Water electrolysis equipment

Abstract

The invention relates to water electrolysis equipment. The water electrolysis equipment comprises an electrolysis container, an anode and a cathode, the electrolysis container comprises a first electrolysis pipeline, a first connecting pipeline, a second connecting pipeline and a second electrolysis pipeline which are communicated in sequence, the first connecting pipeline and the second connecting pipeline are both inclined to the horizontal plane, an included angle is formed between every two adjacent pipelines, and the higher end of the first connecting pipeline is connected with the higher end of the second connecting pipeline; the lower end of the first connecting pipeline is connected with the lower end of the first electrolysis pipeline, and the lower end of the second connecting pipeline is connected with the lower end of the second electrolysis pipeline; the anode is arranged in the first electrolysis pipeline, and the cathode is arranged in the second electrolysis pipeline. According to the structural design, exchange of electrolyte after electrolysis can be well reduced, mixing of oxygen and hydrogen dissolved in the electrolyte is reduced, and the gas purity is improved. According to the water electrolysis equipment, a diaphragm does not need to be arranged, and high gas purity can be obtained under the condition that the power supply is low in power.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic hydrogen production, and in particular to a water electrolysis device. Background Art

[0002] As a clean energy, the carbon emission problem in the production process of hydrogen is increasingly concerned. The traditional method of producing hydrogen from fossil fuels still produces a large amount of carbon dioxide emissions. Using renewable energy to produce hydrogen through water electrolysis provides a solution, but the current renewable energy hydrogen production technology is affected by technical limitations, and energy fluctuates with the weather; in the traditional water electrolysis hydrogen production system, the gas purity produced by the diaphragm at low power is low, and when the gas purity is low to a certain extent, the equipment will be locked. In addition, due to the presence of the diaphragm, the mass transfer efficiency is slowed down, and a certain resistance will be formed, affecting the efficiency of hydrogen production. Summary of the invention

[0003] Based on this, it is necessary to provide a water electrolysis device to solve the problem of low purity of gas produced at low power.

[0004] The scheme of the present invention is as follows:

[0005] A water electrolysis device comprises an electrolysis container, an anode and a cathode;

[0006] The electrolysis container includes a first electrolysis pipe, a first connecting pipe, a second connecting pipe and a second electrolysis pipe which are connected in sequence, wherein the first connecting pipe and the second connecting pipe are both arranged obliquely to a horizontal plane, and adjacent pipes are arranged at an angle, wherein the higher end of the first connecting pipe is connected to the higher end of the second connecting pipe, the lower end of the first connecting pipe is connected to the lower end of the first electrolysis pipe, and the lower end of the second connecting pipe is connected to the lower end of the second electrolysis pipe; the anode is arranged in the first electrolysis pipe, and the cathode is arranged in the second electrolysis pipe.

[0007] In one embodiment, the first electrolysis pipe is arranged to be inclined with respect to a horizontal plane, and the anode extends along the axial direction of the first electrolysis pipe and is arranged on the upper inner wall of the first electrolysis pipe.

[0008] In one embodiment, the second electrolysis pipe is arranged obliquely to a horizontal plane, and the cathode extends along the axial direction of the second electrolysis pipe and is arranged on the upper inner wall of the second electrolysis pipe.

[0009] In one embodiment, the angle between the first electrolysis pipe and the first connecting pipe is 30°~60°.

[0010] In one embodiment, the angle between the second electrolysis pipe and the second connecting pipe is 30° to 60°.

[0011] In one embodiment, a first exhaust hole is provided at the higher end of the first electrolysis pipe.

[0012] In one embodiment, a second exhaust hole is provided at the higher end of the second electrolysis pipe.

[0013] In one embodiment, an exhaust hole is provided on the upper side of the connection position between the first connecting pipe and the second connecting pipe.

[0014] In one embodiment, the water electrolysis equipment further includes a first vibration device, and the first vibration device is connected to the first connecting pipe.

[0015] The water electrolysis equipment further includes a second vibration device, and the second vibration device is connected to the second connecting pipe.

[0016] In one embodiment, the water electrolysis equipment also includes an electrolyte circulation purification device, which includes an electrolyte storage container and an electrolyte purification component. The electrolysis container is provided with a liquid inlet and a liquid outlet. The electrolyte storage container is connected to the liquid inlet, and the electrolyte purification component is connected to the liquid outlet. The electrolyte purification component is connected to the electrolyte storage container to supply purified electrolyte to the electrolyte storage container.

[0017] In one embodiment, the liquid inlet is respectively provided at the lower end of the first electrolysis pipe and the lower end of the second electrolysis pipe.

[0018] The first connecting pipe is provided with the liquid outlet between the lower end and the upper end, and the second connecting pipe is also provided with the liquid outlet between the lower end and the upper end.

[0019] In one embodiment, the anode and / or the cathode are prepared by the following steps:

[0020] Add titanium aluminum carbide dropwise to an acidic solution containing lithium fluoride, stir and heat to react, wash the reaction product until the pH value is 6-7, and then perform ultrasonic treatment to obtain a colloidal solution;

[0021] Place porous nickel in the colloidal solution, react at 40° C. to 60° C. for 12 h to 24 h to obtain a hydrophilic catalyst;

[0022] Placing the hydrophilic catalyst as a working electrode in a first precursor electrolyte, wherein the first precursor electrolyte comprises 10 to 30 parts of water, 1 to 2 parts of nickel nitrate, 0.5 to 1 part of ferric sulfate and 10 to 30 parts of ethylene glycol, and performing a first electrochemical deposition treatment to obtain a pre-deposition product;

[0023] The pre-deposited product is placed as a working electrode in a second precursor electrolyte, wherein the second precursor electrolyte contains 30 to 50 parts of water, 0.3 to 0.4 parts of nickel nitrate, 0.1 to 0.2 parts of ferric nitrate, 7 to 8 parts of thiourea and 0.5 parts of potassium dihydrogen phosphate, and a second electrochemical deposition treatment is performed to obtain the electrode material.

