An ultra-durable solar-driven seawater electrolysis hydrogen production device and hydrogen production method

Abstract

A super-durable solar-powered seawater electrolysis hydrogen production device and method, belonging to the field of new energy seawater desalination technology. The solar evaporator is an evaporator with a three-dimensional bionic microstructure on the upper portion and microchannels on the lower portion. The three-dimensional bionic microstructure is super-hydrophilic, and the bottom interface of the microchannel is hydrophilic. The super-hydrophilicity causes water flowing out of the microchannel to diffuse along the three-dimensional bionic microstructure. The electrolysis hydrogen production system includes an electrolytic cell, a cathode copper plate, a diversion hopper, a gas collecting pipe, and a film with a Janus structure. The method includes assembling a hydrogen production device; solar energy photothermal conversion forms a temperature gradient within the water film and creates a Marangoni effect. The Marangoni effect's brine microcirculation prevents salt crystallization and collects fresh water; a power supply system supplies electricity to the cathode copper plate and anode graphite plate to perform the water electrolysis reaction. This application significantly improves the durability and service life of the device.

Description

Technical Field

[0001] The present invention relates to a seawater evaporation hydrogen production device and method, and in particular to an ultra-durable solar-driven seawater electrolysis hydrogen production device and method, belonging to the field of new energy seawater desalination technology. Background Art

[0002] As the most abundant water resource on earth, seawater has great potential when combined with electrolysis to produce hydrogen. - Extreme corrosion of the anode and Mg 2+ and Ca 2+ The reaction at the cathode produces solid matter, and the ions in seawater hinder the direct electrolysis of seawater, thereby reducing the electrolysis efficiency; in addition, traditional seawater desalination consumes fossil fuels and emits large amounts of carbon dioxide, threatening human survival.

[0003] Solar-powered seawater desalination for electrolytic hydrogen production has attracted attention in recent years. However, traditional solar evaporation technology is susceptible to problems such as salt crystallization and corrosion under high salt concentrations, which greatly affects the service life and performance of the equipment.

[0004] Therefore, how to improve the above problems has become a task that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0005] In order to overcome the shortcomings of the existing technology, the present invention provides an ultra-durable solar-driven seawater electrolysis hydrogen production device and hydrogen production method. The device has a reasonable structure and has efficient hydrogen production and salt resistance.

[0006] To address the high salt concentration and strong corrosiveness of seawater, the evaporator in the device adopts a three-dimensional bionic microstructure with microchannels at the bottom, giving it Janus characteristics, allowing it to operate stably for a long time in the harsh marine environment during the salt water evaporation process;

[0007] To address the problem of low hydrogen production efficiency, the device uses a Janus-structured membrane and electrode integrated structure to achieve rapid one-way transport of hydrogen bubbles.

[0008] In view of the above: This application provides the following solutions:

[0009] An ultra-durable solar-driven seawater electrolysis hydrogen production device comprising:

[0010] A seawater evaporation freshwater collection system is used to recover freshwater and feed it into the electrolytic hydrogen production system. The seawater evaporation freshwater collection system comprises a connected solar evaporator, an open container, a freshwater collection container, and a transparent cover; the solar evaporator, the open container, and the transparent cover enclose an evaporation space;

[0011] Electrolysis hydrogen production system, used for water electrolysis to produce hydrogen;

[0012] A power supply system, used to provide electrical energy to the electrolysis hydrogen production system;

[0013] The solar evaporator is an evaporator having a three-dimensional bionic microstructure on the upper part and a microchannel on the lower part. The three-dimensional bionic microstructure is superhydrophilic, and the bottom interface of the microchannel is hydrophilic. The superhydrophilicity enables water flowing out of the microchannel to diffuse along the three-dimensional bionic microstructure.

