CN111172557A

CN111172557A - Water electrolysis tubular electrode, water electrolysis device comprising same and application

Info

Publication number: CN111172557A
Application number: CN202010113147.7A
Authority: CN
Inventors: 邝允; 孙晓明; 李佳伟; 王士元
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2020-02-24
Filing date: 2020-02-24
Publication date: 2020-05-19

Abstract

The invention belongs to the technical field of water electrolysis, and particularly relates to an electrolytic water tubular electrode, a water electrolysis device comprising the same and application of the electrolytic water tubular electrode. The tubular electrode (10) comprises an ion exchange membrane (2), a hollow inner layer tube (1) and a hollow outer layer tube (3) which are coaxially arranged; wherein the ion exchange membrane (2) is filled between the inner layer tube (1) and the outer layer tube (3); the inner layer tube (1) is an electrolytic water anode tube, and the outer layer tube (3) is an electrolytic water cathode tube; or the inner layer tube (1) is an electrolytic water cathode tube, and the outer layer tube (3) is an electrolytic water anode tube; the inner layer pipe (1) and the outer layer pipe (3) are conductive pipes with air-permeable and water-permeable pipe walls. The invention designs the electrolysis device comprising the water electrolysis tubular electrodes, the installation is convenient, a plurality of water electrolysis tubular electrodes can be arranged in the electrolysis device side by side, the electrolysis efficiency is high, the diameter of hydrogen bubbles in hydrogen-rich water generated by electrolysis is mainly distributed below 350nm, and the highest hydrogen content in the hydrogen-rich water can reach 2.5 ppm.

Description

Water electrolysis tubular electrode, water electrolysis device comprising same and application

Technical Field

The invention belongs to the technical field of water electrolysis, and particularly relates to an electrolytic water tubular electrode, a water electrolysis device comprising the same and application of the electrolytic water tubular electrode.

Background

Hydrogen is the smallest and simplest molecule in nature and has a very important role in life. Hydrogen can neutralize active oxygen with strong oxidizability in vivo, and when water solution rich in micro or nano hydrogen bubbles enters daily life, a large number of researches show that the hydrogen-rich water can regulate and control the activity of oxidative metabolism and has the physiological effects of fatigue resistance, cancer resistance, inflammation resistance and the like. Therefore, the hydrogen-rich water can be used as a novel drinking water resource, is an ideal antioxidant and can even provide effective help for preventing and treating chronic diseases.

The market is also expanding for hydrogen rich water, especially for portable hydrogen rich cups. However, the following problems currently exist:

1. the electrodes of the electrolytic water in the hydrogen-rich cup are mostly of a stacked sheet structure, the structure is small in contact area with the water body, large in occupied space, not suitable for free combination use of a multi-electrode structure, low in electrolytic water efficiency, and low in hydrogen concentration in the prepared hydrogen-rich water.

2. Most of hydrogen bubbles generated by the conventional electrolytic water electrode are micron-sized, and the hydrogen bubbles with the micron-sized are not high in solubility in water and cannot exist stably. If the hydrogen bubbles with nanometer size can be generated, the concentration of the hydrogen dissolved in the water is greatly increased, and the hydrogen bubbles with nanometer size can stably exist in the water for a long time.

3. In addition, the existing sheet-shaped electrolytic water electrode is not suitable for free combination of a multi-electrode structure, is only suitable for being used in small devices such as hydrogen-rich cups, and cannot meet the requirements of places requiring a large amount of hydrogen-rich water in daily life, industry, agriculture and the like.

The present invention has been made to solve the above problems.

Disclosure of Invention

The invention provides an electrolytic water tubular electrode 10, wherein the tubular electrode 10 comprises an ion exchange membrane 2, a hollow inner layer tube 1 and a hollow outer layer tube 3 which are coaxially arranged;

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 electrolytic water anode tube, and the outer layer tube 3 is an electrolytic water cathode tube; or the inner layer tube 1 is an electrolytic water cathode tube, and the outer layer tube 3 is an electrolytic water anode tube;

the ion exchange membrane 2 comprises a proton exchange membrane or an anion exchange membrane;

the inner layer tube 1 and the outer layer tube 3 are conductive tubes with air-permeable and water-permeable tube walls.

The ion exchange membrane 2 is substantially impermeable to air and water, which in use is wetted by the slightly permeable water.

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

Preferably, the pipe wall of the inner layer pipe 1 is provided with a plurality of first air generating holes 1-1, and the pipe wall of the outer layer pipe 3 is provided with a plurality of second air generating holes 3-1.

Preferably, the tubular electrode 10 further comprises a hollow insulating gas permeable support tube disposed in the inner layer of the inner tube 1 and coaxially arranged therewith. The purpose is to discharge the gas generated by the electrolysis of water.

Preferably, the pipe wall of the supporting pipe is provided with a plurality of air vents.

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

The term "air-permeable" as used herein refers to any material or structure that can perform the function of air-permeability, such as a material having microscopic or macroscopic through-holes for air-permeability and water-permeability.

Preferably, the electrolytic water anode tube is of any suitable tubular construction known in the art that can be used as an anode in electrolytic water.

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

non-noble metal catalysts such as oxides, hydroxides, carbides, nitrides, sulfides, selenides, phosphides, borides, and the like, which are coated or grown on the surface of the catalyst, with elements such as iron, cobalt, nickel, tungsten, molybdenum, copper, and the like; or noble metals such as platinum, ruthenium, iridium, palladium, rhodium, silver and the like and oxide catalysts thereof are used for the anodic oxygen evolution reaction; the material of the pipeline is metal or carbon-based porous conductive material. Here, porous means that the material has micro or macro through holes for air and water permeation.

Preferably, the cathode tube of electrolyzed water is a tubular structure of any suitable material now available for use as a cathode in electrolyzed water.

