalic acid, and the mass fraction is 5% - 50%.

[0045] Preferably, in the mixed solution in step (2), the soluble platinum solution is chloroplatinic acid or potassium chloroplatinate solution, with a concentration of 0.2 - 10 mmol / L, and the concentration of chloride in the mixed solution is 20 - 200 mmol / L.

[0046] Preferably, the reaction in step (3) is carried out in a constant temperature water bath at a temperature of 0 - 90 °C.

[0047] Preferably, the electrodeposition time in step (3) is 3 - 30 min.

[0048] Preferably, the chloride is potassium chloride or sodium chloride.

[0049] In the second aspect of the present invention, an electrolyzed water device capable of generating micro - nano hydrogen - rich water is provided, which includes the electrolytic tubular electrode 10 described in the first aspect.

[0050] Preferably, when the inner tube 1 is an anode tube and the outer tube 3 is a cathode tube, water is outside the outer tube 3 during use.

[0051] The design of the electrolyzed water device is as follows:

[0052] The electrolyzed water device is a hydrogen - rich cup or a hydrogen - rich machine, which includes an electrolysis device base, and on the electrolysis device base are provided: an insulating fixing plate 101 with through - holes and at least one tubular electrode 10 described in the first aspect of the present invention;

[0053] Wherein, each of the tubular electrodes 10 is arranged on the fixing plate 101 with the sealed end facing upwards, and the arrangement is such that all the through - holes on the fixing plate 101 are surrounded inside the anode tube;

[0054] The cup body of the hydrogen - rich cup or the body of the hydrogen - rich machine is connected to the electrolysis device base.

[0055] Preferably, when the inner tube 1 is an anode tube and the outer tube 3 is a cathode tube, water is outside the outer tube 3 during use.

[0056] The design of the electrolyzed water device is as follows:

[0057] The electrolyzed water device is a pipeline for producing hydrogen-rich water, which includes a base of the electrolysis device. On the base of the electrolysis device, there are provided: an insulating fixing plate 101 with through holes and at least one tubular electrode 10 as described in the first aspect of the present invention. Among them, each of the tubular electrodes 10 is arranged on the fixing plate 101 with the sealed end facing upward, and the arrangement is such that all the through holes on the fixing plate 101 are surrounded inside the anode tube, and each anode tube surrounds a through hole. The periphery of the base of the electrolysis device is sealed by the pipe wall, and only a pipe water inlet 20 and a pipe water outlet 21 are provided. The fixing plate 101 itself is a part of the pipe wall.

[0058] Preferably, when the inner tube 1 is a cathode tube and the outer tube 3 is an anode, during use, water is outside the inner tube 1.

[0059] The design of the electrolyzed water device is as follows:

[0060] The electrolyzed water device includes two parallel insulating fixing plates 101 with through holes, at least one tubular electrode 10 as claimed in claim 1, and a cylindrical sealed housing 102. On the cylindrical sealed housing 102, there are provided a water inlet 102-1, a water outlet, and an oxygen outlet 102-2.

[0061] Among them, both ends of each of the tubular electrodes 10 are arranged on the fixing plate 101 and the arrangement is such that all the through holes on the fixing plate 101 are surrounded inside the cathode tube.

[0062] The water inlet 102-1 and the water outlet are both communicated with the through holes.

[0063] The oxygen outlet 102-2 is isolated from the through holes.

[0064] The outer diameter of the fixing plate 101 is equal to the inner diameter of the housing 102.

[0065] The material of the above-mentioned anode tube is any electrolyzed water anode material for existing electrolyzed water.

[0066] The third aspect of the present invention provides a use of an electrolyzed water device that can generate micro-nano hydrogen-rich water, and it can also be used to supply oxygen and oxygen-rich water. That is, the electrolyzed water device can be used to supply hydrogen-rich water, oxygen, and oxygen-rich water simultaneously.

[0067] The purity of the oxygen is greater than 99.99%. The diameter of the hydrogen bubbles in the hydrogen-rich water is mainly distributed below 350 nm. When the placement time reaches 60 minutes, the number of nano-bubbles is mainly concentrated below 200 nm. The hydrogen content in the hydrogen-rich water reaches up to 2.5 ppm at most, and the average hydrogen concentration is 2.1 ppm.

[0068] In addition, the above-mentioned electrolyzed water device can be applied to a hydrogen-rich water machine for human or animal drinking; it can be used in a large-scale hydrogen-rich water device and can be applied to bathing or agricultural irrigation; it can produce hydrogen and be used as a core component in a hydrogen inhalation device, a hydrogen chamber health care device, or a food preservation device such as a refrigerator or a large-scale preservation chamber or preservation room.

[0069] The above-mentioned electrolyzed water device that can supply oxygen can also be used in aquaculture, sewage treatment, or an oxygen inhalation device.

[0070] On the premise of no contradiction, the above-mentioned technical solutions can be freely combined.

[0071] The porous electrode used in the cathode tube of the present invention has the following beneficial effects:

[0072] (1) High hydrogen production efficiency and strong stability. The porous electrode structure of the present invention is obtained for the first time. The surface of the conductive substrate has an arrayed secondary structure. Each unit of the primary array structure is at least a part of a spherical or ellipsoidal shape. This structure can be more firmly combined with the conductive substrate compared with a sheet-like or rod-like structure and is not easily damaged or detached; the secondary nanostructure is a sheet-like, conical, or spiky structure radially growing on the surface of each unit of the primary array structure, which not only increases the specific surface area of the material but also can expose more active sites for electrochemical reactions and improve the efficiency of electrochemical reactions.