[0014] The electrolytic hydrogen production system includes an electrolytic cell, a cathode copper plate, a guide hopper, a gas collecting pipe and a film with a Janus structure, wherein the film can produce a layer of air film when immersed in water; the electrolytic cell is suitable for placing electrolyte; the anode plate is placed in the electrolytic cell, the cathode copper plate is laid flat on the bottom of the electrolytic cell, the film is arranged on the upper surface of the cathode copper plate and there is a gap between the two, the gap allows hydrogen bubbles to be generated on the surface of the cathode copper plate during electrolysis, the film has an air channel, the guide hopper is arranged above the film, the guide hopper inlet covers the film, the guide hopper outlet is arranged in the inverted gas collecting pipe inlet, the gas collecting pipe is suitable for being filled with water for collecting hydrogen, the anode graphite plate and the cathode copper plate are electrically connected to the positive and negative poles of the power supply system respectively.

[0015] Furthermore, the solar evaporator is obtained by: first modeling the evaporator using SolidWorks software to obtain a 3D model, then saving the 3D model in STL format, importing the STL file of the 3D model into slicing software to slice and obtain a 2D slice model image, and importing the image into a light-curing 3D printer; at the same time, selecting carbon nanotubes and photosensitive resin with a mass ratio of 1:100, pouring the prepared carbon nanotubes and photosensitive resin into a container and stirring them thoroughly until they are evenly mixed, and after stirring, pouring the mixed material into the printing tank of the light-curing 3D printer for printing;

[0016] The printed evaporation device was removed from the printing platform and ultrasonically cleaned with a 95% ethanol solution. After cleaning, the evaporation device was removed and the ethanol solution on the surface of the evaporation device was blown off with a nitrogen pump. This process was repeated multiple times until there was no residual ethanol solution and resin on the surface of the evaporation device. After that, it was vacuum dried to remove all moisture. After drying, the upper part of the evaporator was treated with oxygen plasma to make the upper surface superhydrophilic. The evaporation device was then left to stand until room temperature, resulting in a solar evaporator with salt resistance in saturated brine.

[0017] With this design, the solar evaporator obtained above has Janus characteristics, which improves the evaporation efficiency while preventing salt crystallization when the device works in a harsh seawater environment with high salt concentration, significantly improving the durability of the device and increasing its service life.

[0018] An ultra-durable solar-driven seawater electrolysis hydrogen production method is implemented based on the solar-driven seawater electrolysis hydrogen production device, and the hydrogen production method comprises the following steps:

[0019] S1. Place seawater in the open container, place the solar evaporator in the open container filled with seawater, float the solar evaporator on the water, and cover it with a transparent cover;

[0020] S2. The light source is directed directly onto the solar evaporator, causing seawater to evaporate and the salt water to be transported upward along the microchannel. Under the action of Laplace pressure, a thin water film is formed on the surface of the three-dimensional bionic microstructure. The solar thermal conversion forms a temperature gradient within the water film, creating a Marangoni effect. The microcirculation of salt water due to the Marangoni effect prevents salt crystallization.

[0021] S3. The glass cover condenses the generated water vapor into droplets, which flow into the fresh water collection container under the action of gravity. The collected fresh water flows into the electrolytic cell through the pipeline;

[0022] S4. The power supply system supplies electricity to the cathode copper plate and the anode plate to carry out the electrolysis reaction of water. During the electrolysis process, the air film generated by the film with the janus structure allows the hydrogen bubbles generated by the electrolysis to be quickly transported in one direction after passing through the air channel. Under the action of the hydrophobic layer, the hydrogen bubbles are prompted to gather above the hydrophobic layer. When they gather to a certain volume, the bubbles float upward, and under the diversion action of the diversion bucket, the hydrogen is collected into the gas collecting pipe.

[0023] Furthermore, the substrate of the film with the janus structure is a mesh plate, the upper surface of the mesh plate is coated with a hydrophobic layer, and the hydrophobic layer can form an air film when immersed in water.

[0024] Preferably, the material of the hydrophobic layer is nano-scale silica particles, which has the function of reducing the surface tension of the coating. When the film with a Janus structure is immersed in water, the super-hydrophobic treated silica particles form a smooth air film. The air film has Janus characteristics and has the function of rapid unidirectional transport of hydrogen bubbles.

[0025] Furthermore, the fresh water collection container and the open container are made by fused deposition modeling 3D printing, which has a simple structure and low cost.

[0026] Furthermore, the solar evaporator is made by photocuring 3D printing, and the grid plate is made by photocuring 3D printing. This production method improves product accuracy and printing speed.