Preferably, the inner surface and/or the outer surface of the tubular structure of the electrolytic water cathode tube is coated/grown with a cathode catalyst; non-noble metal catalysts such as oxides, hydroxides, carbides, nitrides, sulfides, selenides, phosphides, borides, and the like, which are coated or grown on the surface of the catalyst, with elements such as iron, cobalt, nickel, tungsten, molybdenum, copper, and the like; or noble metals such as platinum, ruthenium, iridium, palladium, rhodium, silver and the like and oxide catalysts thereof are used for the cathodic hydrogen evolution reaction; the pipeline is made of metal or carbon-based porous conductive materials.

Preferably, the cathode tube is selected from a titanium tube grown with a platinum nano-array. The anode tube is selected from a titanium tube, such as a tube body made of titanium sheet, titanium felt, titanium mesh, or titanium foam.

In the invention, when the pipe body is made of titanium felt, titanium mesh or titanium foam, the pipe body is naturally a conductive pipe with a permeable and water-permeable pipe wall because the titanium felt, the titanium mesh or the titanium foam has microscopic pores.

When the tube body is made of titanium sheets, the tube wall of the tube body is provided with a plurality of first air generating holes 1-1 or a plurality of second air generating holes 3-1, so that the tube is a conductive tube with a permeable and water-permeable tube wall.

Here, the gas generating hole is used to make the cathode/anode tube and the ion exchange membrane permeable to air and water so that the hydrogen/oxygen reaction of the electrolyzed water can be performed, and thus may be called as a gas generating hole.

Preferably, a porous array electrode is disposed on the cathode tube, and the porous array electrode includes:

a porous electrically conductive substrate and a primary array structure grown on the porous electrically conductive substrate, each cell of the primary array structure being at least a portion of a sphere or an ellipsoid in shape; secondary nanostructures in the form of platelets, cones, or spikes radially grown on the surface of each unit of the primary array structure.

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

Preferably, the primary array structure and the secondary nanostructure are both platinum.

Preferably, the preparation method of the porous array electrode comprises the following steps:

(1) etching the porous conductive substrate by using a certain mass fraction of acid solution, and then washing to obtain the porous conductive substrate with a rough structure on the surface;

(2) preparing a soluble platinum solution with a certain concentration in an electrolyte solution of chloride with a certain concentration to obtain a mixed solution;

(3) in the mixed solution obtained in the step (2), performing electrodeposition by adopting a three-electrode system, wherein the porous conductive substrate obtained in the step (1) is a working electrode, and a saturated calomel electrode is a reference electrode; and taking out, cleaning and drying the electrode after a period of electrodeposition to obtain the porous array electrode.

Preferably, in the porous array electrode:

when the secondary nanostructure is conical or spiky, the length of the secondary nanostructure is H1, the overall maximum length of the primary array structure and the secondary nanostructure is recorded as H2, and H1 is less than or equal to 1/2H 2;

the length of the secondary structure in the shape of a sheet, a cone or a spike is 50-800 nanometers, and the width of the secondary structure is 50-800 nanometers; the thickness of the sheet-like secondary structure is 4-10 nanometers; the maximum distance between the centers of the conical or spiked top ends of the adjacent secondary nanostructures is greater than 80 nm.

Preferably, when the secondary nanostructures are cone-shaped or spike-shaped, the average distance between the top centers of the adjacent secondary nanostructures is 80-200 nm. When the pitch is too large, the size of the generated hydrogen bubbles is too large. When the average value of the intervals is 80 to 200nm, hydrogen bubbles having a size in the order of nanometers can be generated.

The surface of the porous conductive substrate is provided with 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 is provided with a plurality of first air generating holes 1-1 or a plurality of second air generating holes 3-1, so that the manufactured tube body is a conductive tube with a permeable and water-permeable tube wall.

Preferably, in the method for preparing the porous array electrode:

the counter electrode in the three-electrode system is a platinum electrode or graphite paper; preparing a soluble platinum solution with a certain concentration in an electrolyte solution of nitrate with a certain concentration to obtain a second mixed solution; in the electrodeposition step, firstly, electrodeposition is carried out in the mixed solution containing the chloride salt obtained in the step (2) for a period of time, and then the electrodeposition is carried out in the second mixed solution for a period of time; the electrodeposition is constant potential electrodeposition or constant current electrodeposition, the constant potential is-0.4 to-1V, and the constant current is-0.4 to-60 mA/cm²。

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

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

Preferably, the reaction of step (3) is carried out in a thermostated water bath at a temperature of 0-90 ℃.

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

Preferably, the chloride is potassium chloride, or sodium chloride.

The invention provides a water electrolysis device capable of generating micro-nano hydrogen-rich water, which comprises the tubular electrode 10 for water electrolysis.

Preferably, when the inner layer tube 1 is an anode tube and the outer layer tube 3 is a cathode tube, water is outside the outer layer tube 3 during use;

the design of the water electrolysis device is as follows:

the water electrolysis device is a hydrogen-rich cup or a hydrogen-rich machine and comprises an electrolysis device base, wherein the electrolysis device base is provided with: an insulating fixing plate 101 having a through hole and at least one tubular electrode 10 according to the first aspect of the present invention;

wherein each tubular electrode 10 is arranged on the fixing plate 101 with the sealed end facing upwards in such a way that all through holes on the fixing plate 101 are enclosed inside the anode tube;

the cup body of the hydrogen-rich cup or the body of the hydrogen-rich machine is connected with the electrolysis device base.

the design of the water electrolysis device is as follows:

the water electrolysis device is a pipeline for producing hydrogen-rich water, and comprises an electrolysis device base, wherein the electrolysis device base is provided with: an insulating fixing plate 101 having a through hole and at least one tubular electrode 10 according to the first aspect of the present invention; wherein each tubular electrode 10 is arranged on the fixing plate 101 with the sealed end facing upwards, and is arranged in a way that all through holes on the fixing plate 101 are enclosed inside the anode tube, and each anode tube is internally enclosed with the through holes, the periphery of the electrolyzer base is sealed by the tube wall of the pipeline, only a pipeline water flow inlet 20 and a pipeline water flow outlet 21 are arranged, and the fixing plate 101 is a part of the tube wall of the pipeline.