[0073] (2) It is easier to generate small-sized or even nano-sized hydrogen bubbles. In order to obtain nano-sized bubbles, the gas evolution reaction needs to quickly detach from the electrode surface and mass transfer to the liquid phase. The overall secondary structure of the porous electrode of the present invention is, for example, spherical flake-shaped or sea urchin-shaped. When used as the cathode material for the hydrogen evolution reaction, this highly ordered array structure can effectively cut the contact area between the electrode surface and the bubbles, resulting in a smaller contact area between the electrode surface and the bubbles, thus showing a very small bubble adhesion force and being conducive to the detachment of the bubbles. In the electrolyzed water hydrogen evolution reaction, the content of nano-sized hydrogen bubbles is as high as 2.5 ppm.

[0074] (3) In a preferred technical solution, the maximum distance between the centers of the tops of adjacent secondary nanostructures on the porous electrode is greater than 80 nm, which makes the formed nano-bubbles not easily contact and fuse with each other, effectively improving the gas hydrophobicity of the electrode surface, enabling the bubbles to detach from the electrode surface at the nano-scale and form nano-bubbles that are soluble in water. The diameters of the hydrogen bubbles in the hydrogen-rich water are mainly distributed below 350 nm. When the placement time reaches 60 minutes, the number of nano-bubbles mainly concentrates below 200 nm. The highest hydrogen content in the hydrogen-rich water reaches 2.5 ppm, and the average hydrogen concentration is 2.1 ppm.

[0075] (4) In the preferred technical solution, the surface of the conductive substrate is etched, so that the platinum electrodeposited in the etched channels is not easily contacted with the outside world, has higher stability and is more difficult to fall off.

[0076] (5) The present invention discovers for the first time that in the preparation method, in the electrodeposition step, electrodeposition is first carried out in a chloride solution for a period of time, and then in a nitrate solution, which will make the spikes more prominent, that is, longer and thicker.

[0077] (6) The present invention discovers for the first time that during constant current deposition, the current is controlled at -0.4 to -60 mA / cm 2 , and during constant potential deposition, the potential is controlled at -0.4 to -1 V, which can accurately maintain the formation of the secondary structure. If it is not within this range, secondary structures such as spherical flakes and sea urchin shapes cannot be obtained.

[0078] (7) In the preferred technical solution, the counter electrode for electrodeposition is made of platinum. During the reaction, the platinum electrode is continuously consumed. Compared with the counter electrode made of non-platinum materials, this can keep the concentration of platinum ions in the electrodeposition mixed solution stable and ensure the stable progress of the electrodeposition effect.

[0079] (8) The synthesis method of the present invention is simple and easy to implement, has high repeatability, and the electrode material is safe and harmless to the human body. The preparation process is simple and is very suitable for industrial scale-up production.

[0080] The electrolytic water tubular electrode of the present invention has the following beneficial effects:

[0081] When the inner tube is a cathode tube and the outer tube is an anode tube, when in use, the water flows inward, and it has the following advantages:

[0082] 1. The electrolysis area of the electrode is greatly increased. And the hydrogen generated by electrolysis mixes with water inside the tube to generate hydrogen-rich water, and the oxygen overflows from the outside of the tubular electrode. It can be used as a core component and combined with various hydrogen-rich water production devices.

[0083] 2. The present invention also designs an electrolysis device including the electrolytic water tubular electrode. The structure is novel and the installation is convenient. A plurality of electrolytic water tubular electrodes can be arranged side by side inside it, and the electrolysis efficiency is high. As long as the outside water flows through the hydrogen-rich water pipe, its outlet water is hydrogen-rich water containing a large amount of hydrogen, and the oxygen generated by electrolysis is also collected and discharged from the oxygen outlet, which can be used to supply hydrogen-rich water, oxygen, and / or oxygen-rich water at the same time. The oxygen-rich water can be used in the aquaculture industry.

[0084] When the inner tube is an anode tube and the outer tube is a cathode tube, when in use, the water flows outward, and it has the following advantages:

[0085] 1. The hydrogen generated by electrolysis mixes with water outside the tube to generate hydrogen-rich water, and the oxygen overflows from the inside of the tubular electrode. It can be used as a core component and combined with various hydrogen-rich water production devices.

[0086] 2. The present invention also designs a hydrogen-rich cup / machine including an electrolytic water tubular electrode. The structure of the hydrogen-rich cup / machine is novel and easy to install. A plurality of electrolytic water tubular electrodes can be arranged side by side inside it, and the electrolysis efficiency is high.

[0087] 3. The present invention also designs a pipeline for producing hydrogen-rich water including an electrolytic water tubular electrode. The structure is novel and easy to install. A large number of electrolytic water tubular electrodes can be arranged side by side inside it, and the electrolysis efficiency is high. As long as external water flows through the pipeline, the water output is hydrogen-rich water containing a large amount of hydrogen. This pipeline can also be connected in series with the daily life washing and bathing water pipes, so that people can use hydrogen-rich water in daily life to play a health care role. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 It is an exploded view of the structure of a single tubular electrode 10 in Example 1.