[0027] The beneficial effects of the present application are as follows: the present application uses solar-driven seawater electrolysis to produce hydrogen, relying entirely on renewable solar energy as energy, which not only reduces dependence on traditional power grids but also avoids the use of fossil energy, thereby effectively reducing carbon emissions. In response to the problems of high salinity and corrosiveness in the marine environment, the evaporation device in the device of the present invention uses a solar evaporator with a microstructure and microchannels. The 3D micro-nano structure of the evaporator is super-hydrophilic, and the bottom interface of the microchannel is hydrophilic, exhibiting Janus characteristics, which can prevent salt crystallization when the device is working in a harsh seawater environment with high salt concentration, significantly improving the durability and service life of the device. Compared with traditional freshwater electrolysis hydrogen production technology, the present invention uses seawater as raw material, making full use of seawater resources that are widely distributed around the world, solving the problem of freshwater resource shortage, reducing the water source cost in the hydrogen production process, and improving the sustainability and economy of production.

[0028] In order to make the above-mentioned objects, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a schematic diagram of the ultra-durable solar-driven seawater electrolysis hydrogen production device of this application;

[0030] Figure 2 This is a main cross-sectional view of the seawater evaporation freshwater collection system of the present application;

[0031] Figure 3 This is an electron microscope image of a 3D bionic solar evaporator in the embodiment;

[0032] Figure 4 is a main cross-sectional view of the electrolysis hydrogen production system in the embodiment;

[0033] Figure 5 is a top view of a film having a Janus structure in an embodiment;

[0034] Figure 6 A diagram showing the structure and arrangement of the cathode copper plate and the thin film with a Janus structure in the embodiment;

[0035] Figure 7 This is a salt resistance test diagram of the solar evaporator of the present application in the embodiment;

[0036] Figure 8 This is a graph showing the fresh water collection rate obtained by outdoor testing using the device of the present application in the examples;

[0037] Figure 9 This is a graph showing the relationship between the amount of hydrogen collected and the time of the device of the present application when working outdoors in an embodiment;

[0038] Figure 10 This is a stability test diagram of the ultra-durable solar-driven seawater electrolysis hydrogen production device of the present application in the embodiment. DETAILED DESCRIPTION

[0039] Unless otherwise specified, the technical terms or scientific terms used in this embodiment have the common meanings understood by those skilled in the art to which this application belongs.

[0040] Reference Figure 1-Figure 3 , an ultra-durable solar-driven seawater electrolysis hydrogen production device comprising:

[0041] The seawater evaporation fresh water collection system 1 is used to recycle fresh water and replenish it into the electrolysis hydrogen production system 2, such as Figure 2 As shown, the seawater evaporation freshwater collection system 1 comprises a connected solar evaporator 11, an open container 12, a freshwater collection container 13 and a transparent cover 14; the solar evaporator 11, the open container 12 and the transparent cover 14 enclose an evaporation space;

[0042] Electrolysis hydrogen production system 2, used for water electrolysis to produce hydrogen;

[0043] The power supply system 3 is used to provide electric energy to the electrolysis hydrogen production system 2;

[0044] like Figure 3 As shown, the solar evaporator 11 is an evaporator having a three-dimensional bionic microstructure on the upper part and a microchannel (such as a capillary channel) on the lower part. The three-dimensional bionic microstructure has superhydrophilicity, and the bottom interface of the microchannel has hydrophilicity. The superhydrophilicity enables the water flowing out of the microchannel to spread and diffuse along the three-dimensional bionic microstructure.

[0045] Figure 4-Figure 6The electrolytic hydrogen production system 2 includes an electrolytic cell 21, a cathode copper plate 22, a flow guide hopper 23, a gas collecting pipe 24, and a film 25 with a Janus structure. The film 25 can produce an air film when immersed in water. The electrolytic cell 21 is suitable for placing electrolyte. The anode plate 26 is placed in the electrolytic cell 21. The cathode copper plate 22 is laid flat on the bottom of the electrolytic cell 21. The film 25 is set on the upper surface of the cathode copper plate 22 with a gap between them. The gap allows hydrogen bubbles to form on the surface of the cathode copper plate 22 during electrolysis. The film 25 has an air channel 251. The diversion hopper 23 is positioned above the film 25. The inlet of the diversion hopper 23 covers the film 25. The outlet of the diversion hopper 23 is positioned within the inverted inlet of the gas collecting pipe 24. The gas collecting pipe 24 is adapted to be filled with water for collecting hydrogen. The anode graphite plate 26 and the cathode copper plate 22 are electrically connected to the positive and negative electrodes of the power supply system 3, respectively. An air film is distributed at the top of the grid plate and forms a gas channel with the sidewalls of the grid plate. The purpose of this channel is to capture, adsorb, and transport the expanding bubbles below.