Preferably, when the inner tube 1 is a cathode tube and the outer tube 3 is an anode tube, water is outside the inner tube 1 during use;

the design of the water electrolysis device is as follows:

the water electrolysis device comprises two insulating fixing plates 101 which are arranged in parallel and are provided with through holes, at least one tubular electrode 10 as claimed in claim 1, and a cylindrical sealed shell 102, wherein a water inlet 102-1, a water outlet and an oxygen outlet 102-2 are arranged on the cylindrical sealed shell 102;

wherein both ends of each tubular electrode 10 are disposed on the fixing plate 101 in such a manner that all the through holes on the fixing plate 101 are surrounded inside the cathode tube;

the water inlet 102-1 and the water outlet are communicated with the through hole;

the oxygen outlet 102-2 is isolated from the through hole;

the outer diameter of the fixing plate 101 is equal to the inner diameter of the housing 102.

The anode tube is made of any water electrolysis anode material for the existing water electrolysis.

The third aspect of the invention provides application of the water electrolysis device capable of generating micro-nano hydrogen-rich water, and the device can also be used for supplying oxygen and oxygen-rich water. That is, the electrolytic water device can be used to supply hydrogen-rich water, oxygen, and oxygen-rich water at the same time.

The purity of the oxygen is more than 99.99%. The hydrogen bubble diameter in the hydrogen-rich water is mainly distributed below 350nm, and the quantity of the nano bubbles is mainly concentrated below 200nm when the standing time reaches 60 minutes. The hydrogen content in the hydrogen-rich water can reach 2.5ppm at most, and the average hydrogen concentration is 2.1 ppm.

In addition, the water electrolysis device can be applied to a hydrogen-rich water machine for human or animal drinking; can be used for large-scale hydrogen-rich water devices, and can be applied to bathing or agricultural irrigation; the hydrogen can be prepared and used as a core device to be applied to a hydrogen absorption device, a hydrogen cabin health-care device, or a food fresh-keeping device such as a refrigerator, a large-scale fresh-keeping cabin, a fresh-keeping chamber and the like.

The water electrolysis device capable of supplying oxygen can also be used for aquaculture, sewage treatment or oxygen inhalation devices.

The technical scheme can be freely combined on the premise of no contradiction.

The porous electrode used by the cathode tube has the following beneficial effects:

(1) high hydrogen production efficiency and strong stability. The porous electrode structure is obtained for the first time, the surface of the conductive substrate is provided with an arrayed secondary structure, each unit of the primary array structure is at least one part of a sphere or an ellipsoid, and compared with a sheet-shaped or rod-shaped structure, the porous electrode structure can be more firmly combined with the conductive substrate and is not easy to damage and fall off; the secondary nano structure is a sheet-shaped, conical or spiky structure which radially grows on the surface of each unit of the primary array structure, so that the specific surface area of the material is improved, more active sites can be exposed for electrochemical reaction, and the electrochemical reaction efficiency is improved.

(2) It is easier to generate hydrogen bubbles with small size and even nanometer size. In order to obtain nano-scale bubbles, the gas evolution reaction needs to be separated from the electrode surface and transfer mass to the liquid phase as soon as possible. The porous electrode secondary structure is integrally in a spherical sheet shape and a sea urchin shape, and when the highly ordered array structure is used for a cathode material for hydrogen evolution reaction, the contact area between the surface of the electrode and bubbles can be effectively cut, so that the contact area between the surface of the electrode and the bubbles is smaller, the adhesion force of the bubbles is small, and the bubbles can be favorably separated. In the electrolytic water hydrogen evolution reaction, the content of the nano-scale hydrogen bubbles reaches 2.5 ppm.

(3) In the preferable technical scheme, the maximum distance between the top centers of the adjacent secondary nanostructures on the porous electrode is greater than 80nm, so that the formed nano bubbles are not easy to contact and fuse with each other, the gas permeability of the surface of the electrode is effectively improved, the bubbles can be separated from the surface of the electrode in a nano scale, and water-soluble nano bubbles are formed. The diameters of hydrogen bubbles in the hydrogen-rich water are mainly distributed below 350nm, and when the standing time reaches 60 minutes, the quantity of nano bubbles is mainly concentrated below 200 nm. The hydrogen content in the hydrogen-rich water can reach 2.5ppm at most, and the average hydrogen concentration is 2.1 ppm.

(4) In the preferred technical scheme, the surface of the conductive substrate is etched, so that the platinum electrodeposited in the etched pore channel is not easy to contact with the outside, has higher stability and is difficult to fall off.

(5) The invention discovers for the first time that in the preparation method, the electrodeposition step is performed in a chloride solution for a period of time, and then the electrodeposition step is performed in a nitrate solution, so that the spikes are more prominent, namely longer and thicker.

(6) The invention discovers for the first time that the current is controlled to be-0.4 to-60 mA/cm during constant current deposition²And during constant potential deposition, the potential is controlled to be-0.4 to-1V, so that the formation of a secondary structure can be accurately maintained. If not, secondary structures such as spherulites and echinoids cannot be obtained.

(7) In the preferred technical scheme, the counter electrode for electrodeposition adopts platinum, the platinum electrode is continuously consumed in the reaction, and compared with the counter electrode adopting a non-platinum material, the concentration of platinum ions in the electrodeposition mixed solution can be kept stable, and the stable performance of the electrodeposition effect is ensured.

(8) The synthesis method is simple and easy to implement, has high repeatability, and the electrode material is safe and harmless to human bodies. The preparation process is simple and is suitable for industrial production.