[0089] Figure 2 It is a schematic perspective view of a single tubular electrode 10 in Example 1.

[0090] Figure 3 It is a schematic perspective view of a single tubular electrode 10 in Example 2.

[0091] Figure 4 It is an exploded view of the structure of the electrolysis device in Example 4.

[0092] Figure 5 It is a schematic external view of the electrolysis device in Example 4.

[0093] Figure 6 It is an exploded view of the structure of the electrolysis device in Example 5.

[0094] Figure 7 It is a schematic external view of the electrolysis device in Example 5.

[0095] Figure 8 It is a schematic view of the base structure of the hydrogen-rich cup electrolysis device in Example 6.

[0096] Figure 9 It is a schematic view of the base structure of the pipeline electrolysis device for producing hydrogen-rich water in Example 7.

[0097] Figure 10 It is a schematic view of the structure before installation of the pipeline for producing hydrogen-rich water in Example 7.

[0098] Figure 11 It is a schematic view of the overall external structure of the pipeline for producing hydrogen-rich water in Example 7.

[0099] Figure 12 It is a scanning electron micrograph of the internal structure of the titanium felt in Example 8.

[0100] Figure 13SEM image of the porous array electrode in Example 8.

[0101] Figure 14 Photograph of the contact angle of the porous array electrode - water droplet in Example 8.

[0102] Figure 15 Photograph of the contact angle of the porous array electrode - air bubble in Example 8.

[0103] Figure 16 Adhesion force curve of the porous array electrode in Example 8.

[0104] Figure 17 SEM image of the etched titanium sheet substrate in Example 9.

[0105] Figure 18 SEM image of the porous array electrode in Example 9.

[0106] Figure 19 Photograph of the contact angle of the porous array electrode - water droplet in Example 9.

[0107] Figure 20 Photograph of the contact angle of the porous array electrode - air bubble in Example 9.

[0108] Figure 21 Adhesion force curve of the porous array electrode in Example 9.

[0109] Figure 22 SEM image of the porous array electrode in Example 10.

[0110] Figure 23 SEM image of the porous array electrode in Example 11.

[0111] Figure 24 SEM image of the porous array electrode in Example 12.

[0112] Figure 25 Histogram of hydrogen bubble size distribution in Example 13.

[0113] Figure 26 Histogram of hydrogen concentration distribution in water in Example 13.

[0114] Figure 27 Histogram of hydrogen bubble size distribution in Example 14.

[0115] Figure 28 Histogram of hydrogen concentration distribution in water in Example 14.

[0116] Figure 29 Histogram of hydrogen bubble size distribution in Example 15.

[0117] Figure 30It is a bar chart of the hydrogen concentration distribution in water in Example 15.

[0118] Figure 31 It is a scanning electron microscope image of the pine-branch-shaped Pt nanoarray material in Comparative Example 1.

[0119] Figure 32 It is the (A) partially enlarged scanning electron microscope image, (B) transmission electron microscope image, (C) high-resolution transmission electron microscope image of the branch-like structure part, and (D) serrated structure on each branch of the pine-branch-shaped Pt nanoarray material in Comparative Example 1.

[0120] List of reference numerals:

[0121] 1. Inner layer tube, 1-1. First gas production hole, 2. Ion exchange membrane, 3. Outer layer tube, 3-1. Second gas production hole, 10. Tubular electrode, 101. Fixed plate, 101-1. Fixed card slot, 102. Sealed housing, 102-1. Water flow inlet, 102-2. Oxygen outlet. 20. Pipeline water flow inlet, 21. Pipeline water flow outlet. Detailed implementation manners

[0122] The content of the present invention will be further described below through specific implementation manners.

[0123] Example 1

[0124] Such as Figure 1 And Figure 2 , an electrolytic water tubular electrode 10 with an internal water flow, the tubular electrode 10 includes a proton exchange membrane 2, a hollow inner layer tube 1 (cathode tube) and a hollow outer layer tube 3 (anode tube) arranged coaxially; the inner layer tube 1 and the outer layer tube 3 are respectively connected to the negative electrode and the positive electrode corresponding to the power supply.

[0125] Wherein, the gap between the cathode tube and the anode tube is completely filled with the proton exchange membrane 2; the tube wall of the inner layer cathode tube has a plurality of first gas production holes 1-1, and the tube wall of the outer layer anode tube has a plurality of second gas production holes 3-1. Both ends of the tubular electrode 10 are open. The porous electrode material prepared in Example 7 is provided on the inner wall of the cathode tube.

[0126] Figure 1 It is an exploded view of the structure of a single tubular electrode 10 in Example 1.

[0127] Figure 2 It is a three-dimensional structure schematic diagram of a single tubular electrode 10 in Example 1.

[0128] Example 2

[0129] Such as Figure 3, An electrolytic water tubular electrode 10 with external water flow, which is only different from that in Embodiment 1 in that: in Embodiment 2, the outer tube 3 is a cathode tube, the inner tube 1 is an anode tube, and one end of the cathode tube is sealed to form the sealed end of the tubular electrode 10. The porous electrode material prepared in Embodiment 8 is provided on the outer wall of the cathode tube.