[0046] The device of the present invention has a reasonable structure and has the advantages of high evaporation rate and efficient hydrogen production. To address the problems of high salt concentration and strong corrosiveness in seawater, the evaporation device in the device adopts a solar evaporator with microstructure and microchannels. The 3D micro-nano structure of the evaporator is super hydrophilic, and the bottom interface of the microchannel is hydrophilic, exhibiting Janus characteristics, enabling it to operate stably for a long time in harsh marine environments and having excellent salt resistance.

[0047] Figure 7 The salt tolerance test of the solar evaporator of the present application is demonstrated. 50 ml of water is added to three 100 ml beakers, and 5.56 g, 8.82 g, and 17.57 g of NaCl are added to the three beakers, respectively. After thorough stirring, 10 wt%, 15 wt%, and 26 wt% salt water is obtained. The salt water is poured into a petri dish, and then the 3D bionic solar evaporator developed by the present application is placed in the 10 wt%, 15 wt%, and 26 wt% salt water for 8 hours, and the light intensity is 1000 Wm -2 Then, ordinary solar evaporators were placed in 10wt%, 15wt% and 26wt% brine respectively and evaporated for 8 hours under the same light intensity (indoors, the light source can be a simulated daylight xenon lamp to provide solar energy, and outdoors, direct solar radiation is used). Figure 7 It can be seen that there are a large number of salt crystals on the surface of ordinary evaporators, while the 3D bionic solar evaporator of this application can evaporate for a long time in high-concentration salt water without salt crystallization, demonstrating super durability and super salt resistance.

[0048] In order to verify the device's ability to efficiently desalinate seawater and collect fresh water through condensation, the inventors conducted an outdoor test of evaporating and collecting fresh water. The salt water concentration used in the test was 3.5 wt% (the world's average seawater concentration). Figure 8 As shown, the device can collect up to 0.58Lm in one hour outdoors. -2 of fresh water, the lowest is 0.44Lm -2 .

[0049] Based on the above embodiments, the following examples are given to illustrate the detailed parts and connection relationships of the device.

[0050] Example 1: The fresh water collection container 13 is in a truncated cone shape, and the cross-sectional area of ​​the top is larger than the area of ​​the open container. The fresh water collection container 13 has a support 15 inside, and the top of the support 15 fixes the open container 12.

[0051] The support 15 can be independently arranged vertically, or arranged obliquely, or made integrally with the fresh water collection container 13. The frustum-shaped collection container with a larger top and a smaller bottom is conducive to the flow and collection of condensed droplets on the inner wall of the transparent cover 14.

[0052] Example 2: A hemispherical glass cover is placed above the open container 12 and snapped onto the fresh water collection container 13. The diameter of the hemispherical glass cover is larger than the cross-sectional diameter of the open container 12, but smaller than the cross-sectional diameter of the top of the fresh water collection container 13. This design ensures sufficient evaporation space and ensures that condensed droplets can be smoothly recovered by the fresh water collection container.

[0053] For example, the radius of the transparent glass cover is 14 cm. During the evaporation process, water vapor condenses on the glass cover to form small droplets. As the evaporation time increases, the droplets on the surface of the glass cover gradually grow larger and finally flow downward under the action of gravity to the collected fresh water collection container 13.

[0054] Example 3: A pipe 16 is provided at the bottom of the fresh water collection container 13, extending to the top of the electrolytic cell 21. The collected fresh water flows into the electrolytic cell 21 through the pipe 16. The pipe-connected collection method facilitates the arrangement and disassembly of the various systems of the device, and can be operated both indoors and outdoors.