The electrolytic water tubular electrode of the invention has the following beneficial effects:

when the inner layer tube is a cathode tube and the outer layer tube is an anode tube, water flows in when the water-cooled water-:

1. the electrolytic area of the electrode is greatly increased. And hydrogen generated by electrolysis is mixed with water from the inside of the tube to generate hydrogen-rich water, and oxygen overflows from the outside of the tubular electrode and can be used as a core component to be combined with various devices for generating hydrogen-rich water.

2. The invention also designs the electrolysis device comprising the water electrolysis tubular electrodes, the structure is novel, the installation is convenient, a plurality of water electrolysis tubular electrodes can be arranged in the electrolysis device side by side, and the electrolysis efficiency is high. As long as the external water flows through the hydrogen-rich water pipe, the outlet water is the hydrogen-rich water containing a large amount of hydrogen, and the oxygen generated by electrolysis is collected and discharged from the oxygen outlet and can be simultaneously used for supplying the hydrogen-rich water, the oxygen and/or the oxygen-rich water. The oxygen-enriched water can be used in aquaculture industry.

When the inner layer tube is an anode tube and the outer layer tube is a cathode tube, water flows out when the tube is used, and the tube has the following advantages:

1. the hydrogen produced by electrolysis is mixed with water from the outside of the tube to generate hydrogen-rich water, and the oxygen overflows from the inside of the tubular electrode and can be used as a core component to be combined with various devices for producing hydrogen-rich water.

2. The invention also designs a hydrogen-rich cup/machine comprising the tubular electrodes for electrolyzing water, the hydrogen-rich cup/machine has novel structure and convenient installation, a plurality of tubular electrodes for electrolyzing water can be arranged in parallel in the hydrogen-rich cup/machine, and the electrolysis efficiency is high.

3. The invention also designs a pipeline for producing hydrogen-rich water, which comprises the electrolytic water tubular electrodes, the pipeline is novel in structure and convenient to install, a large number of electrolytic water tubular electrodes can be arranged in the pipeline side by side, the electrolytic efficiency is high, and the outlet water of the pipeline is the hydrogen-rich water containing a large amount of hydrogen as long as external water flows through the pipeline. The pipeline can be connected with washing and bathing water pipes in daily life in series, and hydrogen-rich water can be used in daily life to achieve the health-care effect.

Drawings

Fig. 1 is an exploded view of the structure of a single tubular electrode 10 of example 1.

Fig. 2 is a schematic perspective view of a single tubular electrode 10 according to example 1.

Fig. 3 is a schematic perspective view of a single tubular electrode 10 according to example 2.

FIG. 4 is an exploded view of the electrolyzer of example 4.

FIG. 5 is a schematic view of the electrolytic apparatus according to example 4.

FIG. 6 is an exploded view of the electrolyzer of example 5.

FIG. 7 is a schematic view of the electrolytic apparatus according to example 5.

FIG. 8 is a schematic view showing the structure of a base of a hydrogen-rich cup electrolyzer in accordance with example 6.

FIG. 9 is a schematic structural view of a base of a conduit electrolyzer for producing hydrogen-rich water in accordance with embodiment 7.

FIG. 10 is a schematic view showing the structure of embodiment 7 before piping installation of hydrogen-rich water.

FIG. 11 is a schematic view of the entire appearance of a hydrogen-rich water generating pipe according to example 7.

FIG. 12 is a scanning electron micrograph of the internal structure of the titanium felt of example 8.

FIG. 13 is a SEM image of the porous array electrode of example 8.

FIG. 14 is a photograph of the contact angle of the porous array electrode-water droplet in example 8.

FIG. 15 is a photograph of the contact angle of the porous array electrode-bubbles in example 8.

FIG. 16 is a graph showing the adhesion of the porous array electrode of example 8.

FIG. 17 is a SEM image of the etched titanium substrate of example 9.

FIG. 18 is a SEM image of the porous array electrode of example 9.

FIG. 19 is a photograph of the contact angle of the porous array electrode-water droplet in example 9.

FIG. 20 is a photograph of the contact angle of the porous array electrode-bubbles in example 9.

FIG. 21 is a graph showing the adhesion of the porous array electrode in example 9.

FIG. 22 is a SEM image of the porous array electrode of example 10.

FIG. 23 is a SEM image of the porous array electrode of example 11.

FIG. 24 is a SEM image of the porous array electrode of example 12.

FIG. 25 is a histogram of the hydrogen bubble size distribution in example 13.

FIG. 26 is a histogram showing the hydrogen concentration distribution in water in example 13.

FIG. 27 is a histogram of the hydrogen bubble size distribution in example 14.

FIG. 28 is a histogram of the hydrogen concentration distribution in water of example 14.

FIG. 29 is a histogram of hydrogen bubble size distribution in example 15.

FIG. 30 is a histogram of the hydrogen concentration distribution in water in example 15.

Fig. 31 is a scanning electron micrograph of the pine-branched Pt nano-array material of comparative example 1.

Fig. 32 is (a) a local enlarged scanning electron micrograph (B) a transmission electron micrograph, and (C) a dendritic structure portion and (D) a saw tooth structure on each branch of the pine-branched Pt nano-array material in comparative example 1.

List of reference numerals:

1. the device comprises an inner layer pipe 1-1, a first gas generating hole 2, an ion exchange membrane 3, an outer layer pipe 3-1, a second gas generating hole 10, a tubular electrode 101, a fixing plate 101-1, a fixing clamping groove 102, a sealing shell 102-1, a water inlet 102-2 and an oxygen outlet. 20. A pipeline water flow inlet 21 and a pipeline water flow outlet.

Detailed Description

The present invention will be further described with reference to the following embodiments.

Example 1

Referring to fig. 1 and 2, an electrolytic water tubular electrode 10 for water inflow, the tubular electrode 10 comprises a proton exchange membrane 2, a hollow inner layer tube 1 cathode tube and a hollow outer layer tube 3 anode tube which are coaxially arranged; the inner layer tube 1 and the outer layer tube 3 are respectively connected with the corresponding negative pole and the positive pole of the power supply.