[0024] In one embodiment, the acidic solution containing lithium fluoride is prepared by the following steps:

[0025] Take 0.5~1 parts of lithium fluoride and mix with 10~12 parts of hydrochloric acid with a mass concentration of 30%~32%.

[0026] In one embodiment, the mass ratio of the lithium fluoride to the titanium aluminum carbide is (1-2): (1-2).

[0027] In one embodiment, the heating reaction is carried out at a temperature of 40°C to 50°C and for a time of 12h to 36h.

[0028] In one embodiment, the cleaning process includes: centrifugal cleaning with hydrochloric acid having a mass concentration of 5% to 10% at a centrifugal speed of 5000 r / min to 8000 r / min, and then washing with water.

[0029] In one embodiment, the ultrasonic treatment comprises: ultrasonically oscillating the solution after the cleaning treatment for 2h~5h under a protective gas atmosphere, with a vibration power of 200W~300W.

[0030] In one of the embodiments, in the first electrochemical deposition process, a platinum electrode is used as a counter electrode.

[0031] In one embodiment, the voltage of the first electrochemical deposition treatment is 2V~3V, and the time is 200s~500s.

[0032] In one embodiment, in the second electrochemical deposition process, a platinum sheet is used as a counter electrode, and a mixture of silver and silver chloride is used as a reference electrode.

[0033] In one embodiment, the voltage of the second electrochemical deposition process is 2V~3V, and the time is 800s~1000s.

[0034] Compared with the traditional solution, the above water electrolysis equipment has the following beneficial effects:

[0035] The electrolysis container in the above-mentioned electrolysis water device includes a first electrolysis pipeline, a first connecting pipeline, a second connecting pipeline and a second electrolysis pipeline which are connected in sequence, and the adjacent pipelines are arranged at an angle, wherein the first connecting pipeline and the second connecting pipeline are arranged obliquely to the horizontal plane, and the electrolysis container is W-shaped as a whole, and the anode is arranged in the first electrolysis pipeline, and the cathode is arranged in the second electrolysis pipeline. The above-mentioned structural design can better reduce the exchange of the electrolyte after electrolysis at the anode and the electrolyte after electrolysis at the cathode, which is conducive to reducing the mixing of oxygen and hydrogen dissolved in the electrolyte and improving the gas purity. The above-mentioned electrolysis water device does not need to be provided with a diaphragm, and can also obtain a higher gas purity when the power supply is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG1 is a schematic structural diagram of a water electrolysis device according to an embodiment.

[0037] Description of reference numerals:

[0038] 10. Water electrolysis equipment; 100. Electrolysis container; 200. Anode; 300. Cathode; 110. First electrolysis pipeline; 120. First connecting pipeline; 130. Second connecting pipeline; 140. Second electrolysis pipeline; 151. First exhaust hole; 152. Second exhaust hole; 410. First vibration device; 420. Second vibration device; 121. First impact resistance part; 131. Second impact resistance part; 153. Exhaust hole; 500. Electrolyte circulation purification device; 510. Electrolyte storage container; 520. Electrolyte purification component; 531. First liquid supply pipeline; 532. Second liquid supply pipeline; 541. First liquid outlet pipeline; 542. Second liquid outlet pipeline; 550. Reflux pipeline; 561. First delivery pump; 562. Second delivery pump; 563. Third delivery pump; 564. Fourth delivery pump. DETAILED DESCRIPTION

[0039] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present invention, so the present invention is not limited by the specific embodiments disclosed below.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0041] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0042] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0043] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0044] Please refer to FIG. 1 , a water electrolysis device 10 according to an embodiment includes an electrolysis container 100 , an anode 200 , and a cathode 300 .

[0045] The electrolysis container 100 includes a first electrolysis pipe 110, a first connecting pipe 120, a second connecting pipe 130 and a second electrolysis pipe 140 which are connected in sequence. The first connecting pipe 120 and the second connecting pipe 130 are both arranged obliquely to the horizontal plane, and adjacent pipes are arranged at an angle.

[0046] The upper end of the first connecting pipe 120 is connected to the upper end of the second connecting pipe 130. The lower end of the first connecting pipe 120 is connected to the lower end of the first electrolysis pipe 110. The lower end of the second connecting pipe 130 is connected to the lower end of the second electrolysis pipe 140. The anode 200 is disposed in the first electrolysis pipe 110. The cathode 300 is disposed in the second electrolysis pipe 140.

[0047] The electrolysis container 100 in the above-mentioned electrolysis water device 10 includes a first electrolysis pipeline 110, a first connecting pipeline 120, a second connecting pipeline 130 and a second electrolysis pipeline 140 which are connected in sequence, and the adjacent pipelines are arranged at an angle, wherein the first connecting pipeline 120 and the second connecting pipeline 130 are arranged obliquely to the horizontal plane, and the electrolysis container 100 is W-shaped as a whole, and the anode 200 is arranged in the first electrolysis pipeline 110, and the cathode 300 is arranged in the second electrolysis pipeline 140. The above-mentioned structural design can well reduce the exchange of the electrolyte after electrolysis at the anode 200 and the electrolyte after electrolysis at the cathode 300, which is conducive to reducing the mixing of oxygen and hydrogen dissolved in the electrolyte and improving the gas purity. The above-mentioned electrolysis water device 10 does not need to be provided with a diaphragm, and can also obtain a higher gas purity when the power supply is low.

[0048] In some examples, the first electrolysis pipe 110 is arranged to be inclined to the horizontal plane, and the anode 200 extends along the axial direction of the first electrolysis pipe 110 and is arranged on the upper inner wall of the first electrolysis pipe 110. In this way, the oxygen generated at the anode 200 is discharged upward along the upper inner wall of the first electrolysis pipe 110, reducing the oxygen entering the first connecting pipe 120, reducing the mixing of oxygen and hydrogen in the electrolyte, and improving the gas purity.

