Preparation method of hydrogen evolution electrode based on three-period minimal curved surface structure

Abstract

A hydrogen evolution electrode preparation method based on a three-period minimal curved surface structure belongs to the technical field of new energy electrolytic hydrogen production and fluid transportation, and comprises the following steps: constructing a three-dimensional model of the required three-period minimal curved surface structure; performing image slicing processing on the three-dimensional model by using slicing software; printing a required three-period minimal curved surface structure by using a plane projection micro-stereolithography 3D printer; a nanometer ultraviolet lamp is adopted to circularly irradiate the three-period extremely-small curved surface structure; soaking in a sulfuric acid solution and carrying out ultrasonic oscillation; carrying out vacuum drying and carrying out oxygen plasma hydrophilic treatment; depositing a nickel-based compact conductive layer on the three-period minimal curved surface structure by using chemical deposition; depositing a nickel-iron alloy catalyst on the three-period minimal curved surface structure of the nickel substrate by using electro-deposition; and carrying out ultrasonic oscillation with ethanol and vacuum drying. According to the application, collaborative design of catalyst distribution and a macro-microstructure is realized, and a new way is provided for preparation of a high-performance water electrolysis hydrogen production electrode.

Description

Technical Field

[0001] This invention belongs to the field of new energy electrolysis hydrogen production and fluid transport technology, specifically relating to a method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure. Background Technology

[0002] Hydrogen is a clean and efficient secondary energy source with outstanding advantages such as high calorific value, combustion product being only water, wide availability, and diverse utilization forms. It is widely regarded as one of the most promising clean energy sources of the 21st century. However, in the process of producing hydrogen through water electrolysis, bubbles cover the active sites of the electrodes, reducing the effective reaction area and leading to an increase in the actual current density. This, in turn, increases the reaction overpotential and cell voltage, increasing energy consumption. Furthermore, bubbles occupy the electrode surface space, hindering the reaction of reactant ions (such as OH-). - or H + The transport of substances to the active site can be slowed down, but it can also delay the expulsion of products such as hydrogen. Summary of the Invention

[0003] To overcome the shortcomings of existing technologies, this invention provides a method for preparing a hydrogen evolution electrode based on a three-period minimal curved surface structure, aiming to solve the problems of bubble evolution and transport in the existing hydrogen evolution electrode process of water electrolysis.

[0004] The technical solution adopted in this invention is:

[0005] A method for fabricating a hydrogen evolution electrode based on a three-period minimal surface structure, characterized in that it comprises:

[0006] Step 1: Construct a 3D model of the required three-period minimal surface structure;

[0007] Step 2: Use slicing software to perform image slicing processing on the 3D model;

[0008] Step 3: Use a surface projection micro-stereolithography 3D printer to print the required three-period minimal surface structure;

[0009] Step 4: Cyclicly irradiate the three-period minimal surface structure with a nano-ultraviolet lamp;

[0010] Step 5: Immerse the irradiated three-period minimal surface structure in sulfuric acid solution and then ultrasonically vibrate it.

[0011] Step 6: Vacuum drying, followed by oxygen plasma hydrophilic treatment;

[0012] Step 7: Deposit a nickel-based dense conductive layer onto the three-period minimal surface structure using chemical deposition;

[0013] Step 8: Electrodeposition is used to deposit the nickel-iron alloy catalyst onto a three-period minimal surface structure on a nickel substrate;

[0014] Step 9: Use ethanol for ultrasonic oscillation and vacuum drying to prepare a hydrogen evolution electrode with a three-period minimal curved surface structure.

[0015] Furthermore, the three-period minimal surface structure mentioned in step one includes a continuous surface structure and a three-dimensional surface channel. The three-dimensional surface channel is evenly distributed on the six walls of the continuous surface structure. The continuous surface structure and the surface channel drive the bubbles to quickly detach from the surface and diffuse outwards from the electrode under the action of the continuous surface structure, thereby accelerating the flow of electrolyte inside the electrode, accelerating the ion exchange rate and the mass transfer rate, and ultimately accelerating the hydrogen evolution reaction.

[0016] Compared with the prior art, the beneficial effects of the present invention are:

[0017] I. The water electrolysis bubble detachment hydrogen evolution electrode based on the three-period minimal curved surface structure has superior bubble detachment performance and higher hydrogen production efficiency compared with traditional planar electrodes or foam nickel electrodes with disordered internal structure.

[0018] II. The nickel-based nickel-iron alloy catalyst with synergistic coupling of chemical deposition and electrodeposition exhibits an ultra-low hydrogen evolution overpotential and excellent electrochemical stability in long-term tests using both chronoamperometry and chronopotentialography, with no degradation in electrochemical performance and stable bubble control performance.

[0019] Third, based on the three-period minimal curved surface structure, a large-format hydrogen evolution electrode can be prepared by surface projection micro-stereolithography 3D printing technology, and the bubble detachment efficiency, bubble transport performance and electrolysis efficiency are all maintained without any degradation, which demonstrates the stability and innovation of this invention.