[0130] Figure 3 It is a schematic three-dimensional structure diagram of a single tubular electrode 10 in Embodiment 2.

[0131] Embodiment 3

[0132] Replace the proton exchange membrane in Embodiment 1 with an anion exchange membrane.

[0133] Embodiment 4

[0134] As Figure 4 and Figure 5 shown, an electrolytic water tubular device capable of generating micro-nano hydrogen-rich water, which includes the electrolytic water tubular electrode 10 with internal water flow described in Embodiment 1.

[0135] To ensure the flexibility of the tubular device of the electrolytic water device, it is only different from that in Embodiment 1 in that the hollow inner tube 1 electrolytic water cathode tube and the hollow outer tube 3 electrolytic water anode tube arranged coaxially are both composed of long and narrow titanium sheets wound around in a rotating manner, with a certain spacing left. The inner tube 1 and the outer tube 3 are respectively connected to the negative electrode and the positive electrode corresponding to the power supply.

[0136] As long as external water flows through the electrolytic water tubular device of this embodiment, its outlet water is hydrogen-rich water containing a large amount of hydrogen, which can be used in a bathing device.

[0137] Figure 4 It is an exploded view of the structure of the electrolytic device in Embodiment 4. Figure 5 It is a schematic external view of the electrolytic device in Embodiment 4.

[0138] Embodiment 5

[0139] As Figure 6 and Figure 7 shown, an electrolytic water device capable of generating micro-nano hydrogen-rich water, which includes the electrolytic water tubular electrode 10 with internal water flow described in Embodiment 1.

[0140] The electrolytic water device includes two parallel insulating fixing plates 101 with 7 through holes, 7 of the tubular electrodes 10, and a cylindrical sealing housing 102. A water inlet 102-1, a water outlet, and an oxygen outlet 102-2 are provided on the cylindrical sealing housing 102;

[0141] Among them, both ends of each of the tubular electrodes 10 are arranged on the fixing plate 101 and are arranged in such a way that: each end of each of the cathode tubes surrounds one of the through holes;

[0142] The water inlet 102-1 and the water outlet are symmetrically arranged with respect to the water inlet 102-1, Figure 6 which are not shown but are all communicated with the through hole;

[0143] The oxygen outlet 102-2 is isolated from the through hole;

[0144] The outer diameter of the fixing plate 101 is equal to the inner diameter of the outer shell 102.

[0145] The fixing plate 101 is provided with a fixing card slot 101-1, the tubular electrode 10 is installed on the fixing card slot 101-1, and positive and negative power supply interfaces are arranged in the fixing card slot 101-1.

[0146] Moreover, the water inlet 102-1 and the water outlet are only communicated with the through hole, and the outer diameter of the fixing plate 101 is equal to the inner diameter of the outer shell 102, so as to ensure that the water flow is blocked by the fixing plate 101 and can only flow inside the tubular electrode 10. The space between the outside of the tubular electrode 10 and the outer shell 102 is filled with oxygen, and an oxygen outlet 102-2 is provided in this space.

[0147] The tubular electrode 10 and two parallel insulating fixing plates 101 with seven through holes can be integrally designed. The cylindrical sealed outer shell 102 includes a lid with the water inlet 102-1, and the lid is detachably connected to the main body of the cylindrical sealed outer shell 102. This also facilitates the insertion of the tubular electrode 10.

[0148] The fixing plate 101 is provided with fixing card slots 101-1 equal in number to the tubular electrodes 10. The tubular electrodes 10 are installed on the fixing card slots 101-1. The fixing card slots are used for conducting electricity. Each fixing card slot 101-1 is divided into an anode card slot section and a cathode card slot section, and positive and negative power supply interfaces are respectively arranged. The positive and negative power supply interfaces are electrically connected to the cathode tube and the anode tube respectively. Any suitable existing connection method can be used for the specific connection method here.

[0149] As long as external water flows through the electrolyzed water device of this embodiment, the outlet water is hydrogen-rich water containing a large amount of hydrogen, and the oxygen generated by electrolysis is also collected and discharged from the oxygen outlet 102-2, which can be used for supplying hydrogen-rich water and oxygen at the same time.

[0150] Figure 6 It is an exploded view of the structure of the electrolysis device in Embodiment 5.

[0151] Figure 7 It is a schematic view of the appearance of the electrolysis device in Embodiment 5.

[0152] Embodiment 6

[0153] As Figure 8 , a hydrogen-rich cup capable of generating micro-nano hydrogen-rich water, which comprises an electrolysis device base, and is provided on the electrolysis device base: an insulating fixing plate 101 having through holes (not shown) and the tubular electrode 10 described in Embodiment 2.

[0154] The number of the through holes is 7. The number of the tubular electrodes 10 is 7.

[0155] Wherein, each of the tubular electrodes 10 is arranged on the fixing plate 101 with the sealed end facing upward, and is arranged in such a way that each through hole on the fixing plate 101 is surrounded inside each of the anode tubes; the cup body of the hydrogen-rich cup is detachably connected to the electrolysis device base and is arranged above the electrolysis device base.