[0049] The height of the lower end of the anode 200 is preferably higher than the height of the lower end of the first electrolysis pipe 110 to reduce the entry of oxygen into the first connecting pipe 120. For example, in some examples, the distance between the lower end of the anode 200 and the lower end of the first electrolysis pipe 110 is 5 mm to 10 mm, specifically 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, etc.

[0050] The second electrolysis pipe 140 is arranged obliquely to the horizontal plane, and the cathode 300 extends along the axial direction of the second electrolysis pipe 140 and is arranged on the upper inner wall of the second electrolysis pipe 140. In this way, the hydrogen generated at the cathode 300 is discharged upward along the upper inner wall of the second electrolysis pipe 140, reducing the entry of hydrogen into the second connecting pipe 130, reducing the mixing of oxygen and hydrogen in the electrolyte, and improving the gas purity.

[0051] The height of the lower end of the cathode 300 is preferably higher than the height of the lower end of the second electrolysis pipe 140 to reduce the entry of hydrogen into the second connecting pipe 130. For example, in some examples, the distance between the lower end of the cathode 300 and the lower end of the second electrolysis pipe 140 is 5 mm to 10 mm, specifically 5 mm, 6 mm, 7 mm, 8 mm, 9 mm, 10 mm, etc.

[0052] In some examples, the angle between the first electrolysis pipe 110 and the first connecting pipe 120 is an acute angle. For example, in some examples, the angle between the first electrolysis pipe 110 and the first connecting pipe 120 is 30° to 60°, specifically 30°, 35°, 40°, 45°, 50°, 55°, 60°, etc.

[0053] In some of the examples, the angle between the second electrolysis pipe 140 and the second connecting pipe 130 is an acute angle. For example, in some of the examples, the angle between the second electrolysis pipe 140 and the second connecting pipe 130 is 30° to 60°, specifically 30°, 35°, 40°, 45°, 50°, 55°, 60°, etc.

[0054] In some of the examples, the angle between the first connecting pipe 120 and the second connecting pipe 130 is an obtuse angle. For example, in some of the examples, the angle between the first connecting pipe 120 and the second connecting pipe 130 is 30° to 60°.

[0055] In some examples, a first exhaust hole 151 is disposed at a higher end of the first electrolysis pipe 110 . Oxygen generated at the anode 200 is discharged upward through the first exhaust hole 151 along the upper inner wall of the first electrolysis pipe 110 .

[0056] In some examples, a second exhaust hole 152 is disposed at a higher end of the second electrolysis pipe 140 . The hydrogen generated at the cathode 300 is discharged upward through the second exhaust hole 152 along the upper inner wall of the second electrolysis pipe 140 .

[0057] In some of the examples, the water electrolysis device 10 further includes a first vibration device 410, which is connected to the first connecting pipe 120. The gas dissolved in the electrolyte in the first connecting pipe 120 is discharged by the vibration of the first vibration device 410. In some of the examples, the first vibration device 410 is connected to the upper side of the first connecting pipe 120. The upper side of the first connecting pipe 120 is provided with a first impact-resistant portion 121, and the first impact-resistant portion 121 is made of a material with good impact resistance to prevent the first connecting pipe 120 from being damaged by vibration.

[0058] In some of the examples, the water electrolysis device 10 further includes a second vibration device 420, which is connected to the second connecting pipe 130. The gas dissolved in the electrolyte in the second connecting pipe 130 is discharged by the vibration of the second vibration device 420. In some of the examples, the second vibration device 420 is connected to the upper side of the second connecting pipe 130. The upper side of the second connecting pipe 130 is provided with a second impact-resistant portion 131, and the second impact-resistant portion 131 is made of a material with good impact resistance to prevent the second connecting pipe 130 from being damaged by vibration.

[0059] In some examples, an exhaust hole 153 is provided on the upper side of the connection position between the first connecting pipe 120 and the second connecting pipe 130. The gas in the first connecting pipe 120 and the second connecting pipe 130 is discharged through the exhaust hole 153 to avoid gas scattering and improve gas purity.

[0060] In some examples, the water electrolysis device 10 further includes an electrolyte circulation purification device 500. The electrolyte circulation purification device 500 includes an electrolyte storage container 510 and an electrolyte purification component 520. The electrolysis container 100 is provided with an inlet and an outlet. The electrolyte storage container 510 is connected to the inlet. The electrolyte storage container 510 is used to store electrolyte and can supply electrolyte to the electrolysis container 100 through the inlet.

[0061] The electrolyte purification component 520 is connected to the liquid outlet, and the electrolyte in the electrolytic container 100 enters the electrolyte purification component 520 through the liquid outlet for purification. The electrolyte purification component 520 is connected to the electrolyte storage container 510 to supply the purified electrolyte to the electrolyte storage container 510.

[0062] In some examples, a lower end of the first electrolysis pipe 110 and a lower end of the second electrolysis pipe 140 are respectively provided with a liquid inlet.

[0063] In some examples, the first connecting pipe 120 is provided with a liquid outlet between the lower end and the upper end, and the second connecting pipe 130 is also provided with a liquid outlet between the lower end and the upper end.

[0064] As shown in FIG. 1 , in some examples, the electrolyte circulation purification device 500 further includes a first liquid supply pipeline 531, a second liquid supply pipeline 532, a first liquid outlet pipeline 541, a second liquid outlet pipeline 542, and a reflux pipeline 550. One end of the first liquid supply pipeline 531 is connected to the electrolyte storage container 510. The other end of the first liquid supply pipeline 531 is connected to the lower end of the first electrolysis pipeline 110. One end of the second liquid supply pipeline 532 is connected to the electrolyte storage container 510. The other end of the second liquid supply pipeline 532 is connected to the lower end of the second electrolysis pipeline 140. Both ends of the first liquid outlet pipeline 541 are respectively connected to the first connecting pipeline 120 and the electrolyte purification component 520. Both ends of the second liquid outlet pipeline 542 are respectively connected to the second connecting pipeline 130 and the electrolyte purification component 520. Both ends of the reflux pipeline 550 are respectively connected to the electrolyte storage container 510 and the electrolyte purification component 520.