[0055] Example 4: The preparation process of the solar evaporator having a three-dimensional biomimetic microstructure on the upper portion and microchannels on the lower portion is as follows: the evaporator is modeled on a computer using SolidWorks software, and then the model is saved in STL format. The STL file of the model is imported into slicing software for slicing and obtaining a 2D sliced ​​model image, which is then imported into a light-curing 3D printer. Simultaneously, after the modeling is completed, the materials are prepared. A certain mass of carbon nanotubes and photosensitive resin is weighed out using a balance, and the mass ratio of carbon nanotubes to photosensitive resin is 1:100. The carbon nanotubes are used to increase the spectral absorptivity of the solar evaporator surface. The carbon nanotubes are added to the resin and mixed for 3D printing. The weighed carbon nanotubes and photosensitive resin are poured into a beaker and mixed. A magnetic stirrer is used to thoroughly stir them until they are evenly mixed. The stirring time should be greater than 30 minutes. If they are still not evenly mixed after 30 minutes, stirring should be continued until they are fully mixed. After stirring, the mixed resin is poured into the print tank of the light-curing 3D printer, and printing is initiated. The preparation process of ordinary evaporators is the same as that of 3D bionic solar evaporators. The difference between the two lies in their shapes; for example, large-area (14cm×14cm) evaporators and small-area (2cm×2cm) evaporators are both manufactured by the above method.

[0056] After printing is complete, the evaporator is removed from the print platform and ultrasonically cleaned for 2 minutes with a 95% ethanol solution. After cleaning, the evaporator is removed and the ethanol solution on the surface is blown away with a nitrogen pump. This process is repeated three times to ensure that there is no residual ethanol solution or resin on the evaporator surface. The temperature in a vacuum drying oven is raised to 80°C and the evaporator is placed in the drying oven for 1 hour to ensure that all moisture is removed. After drying, the top surface of the evaporator is treated with oxygen plasma to reduce the contact angle to less than 10°, indicating superhydrophilicity. The evaporator is then allowed to cool to room temperature for 30 minutes.

[0057] With this design, the solar evaporator obtained above has Janus characteristics, which improves the evaporation efficiency while preventing salt crystallization when the device works in a harsh seawater environment with high salt concentration, significantly improving the durability of the device and increasing its service life.

[0058] Example 5: After the salt tolerance test was completed, a large-area solar evaporator was designed with an upper surface working area of ​​14 cm×14 cm, which was manufactured using light-curing 3D printing technology.

[0059] A large cylindrical container is designed as an open container 12, with an inner radius of 12.2 cm, a wall thickness of 0.5 cm, and a height of 5 cm, and is manufactured by fused deposition modeling (FDM) 3D printing technology. The container is used to store brine. During the evaporation process, the solar evaporator 11 is placed in the open container 12 and floats above the brine to form an evaporated brine container. The fresh water collection container 13 for desalinated water is truncated cone-shaped, and its radius gradually decreases from top to bottom. The inner radius of the circle at the top of the container is 14.4 cm, the inner radius of the circle at the bottom of the container is 2 cm, and the height of the container is 9 cm. There is a support with a height of 9 cm in the middle of the fresh water collection container 13, which is used to support and fix the open container 12 for evaporating brine. There is a pipe at the bottom of the fresh water collection container 13 for transporting desalinated water to the electrolytic cell.

[0060] In Example 6, the Janus-structured film comprises a mesh substrate coated with a hydrophobic layer on its upper surface. This layer forms an air film when immersed in water. Due to the interfacial wettability differences between the super-hydrophobic top of the mesh and the hydrophilic bottom, an asymmetric wettability structure is formed. This Laplace pressure differential develops at the gas-liquid-solid interface. This Laplace pressure differential traps bubbles in the mesh, allowing them to be rapidly manipulated and transported to the top of the mesh.

[0061] The electrolytic cell in this example is constructed from a transparent acrylic sheet, measuring 25 cm long, 25 cm wide, and 25 cm high. The electrolyte is a dilute sulfuric acid solution with a pH of 1. The volume of the electrolyte is 11 L. The power supply system utilizes solar cells. These cells provide the electricity consumed during the electrolysis process. These cells have a simultaneous charge and discharge function and are currently available.

