CN-121976241-A - Preparation method of hydrogen evolution electrode based on femtosecond laser liquid phase processing

CN121976241ACN 121976241 ACN121976241 ACN 121976241ACN-121976241-A

Abstract

The invention provides a hydrogen evolution electrode preparation method based on femtosecond laser liquid phase processing, and relates to the technical field of femtosecond laser liquid phase micro-processing. The method comprises the steps of performing grid scanning processing on the surface of a conductive substrate by using femtosecond laser in an air environment, constructing a micron-sized columnar microstructure array to obtain a columnar microstructure array substrate, immersing the columnar microstructure array substrate into a CuCl 2 solution, performing transverse scanning processing by using the femtosecond laser in a liquid-phase environment, growing a nickel-copper oxide and nickel-copper alloy composite nanoparticle layer on the surface of the columnar microstructure array substrate in situ to obtain a three-dimensional micro-nano composite structure electrode substrate, and sequentially cleaning, electrochemically activating and drying the electrode substrate to obtain the hydrogen evolution electrode. The electrode has the advantages of high specific surface area and excellent bubble desorption capacity, and can improve interface mass transfer efficiency and hydrogen evolution reaction kinetics and improve long-term working stability.

Inventors

TAO HAIYAN
HE YAOWEN
Tian Mowei
YANG YING
FANG XUAN
SONG LIN

Assignees

长春理工大学

Dates

Publication Date: 20260505
Application Date: 20260311

Claims (10)

1. The preparation method of the hydrogen evolution electrode based on the femtosecond laser liquid phase processing is characterized by comprising the following steps of: Performing grid scanning processing on the surface of a conductive substrate in an air environment by using femtosecond laser so as to construct a micron-sized columnar microstructure array on the surface of the conductive substrate, thereby obtaining a columnar microstructure array substrate; Immersing the columnar microstructure array substrate into a CuCl 2 solution, and performing transverse scanning processing on the columnar microstructure array substrate immersed into the CuCl 2 solution by using femtosecond laser in a liquid phase environment so as to grow a nickel copper oxide and nickel copper alloy composite nano-particle layer on the surface of the columnar microstructure array in situ, thereby obtaining a three-dimensional micro-nano composite structure electrode substrate; Cleaning the electrode substrate of the three-dimensional micro-nano composite structure; Performing electrochemical activation treatment on the cleaned electrode substrate with the three-dimensional micro-nano composite structure to obtain an electrode substrate subjected to electrochemical activation; And drying the electrode substrate subjected to electrochemical activation to obtain the hydrogen evolution electrode.
2. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process according to claim 1, wherein grid scanning process is performed on a surface of a conductive substrate in an air environment by using femtosecond laser to construct a micrometer-sized columnar microstructure array on the surface of the conductive substrate, to obtain a columnar microstructure array substrate, comprising: Providing the conductive substrate; performing linear scanning on the surface of the conductive substrate in a first scanning direction in an air environment; And performing linear scanning on the surface of the conductive substrate in a second scanning direction crossing the first scanning direction to form the grid scanning processing, so as to construct the micron-sized columnar microstructure array on the surface of the conductive substrate and obtain the columnar microstructure array substrate.
3. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process according to claim 1, wherein grid scanning process is performed on a surface of a conductive substrate in an air environment by using femtosecond laser to construct a micrometer-sized columnar microstructure array on the surface of the conductive substrate, to obtain a columnar microstructure array substrate, comprising: setting a scanning interval of the grid scanning process to 40 to 100 micrometers; setting the scanning times of the grid scanning processing to 40 to 80 times; Setting the power of the grid scanning processing to be 5-10 watts; setting a repetition frequency of the grid scanning process to 125 to 1000 kilohertz; The scanning speed of the grid scanning process is set to 0.1 to 0.3 meters per second to obtain the columnar microstructure array substrate.
4. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process as set forth in claim 3, wherein performing grid scan process on a surface of a conductive substrate in an air environment using a femtosecond laser to construct a micrometer-sized columnar microstructure array on the surface of the conductive substrate, obtaining a columnar microstructure array substrate, comprising: Setting a scanning interval of the grid scanning process to 60 micrometers; setting the scanning times of the grid scanning processing to 40 times; Setting the repetition frequency of the grid scanning process to 500 kilohertz; setting the power of the grid scanning process to 6 to 8 watts; the scanning speed of the grid scanning process was set to 0.2 meters per second to obtain the columnar microstructure array substrate.
5. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process as set forth in claim 1, wherein immersing the columnar microstructure array substrate in a CuCl 2 solution, and performing a lateral scanning process on the columnar microstructure array substrate immersed in the CuCl 2 solution with a femtosecond laser in a liquid phase environment to grow a nickel copper oxide and nickel copper alloy composite nanoparticle layer on the surface of the columnar microstructure array in situ, to obtain a three-dimensional micro-nano composite structure electrode substrate, comprising: immersing the columnar microstructure array substrate in 0.5 moles per liter of the CuCl 2 solution; And performing linear scanning on the columnar microstructure array substrate along a transverse scanning direction in the liquid phase environment to form transverse scanning processing, so that a composite nano particle layer formed by the nickel-copper oxide and the nickel-copper alloy grows in situ on the surface of the columnar microstructure array substrate, and the three-dimensional micro-nano composite structure electrode substrate is obtained.
6. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process as recited in claim 5, wherein immersing the columnar microstructure array substrate in a CuCl 2 solution, and performing a lateral scanning process on the columnar microstructure array substrate immersed in the CuCl 2 solution by using a femtosecond laser in a liquid phase environment, so as to grow a nickel copper oxide and nickel copper alloy composite nanoparticle layer on the surface of the columnar microstructure array in situ, thereby obtaining a three-dimensional micro-nano composite structure electrode substrate, comprising: setting a scanning interval of the lateral scanning process to 30 to 50 micrometers; setting the scanning times of the transverse scanning process to 80 to 300 times; Setting the power of the transverse scanning process to 5 to 10 watts; Setting a repetition frequency of the lateral scanning process to 125 to 1000 kilohertz; And setting the scanning speed of the transverse scanning processing to be 0.1-0.3 m/s so as to obtain the electrode substrate of the three-dimensional micro-nano composite structure.
7. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process as recited in claim 5, wherein immersing the columnar microstructure array substrate in a CuCl 2 solution, and performing a lateral scanning process on the columnar microstructure array substrate immersed in the CuCl 2 solution by using a femtosecond laser in a liquid phase environment, so as to grow a nickel copper oxide and nickel copper alloy composite nanoparticle layer on the surface of the columnar microstructure array in situ, thereby obtaining a three-dimensional micro-nano composite structure electrode substrate, comprising: setting the power of the transverse scanning processing to 6 watts; setting the repetition frequency of the transverse scanning process to 500 khz; Setting a scanning interval of the lateral scanning process to 40 micrometers; setting the scanning times of the transverse scanning processing to 100 times; And setting the scanning speed of the transverse scanning processing to be 0.2 meter per second to obtain the three-dimensional micro-nano composite structure electrode substrate.
8. The method for manufacturing a hydrogen evolution electrode based on liquid phase processing of femtosecond laser according to claim 1, wherein a laser wavelength of the femtosecond laser is set to 1030 nm, a pulse width of the femtosecond laser is set to 300 femtoseconds, a repetition frequency of the femtosecond laser is set to 100 to 1000 kilohertz, and a spot radius of the femtosecond laser is set to 45 micrometers.
9. The method for preparing the hydrogen evolution electrode based on the femtosecond laser liquid phase process as set forth in claim 1, wherein the cleaning of the three-dimensional micro-nano composite structure electrode substrate comprises: Ethanol is adopted to clean the electrode substrate of the three-dimensional micro-nano composite structure; and cleaning the electrode substrate of the three-dimensional micro-nano composite structure after ethanol cleaning by adopting deionized water.
10. The method for preparing a hydrogen evolution electrode based on femtosecond laser liquid phase process as set forth in claim 1, wherein the step of performing electrochemical activation treatment on the three-dimensional micro-nano composite structure electrode substrate after the cleaning to obtain an electrochemically activated electrode substrate comprises: performing cyclic voltammetric CV (constant current) circulation on the electrode substrate of the three-dimensional micro-nano composite structure after the cleaning; The number of cycles of the cyclic voltammetric CV cycle was set to 1000 to obtain the electrochemically activated electrode substrate.