[0065] In some examples, the first liquid supply pipeline 531 is provided with a first delivery pump 561, and the first delivery pump 561 is used to deliver the electrolyte from the electrolyte storage container 510 to the first electrolysis pipeline 110 and the first connecting pipeline 120. In some examples, the first delivery pump 561 is disposed at the connection position between the first liquid supply pipeline 531, the first electrolysis pipeline 110 and the first connecting pipeline 120.

[0066] In some examples, the second liquid supply pipeline 532 is provided with a second delivery pump 562, and the second delivery pump 562 is used to deliver the electrolyte from the electrolyte storage container 510 to the second electrolysis pipeline 140 and the second connecting pipeline 130. In some examples, the second delivery pump 562 is disposed at the connection position between the second liquid supply pipeline 532, the second electrolysis pipeline 140 and the second connecting pipeline 130.

[0067] In some examples, the first liquid outlet pipe 541 is provided with a third delivery pump 563 , and the third delivery pump 563 is used to deliver the electrolyte from the first connecting pipe 120 to the electrolyte purification component 520 .

[0068] In some examples, the second liquid outlet pipe 542 is provided with a fourth delivery pump 564 , and the fourth delivery pump 564 is used to deliver the electrolyte from the second connecting pipe 130 to the electrolyte purification component 520 .

[0069] The above structural design enables most of the electrolyte after electrolysis to be transported to the electrolyte purification component 520 for purification, and a small part of the electrolyte is exchanged through the first connecting pipe 120 and the second connecting pipe 130, which can improve the purity of the gas.

[0070] The electrolysis container 100 in the above-mentioned electrolysis water device 10 includes a first electrolysis pipeline 110, a first connecting pipeline 120, a second connecting pipeline 130 and a second electrolysis pipeline 140 which are connected in sequence, and the adjacent pipelines are arranged at an angle, wherein the first connecting pipeline 120 and the second connecting pipeline 130 are arranged obliquely to the horizontal plane, and the electrolysis container 100 is W-shaped as a whole, and the anode 200 is arranged in the first electrolysis pipeline 110, and the cathode 300 is arranged in the second electrolysis pipeline 140. The above-mentioned structural design can well reduce the exchange of the electrolyte after electrolysis at the anode 200 and the electrolyte after electrolysis at the cathode 300, which is conducive to reducing the mixing of oxygen and hydrogen dissolved in the electrolyte and improving the gas purity. The above-mentioned electrolysis water device 10 does not need to be provided with a diaphragm, and can also obtain a higher gas purity when the power supply is low.

[0071] In some of these examples, the anode and / or cathode are made of hydrophilic materials. The hydrophilic design of the electrodes ensures that the generated gas does not adhere to the electrodes, ensuring smooth gas discharge and improving gas purity.

[0072] In some examples, the anode and / or cathode are prepared by the following steps:

[0073] Step S110, titanium aluminum carbide (Ti3AlC2) is added dropwise to an acidic solution containing lithium fluoride (LiF), and the mixture is stirred and heated for reaction. The reaction product is washed until the pH value is 6-7, and then ultrasonically treated to obtain a colloidal solution.

[0074] Through step S110, a MXene catalyst with strong hydrophilicity can be prepared.

[0075] In some of these examples, an acidic solution containing lithium fluoride is prepared by the following steps:

[0076] Take lithium fluoride and hydrochloric acid and mix them. The mass fraction of lithium fluoride is, for example, 0.5 to 1 part, specifically, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, etc. The mass fraction of hydrochloric acid is, for example, 10 to 12 parts, specifically, for example, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, etc. The mass concentration of hydrochloric acid is, for example, 30% to 32%, specifically, for example, 30%, 30.5%, 31%, 31.5%, 32%, etc.

[0077] The lithium fluoride and hydrochloric acid are mixed in, for example, stirring at 25° C. to 35° C. for 10 min to 20 min at a stirring speed of 100 r / min to 500 r / min.

[0078] In some of the examples, the mass ratio of lithium fluoride to titanium aluminum carbide is (1-2):(1-2), specifically 1:1, 1:2, 2:1, 1.5:1, 1:1.5, etc.

[0079] In some of the examples, the titanium aluminum carbide is added at a rate of 0.01 parts of titanium aluminum carbide per 10 seconds.

[0080] In some examples, the temperature of the heating reaction is 40°C to 50°C, specifically 40°C, 42°C, 44°C, 46°C, 48°C, 50°C, etc. The time of the heating reaction is 12h to 36h, specifically 12h, 15h, 18h, 24h, 30h, 36h, etc.

[0081] In some examples, the cleaning process includes: centrifugal cleaning with hydrochloric acid having a mass concentration of 5% to 10%, the centrifugal speed is 5000 r / min to 8000 r / min, and then washing with water. The amount of hydrochloric acid used is, for example, 100 to 200 parts, specifically, for example, 100 parts, 120 parts, 140 parts, 160 parts, 180 parts, 200 parts, etc.

[0082] In some examples, the ultrasonic treatment includes: under a protective gas (such as nitrogen) atmosphere, ultrasonically vibrating the cleaned solution for 2h~5h, specifically 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, etc. The vibration power is 200W~300W, specifically 200W, 220W, 240W, 260W, 280W, 300W, etc.

[0083] Step S120, taking porous nickel and placing it in a colloidal solution, reacting it at 40° C. to 60° C. for 12 h to 24 h to obtain a hydrophilic catalyst.

[0084] Through step S120, a highly hydrophilic nickel-based MXenen catalyst can be prepared, which can reduce the attachment of bubbles, discharge the gas immediately after production, reduce retention, avoid gas exchange underwater, and ensure gas purity and the feasibility of low-power operation.

[0085] Step S130, placing a hydrophilic catalyst as a working electrode in a first precursor electrolyte, the first precursor electrolyte comprising 1-2 parts of nickel nitrate, 0.5-1 parts of ferric sulfate, 10-30 parts of ethylene glycol and 10-30 parts of water, performing a first electrochemical deposition treatment to obtain a pre-deposition product.