[0062] Furthermore, a grid plate with a size of 5cm×5cm was processed and manufactured using photocuring 3D printing technology, in which the smallest unit of the grid was 0.4cm×0.4cm. The material used to process the grid plate does not need to be added with carbon nanotubes, but only needs to be cured layer by layer in the printer through photosensitive resin. 16 pieces of 5cm×5cm grids were processed, and superhydrophobic material was sprayed onto the upper surface of the grid. The superhydrophobicity on the upper surface of the grid plate and the hydrophilicity on the lower surface of the substrate formed a Janus film. When the Janus film was completely immersed in water, a smooth air film was formed on the surface after the superhydrophobic treatment. And 16 pieces of 5cm×5cm grids were pieced together (for example, by bonding by curing resin and curing with ultraviolet light) to form a large-area Janus grid of 20cm×20cm.

[0063] Furthermore, the electrolytic cathode material is copper. A 20cm×20cm copper sheet is attached to a 22cm×22cm base plate, which is a glass plate. The glass base plate secures the copper sheet and sinks it to the bottom of the electrolytic cell. A large-area Janus grid measuring 20cm×20cm is then affixed to the copper sheet, with the lower surface of the grid plate spaced 300-600um apart from the surface of the copper sheet (for example, a spacing of 0.6cm allows the diameter of hydrogen bubbles generated on the copper surface during electrolysis to be approximately 0.6cm). A 2cm-wide conductive copper foil is then connected at one end to the cathode copper plate 22 (the working electrode) and at the other end to the negative electrode lead of a solar cell outside the electrolytic cell to serve as a conductor. The foil is then sealed with waterproof tape to prevent reactions on its surface during the electrolysis process.

[0064] Furthermore, an inverted flow guide hopper 23 is placed above the cathode (for example, an inverted funnel can be used for the flow guide hopper 23 in a small test, and a graduated cylinder can be used for the gas collecting pipe 24, which is fixed to the electrolytic cell 21 by a bracket 27). The flow guide hopper 23 is open at both ends, with one end having a large opening and the other end having a small opening. The large opening is a square with a side length of 25 cm, which can fully cover the entire cathode, including the large area of ​​the Janus structure film 25 and the glass bottom plate. The small opening of the flow guide hopper 23 is inserted into the inverted gas collecting pipe filled with electrolyte. The growing large hydrogen bubbles float upward, and the hydrogen bubbles generated on both sides drift along the inner wall of the flow guide hopper 23 into the gas collecting pipe 24. The flow guide hopper 23 plays a diversion role in the process. Finally, the hydrogen is collected into the gas collecting pipe 24 by the drainage method.

[0065] Furthermore, a square graphite plate with a thickness of 0.5 cm is used as the anode plate 26. The carbon plate is placed vertically in the electrolyte with a quarter of it exposed outside the electrolyte and fixed. The wire coming out of the positive electrode of the solar cell is connected to the exposed part of the carbon plate.

[0066] Example 7: Based on the ultra-durable solar-driven seawater electrolysis hydrogen production device of the above embodiment or any embodiment, an ultra-durable solar-driven seawater electrolysis hydrogen production method is proposed, which comprises the following steps:

[0067] S1. Place seawater in the open container 12, place the solar evaporator 11 in the open container 12 filled with seawater, float the solar evaporator 11 on the water, and cover it with a transparent cover 14;

[0068] S2. The light source is directed toward the solar evaporator 11, causing seawater to evaporate and the salt water to be transported upward along the microchannel. Under the action of Laplace pressure, a thin water film is formed on the surface of the three-dimensional bionic microstructure. The solar thermal conversion forms a temperature gradient within the water film, creating a Marangoni effect. The microcirculation of salt water due to the Marangoni effect prevents salt crystallization.

[0069] S3, the transparent cover 14 condenses the generated water vapor into droplets, which flow into the fresh water collection container 13 under the action of gravity, and the collected fresh water flows into the electrolytic cell 21 through the pipeline;

[0070] S4. The power supply system supplies electricity to the cathode copper plate 22 and the anode graphite plate 26 to perform a water electrolysis reaction. During the electrolysis process, the air film generated by the thin film with the Janus structure allows the hydrogen bubbles generated by the electrolysis to be rapidly transported in one direction after passing through the air channel. Under the action of the hydrophobic layer, the hydrogen bubbles are prompted to gather above the hydrophobic layer. When they gather to a certain volume, the bubbles float upward, and under the diversion action of the diversion bucket 23, the hydrogen is collected in the gas collecting pipe 24.