[0156] The fixing plate 101 has fixing card slots 101-1 equal in number to the tubular electrodes 10. The tubular electrodes 10 are installed on the fixing card slots 101-1. The fixing card slots are used for conducting electricity. Each of the fixing card slots 101-1 is divided into an anode card slot section and a cathode card slot section, and positive and negative power supply interfaces are respectively arranged. The positive and negative power supply interfaces are electrically connected to the anode tube and the cathode tube respectively.

[0157] Figure 8 It is a schematic structural diagram of the electrolysis device base of the hydrogen-rich cup in Embodiment 6. The cup body of the hydrogen-rich cup or the body of the hydrogen-rich machine is connected to the electrolysis device base. The connection method can use any suitable existing connection method, and no schematic diagram is provided.

[0158] Embodiment 7

[0159] As Figures 9 - 11 , a pipeline for producing hydrogen-rich water, which comprises an electrolysis device base, and is provided on the electrolysis device base: an insulating fixing plate 101 having through holes and the tubular electrode 10 described in Embodiment 2; the number of the through holes is the same as the number of the tubular electrodes 10.

[0160] Wherein, each of the tubular electrodes 10 is arranged on the fixing plate 101 with the sealed end facing upward, and is arranged in such a way that each through hole on the fixing plate 101 is surrounded inside each anode tube. The periphery of the electrolysis device base is sealed by the pipe wall of the pipeline, and only a pipeline water inlet 20 and a pipeline water outlet 21 (the same size as the pipeline water inlet 20, not shown in the figure) are provided. The fixing plate 101 itself is a part of the pipe wall of the pipeline.

[0161] The fixing plate 101 has a fixing slot 101-1, the tubular electrode 10 is mounted on the fixing slot 101-1, the fixing slot 101-1 is provided with positive and negative power supply interfaces, and the positive and negative power supply interfaces are electrically connected to the anode tube and the cathode tube respectively. As long as the external water flows through the pipeline of this embodiment, the water outflow is hydrogen-rich water containing a large amount of hydrogen.

[0162] Figure 9 This is a schematic diagram of the base structure of the pipeline electrolysis device for producing hydrogen-rich water in Example 7. Figure 10 This is a schematic diagram of the structure of the pipeline for producing hydrogen-rich water in Example 7 before installation. Figure 11 This is a schematic diagram of the overall appearance structure of the pipeline for producing hydrogen-rich water in Example 7.

[0163] Example 8

[0164] (1) Etch the titanium felt with 10% oxalic acid solution in a 75° water bath for 1 hour. Sonicate the etched titanium felt in an ultrasonic container for 5 minutes with deionized water until the surface of the etched titanium felt is clean.

[0165] (2) A 3 mmol / L chloroplatinic acid solution is prepared in a 120 mmol / L potassium chloride solution and completely dissolved under ultrasound.

[0166] (3) Electrodeposition was performed using a three-electrode system in a constant temperature water bath at 25°C. The titanium felt was used as the working electrode, the platinum sheet was used as the counter electrode, and the saturated calomel electrode was used as the reference electrode. After electroplating for 5 minutes at a constant potential of -0.5V, the electrode was taken out, rinsed with deionized water, and dried in an oven at 120°C to obtain a porous array electrode.

[0167] Characterization of the titanium felt and porous array electrodes mentioned above:

[0168] The internal structure of titanium felt is shown in the scanning electron microscope image. Figure 12 We can clearly see that the titanium felt is made of layers of ultra-fine titanium wires, not just a single thin layer, which makes the secondary array structure on the platinum wire in the middle of the titanium felt less likely to fall off and more stable.

[0169] See the SEM image of the platinum secondary array structure grown on the titanium felt substrate. Figure 13 The overall morphology of the secondary array structure is spherical, that is, the surface of the hemispherical or semi-ellipsoidal primary structure radially grows a thin sheet-like secondary structure, which greatly increases the roughness of the porous array electrode surface and further increases the water wetting ability. Figure 13 It can be seen that the length of the flakes is 50-500 nanometers, the width is 50-300 nanometers, and the thickness of the flakes is 4-20 nanometers.

[0170] Test the wettability of the porous array electrode and the underwater bubble adhesion:

[0171] Figure 14 Photographs were taken of the contact angle between the porous array electrode and the water droplet in Example 8, and the measured contact angle was 53°. Figure 15 Photographs were taken of the contact angle between the porous array electrode and the bubble in Example 8, and the measured contact angle was 154°. Under water, the behavior of the bubble on the electrode surface is opposite to the wetting situation of the water droplet on the electrode surface in air. At the same time, we define a solid surface with a bubble contact angle greater than 150° as a super-hydrophobic surface. Then the surface of this porous array electrode is a super-hydrophobic surface. The underwater bubble adhesion force test is shown in Figure 16 . Figure 16 It shows that: the interaction force between the bubble and the secondary array structure is very small, only 2.5 μN.

[0172] Example 9

[0173] Referring to the method in Example 8, in step (1), the titanium sheet was etched with a 15% mass fraction of oxalic acid solution for 2 hours under a 90° water bath condition. In step (2), a chloroplatinic acid solution with a concentration of 6 mmol / L was prepared in a potassium chloride solution with a concentration of 120 mmol / L and completely dissolved under ultrasound. In step (3), electro-deposition was carried out at a constant current of -15 mA / cm 2 and other conditions were the same as in Example 8, and finally a porous array electrode was obtained.