[0086] Through step S130, a layered double metal hydroxide is prepared on the surface of the nickel-based MXene catalyst, and the two are coupled to improve the catalytic efficiency. S is doped into the layered double metal hydroxide to improve the conductivity and improve the hydrogen production efficiency.

[0087] In some of these examples, the porous nickel is nickel foam.

[0088] In some of the examples, the porous nickel is first cleaned and then placed in a colloidal solution. In some of the examples, the cleaning of the porous nickel includes: washing the porous nickel with anhydrous ethanol, hydrochloric acid with a mass concentration of 8% to 10%, and water in sequence. For example, 100 to 20 parts of anhydrous ethanol are used for 10 to 20 parts of porous nickel, for example, 50 to 100 parts of hydrochloric acid are used, and for example, 300 to 500 parts of water are used. The water is preferably deionized water.

[0089] In some examples, the temperature of the colloidal solution is controlled at 40°C to 60°C, such as 40°C, 45°C, 50°C, 55°C, 60°C, etc. The vibration drying time is 12h to 24h, such as 12h, 15h, 20h, 22h, 24h, etc.

[0090] In some examples, the first precursor electrolyte includes 1-2 parts nickel nitrate, 0.5-1 parts iron sulfate, 10-30 parts ethylene glycol, and 10-30 parts water.

[0091] In some of these examples, the first electrochemical deposition process uses a platinum electrode as a counter electrode.

[0092] In some examples, the voltage of the first electrochemical deposition process is 2V to 3V, specifically 2V, 2.2V, 2.4V, 2.6V, 2.8V, 3V, etc. The time of the first electrochemical deposition process is 200s to 500s, specifically 200s, 250s, 300s, 350s, 400s, 450s, 500s, etc.

[0093] In some examples, after the first electrochemical deposition process is completed, the obtained hydrophilic catalyst is cleaned and dried, for example, with 200-500 parts of deionized water, and then placed in a vacuum drying oven and vacuum dried at 50° C.-70° C. for 8-12 hours.

[0094] Step S140, placing the pre-deposited product as a working electrode in a second precursor electrolyte, the second precursor electrolyte comprising 0.3-0.4 parts of nickel nitrate, 0.1-0.2 parts of ferric nitrate, 30-50 parts of water, 7-8 parts of thiourea and 0.5 parts of potassium dihydrogen phosphate, performing a second electrochemical deposition treatment to obtain an electrode material.

[0095] Through step S140, phosphate ions are used to support the layered double hydroxide to expand the interlayer distance, thereby improving the exchange efficiency of the electrolyte on its surface, improving the mass transfer efficiency, and improving the electrolysis efficiency.

[0096] In some examples, the second precursor electrolyte includes 0.3-0.4 parts of nickel nitrate, 0.1-0.2 parts of iron nitrate, 30-50 parts of water, 7-8 parts of thiourea, and 0.5 parts of potassium dihydrogen phosphate.

[0097] In some of the examples, a platinum sheet was used as a counter electrode and (silver / silver chloride, Ag / AgCl) was used as a reference electrode in the second electrochemical deposition process.

[0098] In some examples, the voltage of the second electrochemical deposition process is 2V-3V, specifically 2V, 2.2V, 2.4V, 2.6V, 2.8V, 3V, etc. The time of the second electrochemical deposition process is 800s-1000s, specifically 800s, 850s, 900s, 950s, 1000s, etc.

[0099] In some examples, after the second electrochemical deposition process is completed, the obtained electrode material is cleaned and dried, for example, using 300 to 500 parts of deionized water with a conductivity of 5 to 10 μS / cm, and then dried.

[0100] The following specific examples are provided to further illustrate the present invention. The present invention provides the following specific examples for a better understanding of the present invention, but is not limited to the specific implementation methods and does not limit the protection scope of the present invention.

[0101] Example 1

[0102] This embodiment provides a water electrolysis device.

[0103] The water electrolysis device 10 includes an electrolysis container 100 , an anode 200 , a cathode 300 , a first vibration device 410 , a second vibration device 420 , and an electrolyte circulation purification device 500 .

[0104] The electrolysis container 100 includes a first electrolysis pipe 110, a first connecting pipe 120, a second connecting pipe 130, and a second electrolysis pipe 140 that are connected in sequence. The first electrolysis pipe 110, the first connecting pipe 120, the second connecting pipe 130, and the second electrolysis pipe 140 are all arranged obliquely to the horizontal plane, and adjacent pipes are arranged at an angle. The angle between the first electrolysis pipe 110 and the first connecting pipe 120 is 30°, the angle between the second electrolysis pipe 140 and the second connecting pipe 130 is 30°, and the angle between the first connecting pipe 120 and the second connecting pipe 130 is 30°.

[0105] The upper end of the first connecting pipe 120 is connected to the upper end of the second connecting pipe 130. The lower end of the first connecting pipe 120 is connected to the lower end of the first electrolysis pipe 110. The lower end of the second connecting pipe 130 is connected to the lower end of the second electrolysis pipe 140. The anode 200 is disposed in the first electrolysis pipe 110. The cathode 300 is disposed in the second electrolysis pipe 140.

[0106] The anode 200 extends along the axial direction of the first electrolysis pipe 110 and is disposed on the upper inner wall of the first electrolysis pipe 110. The cathode 300 extends along the axial direction of the second electrolysis pipe 140 and is disposed on the upper inner wall of the second electrolysis pipe 140.

[0107] A first exhaust hole 151 is provided at a higher end of the first electrolysis pipe 110. A second exhaust hole 152 is provided at a higher end of the second electrolysis pipe 140. An exhaust hole 153 is provided at the upper side of the connection position between the first connecting pipe 120 and the second connecting pipe 130.

[0108] The first vibration device 410 is connected to the first connection pipe 120 . The second vibration device 420 is connected to the second connection pipe 130 .