Wherein the space between the cathode tube and the anode tube is completely filled by the proton exchange membrane 2; the tube wall of the inner layer cathode tube is provided with a plurality of first air generating holes 1-1, and the tube wall of the outer layer anode tube is provided with a plurality of second air generating holes 3-1. The tubular electrode 10 is open at both ends. The porous electrode material prepared as described in example 7 was disposed on the inner wall of the cathode tube.

Example 2

Referring to fig. 3, an electrolytic water tubular electrode 10 for outflow of water only differs from embodiment 1 in that: in example 2, the outer layer tube 3 was a cathode tube, the inner layer tube 1 was an anode tube, and one end of the cathode tube was sealed to form a sealed end of the tubular electrode 10. The porous electrode material prepared in example 8 was disposed on the outer wall of the cathode tube.

Example 3

The proton exchange membrane of example 1 was replaced with an anion exchange membrane.

Example 4

As shown in fig. 4 and 5, an electrolyzed water tubular device capable of producing a micro-nano hydrogen-rich water comprises an electrolyzed water tubular electrode 10 flowing in a water body as described in example 1.

The water electrolysis device is characterized in that in order to ensure the flexibility of the tubular device, the difference from the embodiment 1 is that the hollow inner layer tube 1, the water electrolysis cathode tube and the hollow outer layer tube 3, which are coaxially arranged, are formed by rotating and surrounding thin and long strips of titanium sheets, and a certain distance is reserved between the thin and long strips of titanium sheets. The inner layer tube 1 and the outer layer tube 3 are respectively connected with the corresponding negative pole and the positive pole of the power supply.

As long as the external water flows through the electrolytic water tubular device, the outlet water is the hydrogen-rich water containing a large amount of hydrogen, and the device can be used for bathing devices.

FIG. 4 is an exploded view of the electrolyzer of example 4. FIG. 5 is a schematic view of the electrolytic apparatus according to example 4.

Example 5

As shown in fig. 6 and 7, an electrolytic water device capable of generating a micro-nano hydrogen-rich water includes an electrolytic water tubular electrode 10 for an internal flow of a water body described in example 1.

The water electrolysis device comprises two insulating fixing plates 101 which are arranged in parallel and are provided with 7 through holes, 7 tubular electrodes 10 and a cylindrical sealing shell 102, wherein a water inlet 102-1, a water outlet and an oxygen outlet 102-2 are arranged on the cylindrical sealing shell 102;

wherein both ends of each tubular electrode 10 are disposed on the fixing plate 101 in such a manner that: each end of each cathode tube surrounds one through hole;

the water inlet 102-1 and the water outlet are symmetrically arranged with the water inlet 102-1, and are not shown in fig. 6 and are communicated with the through hole;

the oxygen outlet 102-2 is isolated from the through hole;

The fixing plate 101 is provided with a fixing clamping groove 101-1, the tubular electrode 10 is installed on the fixing clamping groove 101-1, and a positive power supply interface and a negative power supply interface are arranged in the fixing clamping groove 101-1.

The water inlet 102-1 and the water outlet are both connected to the through hole only, and the outer diameter of the fixing plate 101 is equal to the inner diameter of the housing 102, so as to ensure that the water is blocked by the fixing plate 101 and can only flow through the tubular electrode 10. The space between the outside of the tubular electrode 10 and the housing 102 is filled with oxygen, and the space is filled with an oxygen outlet 102-2.

The tubular electrode 10 and the two parallel insulating fixing plates 101 with 7 through holes can be designed in one piece. The cylindrical closure housing 102 includes a cap having the water inlet 102-1, which is removably attached to the main body of the cylindrical closure housing 102. This also facilitates the insertion of the tubular electrode 10.

The fixing plate 101 is provided with fixing clamping grooves 101-1 with the same number as the tubular electrodes 10, the tubular electrodes 10 are installed on the fixing clamping grooves 101-1, the fixing clamping grooves are used for conducting electricity, each fixing clamping groove 101-1 is internally divided into an anode clamping groove section and a cathode clamping groove section, anode power interfaces and cathode power interfaces are respectively arranged in the fixing clamping grooves, and the anode power interfaces and the cathode power interfaces are respectively electrically connected with the cathode tube and the anode tube. Any suitable connection means known in the art may be used for the specific connection means herein.

As long as the external water flows through the water electrolysis device of the embodiment, the outlet water is the hydrogen-rich water containing a large amount of hydrogen, and the oxygen generated by electrolysis is collected and discharged from the oxygen outlet 102-2, which can be used for supplying the hydrogen-rich water and the oxygen simultaneously.

FIG. 6 is an exploded view of the electrolyzer of example 5.

Example 6

As shown in fig. 8, a hydrogen-rich cup capable of generating micro-nano hydrogen-rich water comprises an electrolysis device base, wherein the electrolysis device base is provided with: an insulating fixing plate 101 having a through-hole (not shown) and the tubular electrode 10 described in embodiment 2.

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

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

The fixing plate 101 is provided with fixing clamping grooves 101-1, the number of the fixing clamping grooves is equal to that of the tubular electrodes 10, the tubular electrodes 10 are installed on the fixing clamping grooves 101-1, the fixing clamping grooves are used for conducting electricity, each fixing clamping groove 101-1 is internally divided into an anode clamping groove section and a cathode clamping groove section, anode power interfaces and cathode power interfaces are respectively arranged in the fixing clamping grooves, and the anode power interfaces and the cathode power interfaces are respectively electrically connected with the anode tube and the cathode tube.

FIG. 8 is a schematic view showing the structure of a base of a hydrogen-rich cup electrolyzer in accordance with example 6. The cup body of the hydrogen-rich cup or the body of the hydrogen-rich machine is connected with the electrolysis device base. The connection method can use any suitable connection method in the prior art, and a schematic diagram is not provided.