[0174] Characterize the above titanium sheet and porous array electrode: The scanning electron microscope image of the etched titanium sheet substrate is shown in the appendix Figure 17 . The scanning electron microscope image of the platinum secondary array structure grown on the titanium sheet substrate is shown in Figure 18 , and the overall morphology of the secondary array structure is sea urchin-like, that is, conical secondary structures grow radially on the surface of the hemispherical primary structure, greatly increasing the roughness of the porous array electrode surface and further increasing the water wetting ability. Figure 18 It can be seen that the length of the cone is 50 - 500 nm, and the width of the bottom of the cone is 50 - 300 nm. The secondary nanostructure is spiky, and its length is denoted as H1, and the overall maximum length of the primary array structure and the secondary nanostructure is denoted as H2, and H1 ≤ 1 / 2H2. The distance between the centers of the tops of adjacent secondary nanostructures generally (more than half) has a gap greater than 80 nm, Figure 18 and the gaps exemplified in

[0175] are 80.5 nm and 122.5 nm, so that the formed nanobubbles are not easily in contact and fused with each other, effectively improving the hydrophobicity of the electrode surface, making the bubbles detach from the electrode surface at the nanoscale and form nanobubbles that are soluble in water.

[0176] Figure 19A photograph was taken of the contact angle between the porous array electrode and the water droplet in Example 9, and the measured contact angle was 47°. Figure 20 A photograph was taken of the contact angle between the porous array electrode and the air bubble in Example 9, and the measured contact angle was 130°. The test of the air bubble adhesion force underwater is shown in Figure 21 . Figure 21 It shows that there is a very small interaction force between the air bubble and the secondary array structure, only 7.3 μN.

[0177] Example 10

[0178] Referring to the method in Example 8, in step (3), electrodeposition was carried out using a three-electrode system in a 50 °C constant temperature water bath. Others were the same as in Example 8, and finally a porous array electrode was obtained.

[0179] The above porous array electrode was characterized:

[0180] The scanning electron microscope image of the porous array electrode obtained in Example 10 is shown in Figure 22 . Figure 22 It can be seen that the length of the flake is 50 - 400 nanometers, the width is 50 - 400 nanometers, and the thickness of the flake is 4 - 15 nanometers.

[0181] Example 11

[0182] Referring to the method in Example 8, in step (3), after electrodeposition at a constant potential of -0.6 V for 5 min, it can be taken out. Others were the same as in Example 8, and finally a porous array electrode was obtained.

[0183] The above porous array electrode was characterized:

[0184] The scanning electron microscope image of the obtained porous array electrode is shown in Figure 23 . Figure 23 It can be seen that the length of the flake is 50 - 900 nanometers, the width is 50 - 900 nanometers, and the thickness of the flake is 4 - 10 nanometers.

[0185] Example 12

[0186] Referring to the method in Example 8, in step (3), first deposit in a potassium chloride solution with a concentration of 120 mmol / L at a constant potential of -0.5 V for 3 min, and then deposit in a potassium nitrate solution with a concentration of 120 mmol / L at a constant potential of -0.3 V for 5 min. Others were the same as in Example 8, and finally a porous array electrode was obtained.

[0187] The above porous array electrode was characterized:

[0188] The scanning electron microscope image of the obtained porous array electrode is shown in Figure 24The length of the cone is 200 - 400 nm, and the width of the bottom of the cone is 100 - 800 nm. Generally (more than half), the distance between the centers of the tops of adjacent secondary nanostructures has a gap greater than 80 nm. Figure 24 The gaps exemplified in Figure 24 are 115 nm and 163 nm. In the preparation method, in the electroplating step, electroplating is first carried out in a chloride solution for a period of time, and then electroplating is carried out in a nitrate solution, which will make the spikes more prominent, that is, thicker and longer.

[0189] Example 13

[0190] The porous array electrode prepared in Example 8 was used in the electrolyzed water device of an existing hydrogen-rich cup as the hydrogen evolution cathode. The anode used a titanium electrode, and the proton membrane used the N117 model. The size of the electrode sheet was 5 cm 2 , and the electrolysis current applied under normal pressure was 1 A, and the electrolysis time was 10 min.

[0191] The concentration of dissolved hydrogen in water was measured by a hydrogen detection pen, and the size of dissolved hydrogen bubbles in water was measured by a nanosight instrument.

[0192] Specific data: As Figure 25 shows the hydrogen bubble size distribution. It can be clearly seen that the size of the bubbles is at the nanoscale. In actual multiple measurements, the bubble diameter is mainly distributed below 350 nm. As the placement time increases, the number of nanobubbles mainly concentrates below 200 nm. As Figure 26 shows the change in hydrogen concentration in water. In the test, the average hydrogen concentration was 2.0 ppm, and the highest hydrogen content in water was 2.5 ppm.

[0193] Example 14

[0194] The porous array electrode prepared in Example 9 was used in the electrolyzed water device of an existing hydrogen-rich cup as the hydrogen evolution cathode. The anode used a titanium electrode, and the proton membrane used the N117 model. The size of the electrode sheet was 5 cm 2 , and the electrolysis current applied under normal pressure was 1 A, and the electrolysis time was 10 min.