[0109] The electrolyte circulation purification device 500 includes an electrolyte storage container 510, an electrolyte purification component 520, a first liquid supply pipeline 531, a second liquid supply pipeline 532, a first liquid outlet pipeline 541, a second liquid outlet pipeline 542 and a reflux pipeline 550. The electrolytic container 100 is provided with a liquid inlet and a liquid outlet. The electrolyte storage container 510 is connected to the liquid inlet. The electrolyte storage container 510 is used to store electrolyte and can supply electrolyte to the electrolytic container 100 through the liquid inlet.

[0110] One end of the first liquid supply pipe 531 is connected to the electrolyte storage container 510. The other end of the first liquid supply pipe 531 is connected to the lower end of the first electrolysis pipe 110. One end of the second liquid supply pipe 532 is connected to the electrolyte storage container 510. The other end of the second liquid supply pipe 532 is connected to the lower end of the second electrolysis pipe 140. Both ends of the first liquid outlet pipe 541 are respectively connected to the first connecting pipe 120 and the electrolyte purification component 520. Both ends of the second liquid outlet pipe 542 are respectively connected to the second connecting pipe 130 and the electrolyte purification component 520. Both ends of the reflux pipe 550 are respectively connected to the electrolyte storage container 510 and the electrolyte purification component 520.

[0111] The first liquid supply pipeline 531 is provided with a first delivery pump 561, which is disposed at the connection position between the first liquid supply pipeline 531 and the first electrolysis pipeline 110 and the first connecting pipeline 120. The first delivery pump 561 is used to pump liquid upward to transport the electrolyte from the electrolyte storage container 510 to the first electrolysis pipeline 110 and the first connecting pipeline 120. The second liquid supply pipeline 532 is provided with a second delivery pump 562, which is used to pump liquid upward to transport the electrolyte from the electrolyte storage container 510 to the second electrolysis pipeline 140 and the second connecting pipeline 130. The first liquid outlet pipeline 541 is provided with a third delivery pump 563, which is used to pump liquid downward to transport the electrolyte from the first connecting pipeline 120 to the electrolyte purification component 520. The second liquid outlet pipe 542 is provided with a fourth delivery pump 564 , which is used to pump liquid downward to deliver the electrolyte from the second connecting pipe 130 to the electrolyte purification component 520 .

[0112] The anode and cathode are prepared by the following steps:

[0113] Step 1, weigh 1 part of lithium fluoride and 10 parts of 32% hydrochloric acid, put them into a reactor lined with polytetrafluoroethylene (PTFE), stir them at 25°C for 10 minutes, and the stirring speed is 300r / min.

[0114] Step 2, add 0.8 parts of titanium aluminum carbide to the acidic solution containing lithium fluoride, and the dropping speed is 0.01 parts / 10 seconds. After the addition is completed, the temperature is raised to 40°C at 1°C / minute, the speed is kept unchanged, and stirring is continued for 20 hours. The reaction product is centrifuged and washed with 200 parts of 7% hydrochloric acid, the speed of the centrifuge is set at 5000r / min, and then washed with deionized water with a conductivity of 10μS / cm to a pH of 6. Under nitrogen protection, the solution is ultrasonically vibrated for 2 hours with a vibration power of 200W to obtain a colloidal solution.

[0115] Step 3, take another 10 parts of nickel foam (NF), wash them with 100 parts of anhydrous ethanol, 50 parts of 8% hydrochloric acid, and 300 parts of deionized water in sequence, then put the nickel foam into the above colloidal solution, shake and dry at 40°C for 12 hours to obtain a hydrophilic catalyst.

[0116] Step 4, weigh 1.5 parts of nickel nitrate (Ni(NO3)2·6H2O) and 1 part of ferric sulfate (FeSO4) and add them to a flask, add 130 parts of deionized water to the flask, stir for 10 minutes, and the stirring speed is 200r / min. Then add 10 parts of ethylene glycol to the flask, maintain the stirring speed, and stir for 20 minutes to prepare the first precursor electrolyte. The above-mentioned hydrophilic catalyst is used as the working electrode, and the platinum electrode is placed in the first precursor electrolyte as the counter electrode, and the electrodeposition is carried out at a voltage of 2V for 200s to obtain a pre-deposited product. The pre-deposited product is washed with 200 parts of deionized water, and then placed in a vacuum drying oven for vacuum drying at 50°C for 8h.

[0117] Step 5, weigh 0.3 parts of nickel nitrate (Ni(NO3)2·6H2O) and 0.1 parts of ferric nitrate (Fe(NO3)3·9H2O) and add them to a flask, add 30 parts to the flask and stir for 10 minutes at a stirring speed of 300r / min, then add 7 parts of thiourea, keep the speed constant, stir for 30 minutes, and finally add 0.5 parts of potassium dihydrogen phosphate, keep the speed constant, stir for 5 minutes to prepare a second precursor electrolyte. The above pre-deposited product is used as a working electrode, a platinum sheet is used as a counter electrode, and silver / silver chloride (Ag / AgCl) is used as a reference electrode. It is placed in the second precursor electrolyte for electrodeposition at a voltage of 2.5V for 800s, and then the working electrode is cleaned with 300 parts of deionized water with a conductivity of 5μS / cm to obtain an electrode material.

[0118] Example 2

[0119] This embodiment provides a water electrolysis device.

[0120] The water electrolysis device 10 includes an electrolysis container 100 , an anode 200 , a cathode 300 , a first vibration device 410 , a second vibration device 420 , and an electrolyte circulation purification device 500 .

[0121] The electrolysis container 100 includes a first electrolysis pipe 110, a first connecting pipe 120, a second connecting pipe 130, and a second electrolysis pipe 140 that are connected in sequence. The first electrolysis pipe 110, the first connecting pipe 120, the second connecting pipe 130, and the second electrolysis pipe 140 are all arranged obliquely to the horizontal plane, and adjacent pipes are arranged at an angle. The angle between the first electrolysis pipe 110 and the first connecting pipe 120 is 60°, the angle between the second electrolysis pipe 140 and the second connecting pipe 130 is 60°, and the angle between the first connecting pipe 120 and the second connecting pipe 130 is 60°.