[0020] To make the above-mentioned objectives, features and advantages of this application more apparent and understandable, the specific embodiments of this application will be described in detail below with reference to the accompanying drawings. Attached Figure Description

[0021] Figure 1 A schematic diagram of a water bubble detachment from the hydrogen evolution electrode structure based on a three-period minimal surface structure, as proposed in the embodiment;

[0022] Figure 2 This represents the transport path of bubbles in the hydrogen evolution electrode structure proposed in this application;

[0023] Figure 3 This is a diagram illustrating the dynamic process of bubbles on the surface of the hydrogen evolution electrode before and after the start of the hydrogen evolution reaction in the water electrolysis example.

[0024] Figure 4 Three-dimensional structural diagrams and magnified micrographs of G-type, D-type, and P-type structures classified according to different curve equations;

[0025] In the figure, 1 is a three-dimensional curved channel, 2 is a continuous curved surface structure, 3 is a nickel-based dense conductive layer, and 4 is a nickel-iron (Ni-Fe) alloy catalyst layer. Detailed Implementation

[0026] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0027] Unless otherwise stated, the technical or scientific terms used in this embodiment have the ordinary meaning as understood by one of ordinary skill in the art to which this application pertains.

[0028] In this application, unless otherwise expressly specified and limited, the terms "connection," "fixed," etc., should be interpreted broadly. For example, "fixed" can mean a fixed connection, a detachable connection, or an integral part; it can mean a mechanical connection or an electrical connection; it can mean a direct connection or an indirect connection through an intermediate medium; it can mean the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention patent according to the specific circumstances.

[0029] Example 1: This example provides a method for preparing water electrolysis bubbles detached from the hydrogen evolution electrode using a three-period minimal curved surface structure as the substrate.

[0030] Please refer to Figures 1 to 4 A method for detaching water bubbles from a hydrogen evolution electrode using a three-period minimal surface structure as the substrate is described. The three-period minimal surface structure includes a continuous surface structure and three-dimensional surface channels. The three-dimensional surface channels are evenly distributed on the six walls of the continuous surface structure. The continuous surface structure and the surface channels drive the bubbles to detach rapidly from the surface and diffuse outwards from the electrode under the action of the continuous surface structure. This accelerates the flow of electrolyte inside the electrode, speeds up the ion exchange rate and the mass transfer rate, and ultimately accelerates the hydrogen evolution reaction.

[0031] In this embodiment, the electrode uses a three-period minimal curved surface structure as the substrate, and is integrally formed with a minimal curved surface structure possessing precise three-dimensional through-channels using surface projection micro-stereolithography 3D printing technology (PμSL technology). Subsequently, hydrogen evolution catalytic active materials are uniformly loaded onto the electrode surface and internal channels through chemical deposition and electrodeposition processes to form a composite electrode with a high specific surface area catalytic layer. Therefore, designing and fabricating a hydrogen evolution electrode with efficient water electrolysis bubble detachment is a key technical solution for improving the efficiency of hydrogen production from water electrolysis.

[0032] Example 2: A process for preparing water electrolysis bubbles detaching from the hydrogen evolution electrode using a three-period minimal curved surface structure as the substrate is as follows:

[0033] Step 1: Use 3D digital modeling software to construct the required three-period minimal surface electrode structure. The electrolytic water bubble separation hydrogen evolution electrode based on the three-period minimal surface structure is mainly composed of a continuous surface structure 2 and a three-dimensional surface channel 1 array. The cross-section of the channel can be irregular shapes such as circles and ellipses.

[0034] Step 2: Use slicing software to slice the 3D model into images;

[0035] Step 3: Use a 7.56-micron precision surface projection micro-stereolithography 3D printer to print the required three-period minimal curved surface hydrogen evolution electrode;

[0036] Step 4: Irradiate the sample repeatedly with a 405 nm ultraviolet lamp;

[0037] Step 5: Immerse the irradiated three-period minimal curved surface hydrogen evolution electrode in 1 M sulfuric acid solution and sonicate for 15-20 minutes;

[0038] Step 6: Vacuum dry for 10-15 minutes, and then treat with oxygen plasma hydrophilic treatment for 10 minutes;

[0039] Step 7: Deposit a nickel-based dense conductive layer on the three-period minimal surface structure using chemical deposition (divided into three stages: sensitization, activation, and deposition); deposit the nickel-based dense conductive layer 3 on the electrode structure through chemical deposition to give it conductivity and good adhesion.

[0040] Step 8: Electrodeposit the nickel-iron alloy catalyst onto the three-period minimal surface structure of the nickel substrate; use electrodeposition to deposit the nickel-iron alloy catalyst 4 onto the electrode structure to create a hydrogen evolution electrode with excellent electrochemical performance and bubble removal performance.

[0041] Step 9: Use ethanol to ultrasonically vibrate for 5-10 minutes and then vacuum dry for 5-10 minutes to prepare a three-period minimal curved surface hydrogen evolution electrode.