[0195] The concentration of dissolved hydrogen in water was measured by a hydrogen detection pen, and the size of dissolved hydrogen bubbles in water was measured by a nanosight instrument.

[0196] Specific data: As Figure 27 shows the hydrogen bubble size distribution. It can be clearly seen that the size of the bubbles is at the nanoscale. In actual multiple measurements, the bubble diameter is mainly distributed below 350 nm. As the placement time increases, the number of nanobubbles mainly concentrates below 200 nm. As Figure 28 shows the change in hydrogen concentration in water. In the test, the average hydrogen concentration was 1.9 ppm, and the highest hydrogen content in water was 2.5 ppm.

[0197] Example 15

[0198] The porous array electrode prepared in Example 12 was used as the hydrogen evolution cathode in the electrolytic water device of an existing hydrogen-rich cup. A titanium electrode was used as the anode, and N117 type proton exchange membrane was used. The size of the electrode sheet was 5 cm 2 , and the electrolytic current applied under atmospheric pressure was 1 A, and the electrolysis time was 10 min.

[0199] The dissolved hydrogen concentration in water was measured by a hydrogen test pen, and the size of the dissolved hydrogen bubbles in water was tested by a nanosight instrument.

[0200] Specific data: As Figure 29 For the hydrogen bubble size distribution, it can be clearly seen that the size of the bubbles is in the nanoscale. In actual multiple measurements, the bubble diameter is mainly distributed below 350 nm. As the placement time increases, the number of nanobubbles mainly concentrates below 200 nm. As Figure 30 For the change of hydrogen concentration in water, in the test, the average hydrogen concentration was 2.1 ppm, and the highest hydrogen content in water was 2.6 ppm.

[0201] Comparative Example 1

[0202] In existing research, Li Yingjie et al. (Li, Yingjie, Zhang, Haichuan, Xu, Tianhao, etc. Under-Water Superaerophobic Pine-Shaped Pt Nanoarray Electrode for Ultrahigh-Performance Hydrogen Evolution[J]. Advanced Functional Materials, 25(11): 1737-1744, and his dissertation is: Construction of Novel Nanoarray Electrodes and Their Applications in Gas-Involved Electrocatalytic Reactions[D], Li Yingjie, Beijing, Beijing University of Chemical Technology, 2017) obtained pine-shaped Pt nanoarrays by electrodeposition method with carbon paper as the counter electrode in potassium nitrate solution.

[0203] The structural and parameter characteristics of this pine-shaped Pt nanoarray material are as follows:

[0204] The primary structure is conical, and the secondary structure is serrated. See the attached Figure 31 and Figure 32 .

[0205] The maximum distance between the centers of the tops of adjacent secondary serrated structures is less than 75 nm, the maximum gap between adjacent secondary structures is 72 nm, and the smaller gap distance is only 31 nm.

[0206] The length of the conical primary structure is denoted as H3, and the maximum equivalent diameter length of the globular unit where the conical primary structure is located is denoted as H4, and H3 > 1 / 2H4.

[0207] The above-mentioned pine-branch-like Pt nanoarray material effectively reduces the bubble detachment size. However, its Pt nanoarray is a cone close to the micron level, and the secondary serrated structures are relatively close, so the generated bubbles are likely to fuse with each other, resulting in the bubble detachment size still being at the micron level, and the bubble adhesion force is greater than 10 μN, and nano-sized hydrogen bubbles cannot be generated. The experiment of Li Yingjie was to explore micron-sized bubbles and could not generate nano-bubbles. The electrode of this patent generates nano-bubbles, and the two are at completely different conceptual levels.

[0208] Figure 31 It is the scanning electron microscope image of the pine-branch-like Pt nanoarray material in Comparative Example 1.

[0209] Figure 32 It is the (A) partially enlarged scanning electron microscope image, (B) transmission electron microscope image, (C) dendritic structure part, and (D) high-resolution transmission electron microscope image of the serrated structure on each branch of the pine-branch-like Pt nanoarray material in Comparative Example 1.

[0210] As described above, it is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should all be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. An electrolytic water tubular electrode (10), characterized in that, The tubular electrode (10) includes an ion exchange membrane (2), a coaxial hollow inner layer tube (1), and a hollow outer layer tube (3); Wherein, the space between the inner layer tube (1) and the outer layer tube (3) is filled with the ion exchange membrane (2); The inner layer tube (1) is an anode tube for electrolyzing water, and the outer layer tube (3) is a cathode tube for electrolyzing water; or the inner layer tube (1) is a cathode tube for electrolyzing water, and the outer layer tube (3) is an anode tube for electrolyzing water; The ion exchange membrane (2) includes a proton exchange membrane or an anion exchange membrane; The inner layer tube (1) and the outer layer tube (3) are conductive tubes with breathable and water-permeable tube walls; A porous array electrode is provided on the cathode tube, and the porous array electrode includes: A porous conductive substrate and a primary array structure grown on the porous conductive substrate, each unit of the primary array structure being at least a part of a spherical or ellipsoidal shape; secondary nanostructures in the form of flakes, cones, or spikes radially growing on the surface of each unit of the primary array structure; When the secondary nanostructures are in the form of cones or spikes, the average distance between the centers of the tops of adjacent secondary nanostructures is in the range of 80 - 200 nm; Both the primary array structure and the secondary nanostructures are made of platinum; The preparation method of the porous array electrode includes the following steps: (1) Etch the porous conductive substrate with an acidic solution of a certain mass fraction, and then wash it to obtain a porous conductive substrate with a rough structure on the surface; (2) In an electrolyte solution of a certain concentration of chloride, configure a soluble platinum solution of a certain concentration to obtain a mixed solution; In the mixed solution in step (2), the soluble platinum solution is chloroplatinic acid or potassium chloroplatinate solution, with a concentration of 0.2 - 10 mmol / L, and the concentration of chloride in the mixed solution is 20 - 200 mmol / L; (3) In the mixed solution obtained in step (2), perform electrodeposition using a three - electrode system. Among them, the porous conductive substrate obtained in step (1) is used as the working electrode. After electrodeposition for a period of time, take it out, wash it, and dry it to obtain the porous array electrode; The electrodeposition is potentiostatic electrodeposition or galvanostatic electrodeposition. The potentiostatic value is -0.4 to -1 V, and the galvanostatic value is -0.4 to -60 mA / cm 2 ; The electrodeposition time in step (3) is 3 - 30 min.