Example 7

Referring to fig. 9 to 11, a hydrogen-rich water producing pipe comprises an electrolyzer base on which are disposed: an insulating fixing plate 101 having a through hole and the tubular electrode 10 described in embodiment 2; the number of through holes is the same as the number of tubular electrodes 10.

Wherein each of the tubular electrodes 10 is disposed on the fixing plate 101 with the sealed end facing upward in such a manner that each through-hole on the fixing plate 101 is enclosed inside each anode tube. The circumference of the electrolyzer base is sealed by the pipe wall of the pipe, and only the pipe water inlet 20 and the pipe water outlet 21 (not shown) are provided in the same size as the pipe water inlet 20), and the fixing plate 101 itself is a part of the pipe wall of the pipe.

The fixing plate 101 is provided with a fixing clamping groove 101-1, the tubular electrode 10 is installed on the fixing clamping groove 101-1, a positive power supply interface and a negative power supply interface are arranged in the fixing clamping groove 101-1, and the positive power supply interface and the negative power supply interface are respectively and electrically connected with the anode tube and the cathode tube. As long as the external water flows through the pipeline of the embodiment, the outlet water is the hydrogen-rich water containing a large amount of hydrogen.

FIG. 9 is a schematic structural view of a base of a conduit electrolyzer for producing hydrogen-rich water in accordance with embodiment 7. FIG. 10 is a schematic view showing the structure of embodiment 7 before piping installation of hydrogen-rich water. FIG. 11 is a schematic view of the entire appearance of a hydrogen-rich water generating pipe according to example 7.

Example 8

(1) And etching the titanium felt for 1 hour by using an oxalic acid solution with the mass fraction of 10% under the condition of 75-DEG water bath. And (4) ultrasonically treating the etched titanium felt in an ultrasonic container for 5 minutes by using deionized water until the surface of the etched titanium felt is clean.

(2) In a potassium chloride solution with the concentration of 120 millimole/liter, a chloroplatinic acid solution with the concentration of 3 millimole/liter is prepared and is completely dissolved in ultrasonic.

(3) Electrodeposition is carried out by adopting a three-electrode system under the constant temperature water bath at 25 ℃. Wherein, the titanium felt is used as a working electrode, the platinum sheet is used as a counter electrode, and the saturated calomel electrode is used as a reference electrode. And carrying out electrodeposition for 5min under a constant potential of-0.5V, taking out, washing with deionized water, and drying in an oven at 120 ℃ to obtain the porous array electrode.

The titanium felt and the porous array electrode are characterized:

the scanning electron microscope image of the internal structure of the titanium felt is shown in fig. 12, and people can clearly see that the titanium felt is formed by stacking superfine titanium wires instead of only one layer, so that the secondary array structure on the middle platinum wire of the titanium felt is not easy to fall off and is more stable.

Referring to fig. 13, a scanning electron microscope image of a platinum secondary array structure grown on a titanium felt substrate shows that the secondary array structure is spherical, that is, a flaky secondary structure is radially grown on the surface of a hemispherical or semi-ellipsoidal primary structure, so that the roughness of the surface of the porous array electrode is greatly increased, and the wetting capacity of water is further increased. As can be seen in FIG. 13, the platelets have a length of 50-500 nm, a width of 50-300 nm, and a thickness of 4-20 nm.

The porous array electrode was tested for wettability and bubble adhesion under water:

FIG. 14 is a photograph of a contact angle of the porous array electrode-water droplet in example 8, which was measured to be 53 °. FIG. 15 is a photograph of the contact angle of the porous array electrode-bubbles in example 8, which was measured to be 154 °. Under water, the behavior of air bubbles on the electrode surface is opposite to the wetting condition of water drops in the air on the electrode surface. While we refer to solid surfaces with bubble contact angles greater than 150 deg. as ultraphobic surfaces. The surface of the porous array electrode is a super-porous surface. The bubble adhesion under water test is shown in figure 16. FIG. 16 shows that: the bubbles have a small interaction force with the secondary array structure of only 2.5 μ N.

Example 9

Referring to the method in example 8, step (1) is to etch the titanium sheet with oxalic acid solution with a mass fraction of 15% for 2 hours under the condition of 90 ° water bath. In the step (2), a chloroplatinic acid solution with the concentration of 6 millimoles per liter is prepared in a potassium chloride solution with the concentration of 120 millimoles per liter, and the solution is completely dissolved in ultrasound. In the step (3), the concentration is controlled at-15 mA/cm²Electrodeposition was carried out under constant current, the other steps were the same as in example 8, and a porous array electrode was finally obtained.

The titanium sheet and the porous array electrode are characterized: the scanning electron microscope of the etched titanium sheet substrate is shown in the attached figure 17. The scanning electron microscope image of the platinum secondary array structure grown on the titanium sheet substrate is shown in fig. 18, the overall appearance of the secondary array structure is sea urchin-shaped, namely, a conical secondary structure is radially grown on the surface of the hemispherical primary structure, so that the roughness of the surface of the porous array electrode is greatly increased, and the wetting capacity of water is further increased. As can be seen in FIG. 18, the length of the taper is 50-500 nm, and the width of the base of the taper is 50-300 nm. The secondary nano structure is in a sharp-pointed shape, the length of the secondary nano structure is H1, the overall maximum length of the primary array structure and the secondary nano structure is recorded as H2, and H1 is less than or equal to 1/2H 2. The distance between the top centers of the adjacent secondary nanostructures is generally (more than half) provided with gaps larger than 80nm, and the gaps shown in fig. 18 by way of example are 80.5nm and 122.5nm, so that the formed nano bubbles are not easy to contact and fuse with each other, the gas permeability of the surface of the electrode is effectively improved, the bubbles can be separated from the surface of the electrode in a nanoscale, and water-soluble nano bubbles are formed.