[0071] Using solar-powered seawater evaporation technology, the system condenses and collects water vapor through a hemispherical transparent glass cover to create desalinated water. This water is then piped into an electrolytic cell, where it undergoes electrolysis to generate hydrogen.

[0072] Reference Figures 8-10 , Figure 8 The experiment demonstrated the freshwater collection rate of the hydrogen production device in an 8-day cycle of evaporating brine. The experiment found that, except on rainy days, the freshwater collection rate of the ultra-durable solar-driven seawater evaporation and freshwater collection device was as low as 0.44 L m -2 h -1 , the highest is 0.58L m -2 h -1 .

[0073] Figure 9 The relationship between the amount of hydrogen collected and time when the device is working outdoors shows that the collection rate reaches 1.75-2 L m -2 h -1 .

[0074] As an embodiment, the electric energy in the electrolysis process is provided by a solar cell, which can be charged while in use, and the electric energy obtained during the day can be used by the electrolysis device of the present invention for more than 24 hours. Figure 9 It can be concluded that the hydrogen production device can collect 85mL of hydrogen in 1 hour, and the water consumption in this process is only 0.068mL. The freshwater collection device tested above can collect at least 8.62mL of water in 1 hour, which is far greater than the water consumption of electrolytic hydrogen production. Therefore, the comprehensive experimental test results show that the ultra-durable solar-driven seawater electrolysis hydrogen production device can operate continuously for 24 hours a day.

[0075] In order to verify the stability of the hydrogen production device, the inventor conducted 8 cycle tests outdoors for 1 hour. Figure 10 As shown, the hydrogen production device has excellent stability performance.

[0076] The present invention has been disclosed above with preferred embodiments, but this is not intended to limit the present application. Any technician familiar with this profession can make slight changes or modifications to the above-disclosed structures and technical contents without departing from the scope of the technical solution of the present application, and the equivalent embodiments with equivalent changes are still within the scope of the technical solution of the present application.

Claims

1. An ultra-durable solar-driven seawater electrolysis hydrogen production device, comprising: A seawater evaporation freshwater collection system is used to recover freshwater and feed it into the electrolytic hydrogen production system. The seawater evaporation freshwater collection system comprises a connected solar evaporator, an open container, a freshwater collection container, and a transparent cover; the solar evaporator, the open container, and the transparent cover enclose an evaporation space; Electrolysis hydrogen production system, used for water electrolysis to produce hydrogen; A power supply system, used to provide electrical energy to the electrolysis hydrogen production system; Its characteristics are: The solar evaporator is an evaporator having a three-dimensional bionic microstructure on the upper part and a microchannel on the lower part. The three-dimensional bionic microstructure is superhydrophilic, and the bottom interface of the microchannel is hydrophilic. The superhydrophilicity enables water flowing out of the microchannel to diffuse along the three-dimensional bionic microstructure. The electrolytic hydrogen production system includes an electrolytic cell, a cathode copper plate, a guide hopper, a gas collecting pipe and a film with a Janus structure, wherein the film can generate an air film when immersed in water, the substrate of the film with the Janus structure is a grid plate, the upper surface of the grid plate is coated with a hydrophobic layer, and the hydrophobic layer can form an air film when immersed in water, and the electrolytic cell is suitable for placing electrolyte; the anode graphite plate is placed in the electrolytic cell, the cathode copper plate is laid flat on the bottom of the electrolytic cell, the film is arranged on the upper surface of the cathode copper plate and there is a gap between the two, the gap allows hydrogen bubbles to be generated on the surface of the cathode copper plate during electrolysis, the film has an air channel, the guide hopper is arranged above the film, the guide hopper inlet covers the film, the guide hopper outlet is arranged in the inverted gas collecting pipe inlet, the gas collecting pipe is suitable for being filled with water for collecting hydrogen, and the anode graphite plate and the cathode copper plate are electrically connected to the positive and negative poles of the power supply system respectively.