2. The tubular electrode (10) according to claim 1, characterized in that, The inner surface and / or outer surface of the anode tube for electrolyzing water is coated or grown with an anode catalyst; The anode catalyst is selected from: Non - noble metal catalysts such as oxides, hydroxides, carbides, nitrides, sulfides, selenides, phosphides, and borides of metals iron, cobalt, nickel, tungsten, molybdenum, and copper; or Noble metals such as platinum, ruthenium, iridium, palladium, rhodium, and silver, and oxides of platinum, ruthenium, iridium, palladium, and rhodium; The pipe material of the anode tube is a porous conductive material of metal or carbon - based; 3. The tubular electrode according to claim 1, wherein, One end of the tubular electrode is sealed by an insulating layer, the inner layer tube (1), or the outer layer tube (3).

4. An electrolyzed water device capable of generating micro-nano hydrogen-rich water, characterized in that, It includes the electrolytic water tubular electrode (10) according to any one of claims 1 - 3.

5. The electrolytic water device according to claim 4, characterized in that, When the inner layer tube (1) is the anode tube and the outer layer tube (3) is the cathode tube, water is outside the outer layer tube (3) during use; The design of the electrolytic water device is as follows: The electrolyzed water device is a hydrogen-rich cup or a hydrogen-rich machine, which includes a base of the electrolysis device, and on the base of the electrolysis device are provided: an insulating fixing plate (101) having through holes and at least one tubular electrode (10) as described in claim 2 or 3; Wherein, each of the tubular electrodes (10) is arranged on the fixing plate (101) with the sealed end facing upward, and is arranged in such a way that all the through holes on the fixing plate (101) are surrounded inside the anode tube; The cup body of the hydrogen-rich cup or the body of the hydrogen-rich machine is connected to the base of the electrolysis device.

6. The electrolytic water device according to claim 4, characterized in that, When the inner tube (1) is the anode tube and the outer tube (3) is the cathode tube, water is outside the outer tube (3) during use; The electrolyzed water device is designed as follows: The electrolyzed water device is a pipeline for producing hydrogen-rich water, which includes a base of the electrolysis device, and on the base of the electrolysis device are provided: an insulating fixing plate (101) having through holes and at least one tubular electrode (10) as described in claim 2 or 3; wherein, each of the tubular electrodes (10) is arranged on the fixing plate (101) with the sealed end facing upward, and is arranged in such a way that all the through holes on the fixing plate (101) are surrounded inside the anode tube, and each anode tube surrounds the through holes, the periphery of the base of the electrolysis device is sealed by the pipe wall of the pipeline, only a pipeline water inlet (20) and a pipeline water outlet (21) are provided, and the fixing plate (101) itself is a part of the pipe wall of the pipeline.

7. The electrolytic water device according to claim 4, wherein, When the inner tube (1) is the cathode tube and the outer tube (3) is the anode, water is inside the inner tube (1) during use; The electrolyzed water device is designed as follows: The electrolyzed water device includes two parallel insulating fixing plates (101) having through holes, at least one tubular electrode (10) as described in claim 1, and a cylindrical sealed housing (102), and on the cylindrical sealed housing (102) are provided a water inlet (102-1), a water outlet and an oxygen outlet (102-2); Wherein, both ends of each of the tubular electrodes (10) are arranged on the fixing plate (101) and are arranged in such a way that all the through holes on the fixing plate (101) are surrounded inside the cathode tube (1); The water inlet (102-1) and the water outlet are both communicated with the through holes; The oxygen outlet (102-2) is isolated from the through holes; The outer diameter of the fixing plate (101) is equal to the inner diameter of the housing (102).

8. Use of an electrolyzed water device capable of generating micro-nano hydrogen-rich water according to claim 4, characterized in that, It is used for supplying oxygen and oxygen-rich water.

9. Use of the electrolyzed water device as described in claim 4 in bathing.

10. Use of the electrolyzed water device as described in any one of claims 5-7 in bathing, agricultural irrigation, hydrogen inhalation device, hydrogen-rich cabin health care device or food preservation device.

11. Use of the electrolyzed water device as described in claim 4 in aquaculture, sewage treatment or oxygen inhalation device.

Images