FIG. 19 is a photograph of a contact angle of the porous array electrode-water droplet in example 9, which was measured to be 47 °. FIG. 20 is a photograph of a contact angle of the porous array electrode-bubbles in example 9, which was measured to be 130 °. The bubble adhesion under water test is shown in figure 21. FIG. 21 shows that: the bubbles have a small interaction force with the secondary array structure of only 7.3 μ N.

Example 10

Referring to the method of example 8, electrodeposition was carried out in step (3) using a three-electrode system in a thermostatic water bath at 50 ℃. Otherwise, as in example 8, a porous array electrode was finally obtained.

The porous array electrode is characterized:

a scanning electron micrograph of the porous array electrode obtained in example 10 is shown in FIG. 22. As can be seen in FIG. 22, the platelet has a length of 50-400 nm and a width of 50-400 nm, and the thickness of the platelet is 4-15 nm.

Example 11

Referring to the method in example 8, the film can be taken out after electrodeposition for 5min at a constant potential of-0.6V in step (3). Otherwise, as in example 8, a porous array electrode was finally obtained.

The porous array electrode is characterized:

a scanning electron micrograph of the resulting porous array electrode is shown in FIG. 23. As can be seen in FIG. 23, the platelets have a length of 50-900 nm, a width of 50-900 nm, and a thickness of 4-10 nm.

Example 12

Referring to the method of example 8, in step (3), the solution was first deposited in a 120 mM potassium chloride solution at a constant potential of-0.5V for 3min, and then in a 120 mM potassium nitrate solution at a constant potential of-0.3V for 5 min. Otherwise, as in example 8, a porous array electrode was finally obtained.

The porous array electrode is characterized:

a scanning electron micrograph of the resulting porous array electrode is shown in FIG. 24. The length of the cone is 200-400 nm, and the width of the bottom of the cone is 100-800 nm. The spacing between adjacent secondary nanostructure tip centers is generally (more than half) greater than 80nm with voids of 115nm and 163nm as shown by example in fig. 24. In the preparation method, the electrodeposition step is firstly carried out in a chloride solution for a period of time, and then the electrodeposition step is carried out in a nitrate solution, so that the spikes are more prominent, i.e. thicker and longer.

Example 13

The porous array electrode prepared in example 8 was used as a hydrogen-evolving cathode in an existing water electrolysis apparatus with a hydrogen-enriching cup, a titanium electrode was used as an anode, and an N117 type proton membrane was used. The electrode sheet has a size of 5cm²The electrolysis current applied under normal pressure was 1A, and the electrolysis time was 10 min.

The concentration of the dissolved hydrogen in the water is measured by a hydrogen pen test, and the size of the dissolved hydrogen bubbles in the water is measured by a nanosight instrument.

Specific data: as shown in fig. 25, the hydrogen bubble size distribution is evident that the bubble size is in the nanometer scale, and in actual multiple measurements, the bubble diameter is mainly distributed below 350nm, and the quantity of nanobubbles is mainly concentrated below 200nm with the increase of the standing time. As shown in FIG. 26, the hydrogen concentration in water varied, and the hydrogen concentration in the water averaged 2.0ppm and the hydrogen content in the water was 2.5ppm at the maximum in the test.

Example 14

The porous array electrode prepared in example 9 was used as a hydrogen-evolving cathode in an existing water electrolysis apparatus with a hydrogen-enriching cup, a titanium electrode was used as an anode, and an N117 type proton membrane was used. The electrode sheet has a size of 5cm²The electrolysis current applied under normal pressure was 1A, and the electrolysis time was 10 min.

Specific data: as shown in fig. 27, the hydrogen bubble size distribution is evident that the bubble size is in the nanometer scale, and in actual multiple measurements, the bubble diameter is mainly distributed below 350nm, and the quantity of nanobubbles is mainly concentrated below 200nm with the increase of the standing time. As shown in FIG. 28, the hydrogen concentration in water varied, and the hydrogen concentration in the water averaged 1.9ppm and the hydrogen content in the water was at most 2.5 ppm.

Example 15

The porous array electrode prepared in example 12 was used as a hydrogen-evolving cathode in an existing water electrolysis apparatus with a hydrogen-enriching cup, a titanium electrode was used as an anode, and an N117 type proton membrane was used. The electrode sheet has a size of 5cm²The electrolysis current applied under normal pressure was 1A, and the electrolysis time was 10 min.

Specific data: as shown in fig. 29, which is a hydrogen bubble size distribution, it can be clearly seen that the bubble size is in the nanometer scale, and in actual multiple measurements, the bubble diameter is mainly distributed below 350nm, and the number of nanobubbles is mainly concentrated below 200nm with the increase of the standing time. As shown in FIG. 30, the hydrogen concentration in water varied, and the average hydrogen concentration was 2.1ppm and the hydrogen content in water was 2.6ppm at the maximum in the test.

Comparative example 1

In the prior research, Li Yingjie et al (Li, Yingjie, Zhang, Haichuan, Xu, Tianhao, etc. Under-Water Superporous Pine-Shaped Pt Nanoarray Electrode for ultra high-Performance moisture Evolution [ J ]. Advanced Functional Materials,25(11):1737-1744, the academic papers are that the construction of a novel nano array Electrode and the application thereof in the electro-catalytic reaction of gas participation [ D ], Li Jie, Beijing chemical university, 2017) obtain a dendritic Pt nano array by an electro-deposition method by using carbon paper as a counter Electrode in a potassium nitrate solution.

The structure and parameter characteristics of the pine branch-shaped Pt nano array material are as follows:

the primary structure is cone-shaped, and the secondary structure is saw-toothed, see the attached fig. 31 and 32 of the specification.

The maximum spacing between the centers of the tips of adjacent secondary sawtooth-shaped structures is less than 75nm, the maximum spacing between adjacent secondary structures is 72nm, and the smaller spacing is only 31 nm.

The length of the conical primary structure is H3, and the maximum equivalent diameter length of the spheroidal unit in which the conical primary structure is located is recorded as H4, H3>1/2H 4.