[0122] The upper end of the first connecting pipe 120 is connected to the upper end of the second connecting pipe 130. The lower end of the first connecting pipe 120 is connected to the lower end of the first electrolysis pipe 110. The lower end of the second connecting pipe 130 is connected to the lower end of the second electrolysis pipe 140. The anode 200 is disposed in the first electrolysis pipe 110. The cathode 300 is disposed in the second electrolysis pipe 140.

[0123] The anode 200 extends along the axial direction of the first electrolysis pipe 110 and is disposed on the upper inner wall of the first electrolysis pipe 110. The cathode 300 extends along the axial direction of the second electrolysis pipe 140 and is disposed on the upper inner wall of the second electrolysis pipe 140.

[0124] A first exhaust hole 151 is provided at a higher end of the first electrolysis pipe 110. A second exhaust hole 152 is provided at a higher end of the second electrolysis pipe 140. An exhaust hole 153 is provided at the upper side of the connection position between the first connecting pipe 120 and the second connecting pipe 130.

[0125] The first vibration device 410 is connected to the first connection pipe 120 . The second vibration device 420 is connected to the second connection pipe 130 .

[0126] The electrolyte circulation purification device 500 includes an electrolyte storage container 510, an electrolyte purification component 520, a first liquid supply pipeline 531, a second liquid supply pipeline 532, a first liquid outlet pipeline 541, a second liquid outlet pipeline 542 and a reflux pipeline 550. The electrolytic container 100 is provided with a liquid inlet and a liquid outlet. The electrolyte storage container 510 is connected to the liquid inlet. The electrolyte storage container 510 is used to store electrolyte and can supply electrolyte to the electrolytic container 100 through the liquid inlet.

[0127] One end of the first liquid supply pipe 531 is connected to the electrolyte storage container 510. The other end of the first liquid supply pipe 531 is connected to the lower end of the first electrolysis pipe 110. One end of the second liquid supply pipe 532 is connected to the electrolyte storage container 510. The other end of the second liquid supply pipe 532 is connected to the lower end of the second electrolysis pipe 140. Both ends of the first liquid outlet pipe 541 are respectively connected to the first connecting pipe 120 and the electrolyte purification component 520. Both ends of the second liquid outlet pipe 542 are respectively connected to the second connecting pipe 130 and the electrolyte purification component 520. Both ends of the reflux pipe 550 are respectively connected to the electrolyte storage container 510 and the electrolyte purification component 520.

[0128] The first liquid supply pipeline 531 is provided with a first delivery pump 561, which is disposed at the connection position between the first liquid supply pipeline 531 and the first electrolysis pipeline 110 and the first connecting pipeline 120. The first delivery pump 561 is used to pump liquid upward to transport the electrolyte from the electrolyte storage container 510 to the first electrolysis pipeline 110 and the first connecting pipeline 120. The second liquid supply pipeline 532 is provided with a second delivery pump 562, which is used to pump liquid upward to transport the electrolyte from the electrolyte storage container 510 to the second electrolysis pipeline 140 and the second connecting pipeline 130. The first liquid outlet pipeline 541 is provided with a third delivery pump 563, which is used to pump liquid downward to transport the electrolyte from the first connecting pipeline 120 to the electrolyte purification component 520. The second liquid outlet pipe 542 is provided with a fourth delivery pump 564 , which is used to pump liquid downward to deliver the electrolyte from the second connecting pipe 130 to the electrolyte purification component 520 .

[0129] The anode and cathode are prepared by the following steps:

[0130] Step 1, weigh 1 part of lithium fluoride and 12 parts of 32% hydrochloric acid, put them into a reactor lined with polytetrafluoroethylene (PTFE), stir them at 35°C for 20 minutes, and the stirring speed is 500r / min.

[0131] Step 2, add 1 part of titanium aluminum carbide to the acidic solution containing lithium fluoride at a rate of 0.01 part / 10 seconds. After the addition is completed, the temperature is raised to 50°C at 1°C / minute, the speed is kept constant, and stirring is continued for 36 hours. The reaction product is centrifuged and washed with 200 parts of 10% hydrochloric acid, the speed of the centrifuge is set at 7000r / min, and then washed with deionized water with a conductivity of 10μS / cm to a pH of 7. Under nitrogen protection, the solution is ultrasonically vibrated for 5 hours with a vibration power of 300W to obtain a colloidal solution.

[0132] Step 3, take another 20 parts of nickel foam (NF), wash it with 200 parts of anhydrous ethanol, 100 parts of 10% hydrochloric acid, and 500 parts of deionized water in sequence, then put the nickel foam into the above colloidal solution, shake and dry it at 60°C for 24 hours to obtain a hydrophilic catalyst.

[0133] Step 4, weigh 2 parts of nickel nitrate (Ni(NO3)2·6H2O) and 1 part of ferric sulfate (FeSO4) and add them to a flask, add 30 parts of deionized water to the flask, stir for 20 minutes, and the stirring speed is 200r / min. Then add 30 parts of ethylene glycol to the flask, maintain the stirring speed, and stir for 40 minutes to prepare the first precursor electrolyte. The above-mentioned hydrophilic catalyst is used as the working electrode, and the platinum electrode is placed in the first precursor electrolyte as the counter electrode, and the electrodeposition is carried out at a voltage of 3V for 500s to obtain a pre-deposited product. The pre-deposited product is washed with 500 parts of deionized water, and then placed in a vacuum drying oven for vacuum drying at 70°C for 12h.