2. The ultra-durable solar-driven seawater electrolysis hydrogen production device according to claim 1, characterized in that: The grid plate is made by light-curing 3D printing.

3. The ultra-durable solar-driven seawater electrolysis hydrogen production device according to claim 1, characterized in that: The fresh water collection container is in a truncated cone shape, and the cross-sectional area of ​​the top is larger than the area of ​​the open container. The collection container is provided with a support inside, and the top of the support fixes the open container.

4. The ultra-durable solar-driven seawater electrolysis hydrogen production device according to claim 1, characterized in that: A hemispherical glass transparent cover is arranged above the open container, and the hemispherical glass transparent cover is buckled with the fresh water collection container.

5. The ultra-durable solar-driven seawater electrolysis hydrogen production device according to claim 1, characterized in that: A pipe is provided at the bottom of the fresh water collection container, and the pipe extends to above the electrolytic cell. The collected fresh water flows into the electrolytic cell through the pipe.

6. The ultra-durable solar-driven seawater electrolysis hydrogen production device according to claim 1, characterized in that: The freshwater collection container and open container were made by fused deposition modeling 3D printing, and the solar evaporator was made by stereolithography 3D printing.

7. The ultra-durable solar-driven seawater electrolysis hydrogen production device according to claim 1, characterized in that: The solar evaporator is obtained by the following method: First, the evaporator is modeled using SolidWorks software to obtain a 3D model. The 3D model is then saved in STL format. The STL file of the 3D model is imported into a slicing software for slicing to obtain a 2D sliced ​​model image. The image is then imported into a light-curing 3D printer. At the same time, carbon nanotubes and photosensitive resin with a mass ratio of 1:100 are selected, poured into a container and stirred thoroughly until they are evenly mixed. After stirring, the mixed material is poured into the printing tank of a light-curing 3D printer for printing; The printed evaporation device was removed from the printing platform and ultrasonically cleaned with a 95% ethanol solution. After cleaning, the evaporation device was removed and the ethanol solution on the surface of the evaporation device was blown off with a nitrogen pump. This process was repeated several times until there was no residual ethanol solution and resin on the surface of the evaporation device. After that, it was vacuum dried to remove all moisture. After drying, the upper part of the evaporator was treated with oxygen plasma to make the upper surface superhydrophilic. The evaporation device was then left to stand until room temperature to obtain a solar evaporator with salt resistance in saturated brine.

8. An ultra-durable solar-driven seawater electrolysis method for producing hydrogen, characterized by: The solar-driven seawater electrolysis hydrogen production device according to any one of claims 1 to 7 is implemented, and the hydrogen production method comprises the following steps: S1. Place seawater in the open container, place the solar evaporator in the open container filled with seawater, float the solar evaporator on the water, and cover it with a transparent cover; S2. The light source is directed directly onto the solar evaporator, causing seawater to evaporate and the salt water to be transported upward along the microchannel. Under the action of Laplace pressure, a thin water film is formed on the surface of the three-dimensional bionic microstructure. The solar thermal conversion forms a temperature gradient within the water film, creating a Marangoni effect. The microcirculation of salt water due to the Marangoni effect prevents salt crystallization. S3. The glass cover condenses the generated water vapor into droplets, which flow into the fresh water collection container under the action of gravity. The collected fresh water flows into the electrolytic cell through the pipeline; S4. The power supply system supplies electricity to the cathode copper plate and the anode graphite plate to carry out the water electrolysis reaction. During the electrolysis process, the air film generated by the film with the janus structure allows the hydrogen bubbles generated by the electrolysis to be quickly transported in one direction after passing through the air channel. Under the action of the hydrophobic layer, the hydrogen bubbles are prompted to gather above the hydrophobic layer. When they gather to a certain volume, the bubbles float upward, and under the diversion action of the diversion bucket, the hydrogen is collected into the gas collecting pipe.

9. The ultra-durable solar-driven seawater electrolysis hydrogen production method according to claim 8, characterized in that: Fresh water collection rate is 0.44 L m -2 h -1 -0.58L m -2 h -1 , the hydrogen collection rate is 1.75-2 L m -2 h -1 .

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