The dendritic Pt nano array material effectively reduces the bubble separation size, but the Pt nano array is in a cone shape close to the micron level, the distance of the secondary sawtooth-shaped structure is short, generated bubbles are easy to fuse with each other, the separation size of the bubbles is still in the micron level, the bubble adhesion force is larger than 10 mu N, and nano-scale hydrogen bubbles cannot be generated. The Liangjie experiment is to explore micron-sized bubbles, and cannot generate nano-bubbles. The electrodes of this patent produce nanobubbles, both at a completely different conceptual level.

The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. An electrolytic water tubular electrode (10), characterized in that the tubular electrode (10) comprises an ion exchange membrane (2), a hollow inner layer tube (1) and a hollow outer layer tube (3) which are coaxially arranged;

wherein the ion exchange membrane (2) is filled between the inner layer tube (1) and the outer layer tube (3);

the inner layer tube (1) is an electrolytic water anode tube, and the outer layer tube (3) is an electrolytic water cathode tube; or the inner layer tube (1) is an electrolytic water cathode tube, and the outer layer tube (3) is an electrolytic water anode tube;

the ion exchange membrane (2) comprises a proton exchange membrane or an anion exchange membrane;

the inner layer pipe (1) and the outer layer pipe (3) are conductive pipes with air-permeable and water-permeable pipe walls.

2. The tubular electrode (10) according to claim 1, characterized in that the inner and/or outer surface of the electrolytic water anode tube 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 elements such as metallic 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, rhodium and silver;

the anode tube is made of metal or carbon-based porous conductive material.

3. The tubular electrode (10) according to claim 1, characterized in that the inner and/or outer surface of the electrolytic water cathode tube is coated and/or grown with a cathode catalyst; the cathode catalyst is selected from:

the cathode tube is made of metal or carbon-based porous conductive material.

4. The tubular electrode (10) of claim 1,

the cathode tube is provided with a porous array electrode, and the porous array electrode comprises:

a porous electrically conductive substrate and a primary array structure grown on the porous electrically conductive substrate, each cell of the primary array structure being at least a portion of a sphere or an ellipsoid in shape; secondary nanostructures in the form of platelets, cones, or spikes radially grown on the surface of each element of the primary array structure;

preferably, the primary array structure and secondary nanostructures are selected from platinum, ruthenium, iridium, palladium, rhodium, or silver;

preferably, the primary array structure and the secondary nanostructure are both platinum;

(3) and (3) in the mixed solution obtained in the step (2), performing electrodeposition by adopting a three-electrode system, wherein the porous conductive substrate obtained in the step (1) is a working electrode, and taking out, cleaning and drying after electrodeposition is performed for a period of time to obtain the porous array electrode.

5. The tubular electrode according to claim 1, characterized in that it is sealed at one end by an insulating layer, an inner tube (1) or an outer tube (3).

6. An apparatus for electrolyzing water capable of generating micro-nano hydrogen-rich water, characterized in that it comprises an electrolyzing water tubular electrode (10) according to any one of claims 1 to 5.

7. The water electrolysis device according to claim 6, wherein 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) when in use;

the design of the water electrolysis device is as follows:

the water electrolysis device is a hydrogen-rich cup or a hydrogen-rich machine and comprises an electrolysis device base, wherein the electrolysis device base is provided with: an insulating fixed plate (101) having a through hole and at least one tubular electrode (10) according to claim 2 or 3;

wherein each tubular electrode (10) is arranged on the fixing plate (101) in a manner that the sealed end faces upwards, and in a manner that all through holes on the fixing plate (101) are enclosed inside the anode tube;

8. The water electrolysis device according to claim 6, wherein 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) when in use;

the design of the water electrolysis device is as follows:

the water electrolysis device is a pipeline for producing hydrogen-rich water, and comprises an electrolysis device base, wherein the electrolysis device base is provided with: an insulating fixed plate (101) having a through hole and at least one tubular electrode (10) according to claim 2 or 3; wherein each tubular electrode (10) is arranged on the fixing plate (101) in a manner that the sealed end faces upwards, the tubular electrode is arranged in a manner that all through holes in the fixing plate (101) are enclosed inside the anode tube, the through holes are enclosed in each anode tube, the periphery of the base of the electrolysis device is sealed by the tube wall of the tube, only a tube water flow inlet (20) and a tube water flow outlet (21) are arranged, and the fixing plate (101) is a part of the tube wall of the tube.

9. The water electrolysis device according to claim 6, wherein when the inner tube (1) is a cathode tube and the outer tube (3) is an anode, water is inside the inner tube (1) when in use;

the design of the water electrolysis device is as follows:

the water electrolysis device comprises two insulating fixed plates (101) which are arranged in parallel and are provided with through holes, at least one tubular electrode (10) as claimed in claim 1, and a cylindrical sealed shell (102), wherein a water inlet (102-1), a water outlet and an oxygen outlet (102-2) are arranged on the cylindrical sealed shell (102);

wherein both ends of each tubular electrode (10) are arranged on the fixing plate (101) in a way that all through holes on the fixing plate (101) are enclosed inside the cathode tube (1);

the water inlet (102-1) and the water outlet are communicated with the through hole;

the oxygen outlet (102-2) is isolated from the through hole;

the outer diameter of the fixing plate (101) is equal to the inner diameter of the housing (102).

10. The application of the water electrolysis device capable of generating micro-nano hydrogen-enriched water is characterized in that the device can also be used for supplying oxygen and oxygen-enriched water.

11. Use of an electrolytic water device according to claim 6 in bathing.

12. Use of an electrolytic water device according to any one of claims 7 to 9 in bathing, agricultural irrigation, hydrogen absorption, hydrogen-enriched cabin health care, or food preservation.

13. Use of the electrolytic water device of claim 10 in aquaculture, sewage treatment, or oxygen uptake devices.