[0134] Step 5, weigh 0.4 parts of nickel nitrate (Ni(NO3)2·6H2O) and 0.2 parts of ferric nitrate (Fe(NO3)3·9H2O) and add them to a flask, add 50 parts to the flask and stir for 20 minutes at a stirring speed of 500r / min, then add 8 parts of thiourea, keep the speed constant, stir for 10 minutes, and finally add 0.5 parts of potassium dihydrogen phosphate, keep the speed constant, stir for 5 minutes to prepare a second precursor electrolyte. The above pre-deposited product is used as a working electrode, a platinum sheet is used as a counter electrode, and silver / silver chloride (Ag / AgCl) is used as a reference electrode, and is placed in the second precursor electrolyte for electrodeposition at a voltage of 3V for 1000s, and then the working electrode is cleaned with 500 parts of deionized water with a conductivity of 10μS / cm to obtain an electrode material.

[0135] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0136] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A water electrolysis device, characterized in that: comprising an electrolysis container, an anode and a cathode; The electrolysis container includes a first electrolysis pipe, a first connecting pipe, a second connecting pipe and a second electrolysis pipe which are connected in sequence, wherein the first connecting pipe and the second connecting pipe are both arranged obliquely to a horizontal plane, and adjacent pipes are arranged at an angle, wherein the higher end of the first connecting pipe is connected to the higher end of the second connecting pipe, the lower end of the first connecting pipe is connected to the lower end of the first electrolysis pipe, and the lower end of the second connecting pipe is connected to the lower end of the second electrolysis pipe; the anode is arranged in the first electrolysis pipe, and the cathode is arranged in the second electrolysis pipe.

2. The water electrolysis device according to claim 1, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (2): (1) The first electrolysis pipe is arranged obliquely to a horizontal plane, and the anode extends along the axial direction of the first electrolysis pipe and is arranged on the upper inner wall of the first electrolysis pipe; (2) The second electrolysis pipe is arranged at an angle to a horizontal plane, and the cathode extends along the axial direction of the second electrolysis pipe and is arranged on the upper inner wall of the second electrolysis pipe.

3. The water electrolysis device according to claim 1, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (2): (1) The angle between the first electrolysis pipe and the first connecting pipe is 30° to 60°; (2) The angle between the second electrolysis pipe and the second connecting pipe is 30° to 60°.

4. The water electrolysis device according to claim 1, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (3): (1) A first exhaust hole is provided at the higher end of the first electrolysis pipe; (2) A second exhaust hole is provided at the higher end of the second electrolysis pipe; (3) An exhaust hole is provided on the upper side of the connection position between the first connecting pipe and the second connecting pipe.

5. The water electrolysis device according to claim 1, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (2): (1) The water electrolysis device further includes a first vibration device, wherein the first vibration device is connected to the first connecting pipe; (2) The water electrolysis equipment further includes a second vibration device, and the second vibration device is connected to the second connecting pipe.

6. The water electrolysis device according to any one of claims 1 to 5, characterized in that The water electrolysis equipment also includes an electrolyte circulation purification device, which includes an electrolyte storage container and an electrolyte purification component. The electrolysis container is provided with a liquid inlet and a liquid outlet. The electrolyte storage container is connected to the liquid inlet, and the electrolyte purification component is connected to the liquid outlet. The electrolyte purification component is connected to the electrolyte storage container to supply purified electrolyte to the electrolyte storage container.

7. The water electrolysis device according to claim 6, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (2): (1) The lower end of the first electrolysis pipe and the lower end of the second electrolysis pipe are respectively provided with the liquid inlet; (2) The first connecting pipe is provided with the liquid outlet between the lower end and the upper end, and the second connecting pipe is also provided with the liquid outlet between the lower end and the upper end.

8. The water electrolysis device according to any one of claims 1 to 5 and 7, characterized in that: The anode and / or the cathode are prepared by the following steps: Add titanium aluminum carbide dropwise to an acidic solution containing lithium fluoride, stir and heat to react, wash the reaction product until the pH value is 6-7, and then perform ultrasonic treatment to obtain a colloidal solution; Place porous nickel in the colloidal solution, react at 40° C. to 60° C. for 12 h to 24 h to obtain a hydrophilic catalyst; Placing the hydrophilic catalyst as a working electrode in a first precursor electrolyte, wherein the first precursor electrolyte comprises 10 to 30 parts of water, 1 to 2 parts of nickel nitrate, 0.5 to 1 part of ferric sulfate and 10 to 30 parts of ethylene glycol, and performing a first electrochemical deposition treatment to obtain a pre-deposition product; The pre-deposited product is placed as a working electrode in a second precursor electrolyte, wherein the second precursor electrolyte contains 30 to 50 parts of water, 0.3 to 0.4 parts of nickel nitrate, 0.1 to 0.2 parts of ferric nitrate, 7 to 8 parts of thiourea and 0.5 parts of potassium dihydrogen phosphate, and a second electrochemical deposition treatment is performed to obtain the electrode material.

9. The water electrolysis device according to claim 8, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (5): (1) The acidic solution containing lithium fluoride is prepared by the following steps: Take 0.5-1 parts of lithium fluoride and mix with 10-12 parts of hydrochloric acid with a mass concentration of 30%-32%; (2) The mass ratio of the lithium fluoride to the titanium aluminum carbide is (1-2): (1-2); (3) The heating reaction temperature is 40°C to 50°C and the time is 12h to 36h; (4) The cleaning treatment includes: centrifugal cleaning with hydrochloric acid having a mass concentration of 5% to 10% at a centrifugal speed of 5000 r / min to 8000 r / min, and then washing with water; (5) The ultrasonic treatment comprises: in a protective gas atmosphere, ultrasonically oscillating the solution after the cleaning treatment for 2h~5h, with a vibration power of 200W~300W.

10. The water electrolysis device according to claim 8 or 9, characterized in that: The water electrolysis device meets at least one of the following characteristics (1) to (4): (1) In the first electrochemical deposition process, a platinum electrode is used as a counter electrode; (2) The voltage of the first electrochemical deposition treatment is 2V~3V, and the time is 200s~500s; (3) In the second electrochemical deposition process, a platinum sheet is used as a counter electrode and a mixture of silver and silver chloride is used as a reference electrode; (4) The voltage of the second electrochemical deposition treatment is 2V~3V, and the time is 800s~1000s.

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