[0042] A composite electrode with a high specific surface area catalytic layer is formed by uniformly loading hydrogen evolution catalytic active materials onto the electrode surface and internal channels through chemical deposition and electrodeposition processes. This electrode utilizes the unique continuous surface and fluid optimization characteristics of its minimal curved surface structure to significantly promote mass transfer, charge transfer, and rapid desorption and transport of hydrogen bubbles at the electrode / electrolyte interface during electrolysis. This effectively avoids the bubble shielding effect, continuously reconstructs and exposes the catalytic active area, thereby significantly improving hydrogen evolution efficiency and electrode stability. This embodiment achieves a synergistic design of catalyst distribution and macro- and micro-structure, providing a new approach for the preparation of high-performance water electrolysis hydrogen production electrodes.

[0043] In this embodiment, the efficient water electrolysis using a three-period minimal curved surface structure as the matrix involves the detachment of bubbles from the hydrogen evolution electrode. During hydrogen electrolysis, bubbles are generated on the three-dimensional curved surface channel 1 and the continuous curved surface structure 2 of the electrode. Some bubbles flow within the three-dimensional curved surface channel 1 and eventually precipitate from the side of the electrode. Other bubbles grow and aggregate on the continuous curved surface structure 2, eventually expanding in volume and contacting the three-dimensional curved surface channel 1. Due to the asymmetry of the curved surface channel, a Laplace pressure difference is generated. Under the combined action of buoyancy and the Laplace pressure difference, the bubbles inside the electrode are transported to the outside. This electrode structure with ordered channels guides the rapid vertical release of bubbles, preventing them from stagnating inside the electrode.

[0044] Example 3: Hydrogen evolution electrode prepared based on the method in Example 2.

[0045] The electrode structure is formed based on different curve equations and geometric modeling.

[0046] The hydrogen evolution electrode is classified into G-type, D-type, and P-type structures according to different curve equations.

[0047] The hydrogen evolution electrode is a cuboid with a length of 1 cm, a width of 2 mm, and a height of 1 cm.

[0048] The continuous curved surface structure 2 of the hydrogen evolution electrode has a wall thickness ranging from 60 micrometers to 120 micrometers.

[0049] The hydrogen evolution electrode is formed into a cuboid by an array of cubic monomers, with the side length of each monomer ranging from 0.5 mm to 2.5 mm.

[0050] The bubble contact angle on the surface of the hydrogen evolution electrode ranges from 120° to 150°.

[0051] This application has disclosed the preferred embodiments as above, but it is not intended to limit this application. Any person skilled in the art who can make some changes or modifications to the above-disclosed structure and technical content to create equivalent embodiments without departing from the scope of the technical solution of this application shall still fall within the scope of the technical solution of this application.

Claims

1. A method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure, characterized in that: Include: Step 1: Construct a 3D model of the required three-period minimal surface structure; Step 2: Use slicing software to perform image slicing processing on the 3D model; Step 3: Use a surface projection micro-stereolithography 3D printer to print the required three-period minimal surface structure; Step 4: Cyclicly irradiate the three-period minimal surface structure with a nano-ultraviolet lamp; Step 5: Immerse the irradiated three-period minimal surface structure in sulfuric acid solution and then ultrasonically vibrate it. Step 6: Vacuum drying, followed by oxygen plasma hydrophilic treatment; Step 7: Deposit a nickel-based dense conductive layer onto the three-period minimal surface structure using chemical deposition; Step 8: Electrodeposition is used to deposit the nickel-iron alloy catalyst onto a three-period minimal surface structure on a nickel substrate; Step 9: Use ethanol for ultrasonic oscillation and vacuum drying to prepare a hydrogen evolution electrode with a three-period minimal curved surface structure.

2. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: The three-period minimal surface structure mentioned in step one includes a continuous surface structure and a three-dimensional surface channel. The three-dimensional surface channel is evenly distributed on the six walls of the continuous surface structure. The continuous surface structure and the surface channel drive the bubbles to quickly detach from the surface and diffuse outwards from the electrode under the action of the continuous surface structure, which accelerates the flow of electrolyte inside the electrode, accelerates the ion exchange rate and the mass transfer rate, and ultimately accelerates the hydrogen evolution reaction.

3. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: The three-period minimal surface structure is formed based on different curve equations and geometric modeling.

4. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 2, characterized in that: The three-period minimal surface structure is classified into G-type structure, D-type structure or P-type structure.

5. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: The cross-section of the three-dimensional curved channel is circular or elliptical.

6. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: The wall thickness of the continuous curved surface structure ranges from 60 micrometers to 120 micrometers.

7. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: The bubble contact angle on the electrode surface ranges from 120° to 150°.

8. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: In step four, a 405 nm ultraviolet lamp is used to irradiate the three-period minimal surface structure in a cyclic manner.

9. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: In step five, the irradiated three-period minimal surface structure is immersed in 1M sulfuric acid solution and ultrasonically vibrated for 15-20 minutes.

10. The method for preparing a hydrogen evolution electrode based on a three-period minimal surface structure according to claim 1, characterized in that: In step six, vacuum drying is performed for 10-15 minutes, followed by oxygen plasma hydrophilic treatment for 10 minutes.

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