Description

Preparation method of hydrogen evolution electrode based on femtosecond laser liquid phase processing Technical Field The invention relates to the technical field of femtosecond laser liquid phase micro-machining, in particular to a hydrogen evolution electrode preparation method based on femtosecond laser liquid phase machining. Background With the increase of the duty ratio of hydrogen energy in energy systems, electrochemical hydrogen evolution (HER, hydrogen Evolution Reaction) has become an important path for hydrogen production, and especially alkaline systems and seawater systems have received attention due to equipment scalability and resource availability. Aiming at a HER electrode system, in recent years, research focuses on the expansion from simply improving the catalytic activity to the construction direction of electrode interface engineering and structured carriers, and the efficiency is cooperatively improved by regulating and controlling the reaction interface mass transfer, gas precipitation and charge transfer processes. Meanwhile, in order to improve the effective surface area of the electrode, the exposure of the active site and the wettability of the interface, micro-nano structured materials, three-dimensional multi-level structures and composite metal/metal oxide systems gradually become the main research flow, wherein Ni, niFe, niCo, niCu and other matrixes and oxides/hydroxides have good stability and processability, and have been widely researched in alkaline HER systems. The existing research expands from material chemistry to advanced processing technology, and in particular, the technical paths of laser surface processing, micro-nano etching, chemical etching, electrodeposition and the like are used for constructing an electrode interface structure with micro-nano composite dimensions so as to enhance gas-liquid mass transfer and reaction kinetics. In addition, the ultrafast laser technology (such as femtosecond laser) has unique capability in the aspects of inducing periodic structures (LIPSS), grooves, hole arrays and particle attachment structures on the metal surface due to the advantages of ultra-short pulse width, cold working, strong material adaptability and the like. Meanwhile, heterostructures and multicomponent synergic catalysis (such as Ni-Cu, ni-Co, ni-Fe, and the like) are an important direction in recent years because of being capable of reducing HER reaction energy barriers and regulating and controlling electronic structures, so that electrodes exhibit better catalytic dynamics. Although the current HER electrodes have progressed in terms of catalytic performance, there are several shortcomings: Firstly, most structured electrodes are constructed by adopting photoetching, electroplating, cold spraying, electrodeposition or chemical corrosion, and do not have the capability of directly forming a three-dimensional micro-nano structure on a metal matrix; secondly, the traditional processing route is difficult to realize the hierarchical recombination of the micrometer scale and the nanoparticle structure, so that the effective surface area and the catalytic efficiency of the interface are not fully exerted; Thirdly, multiple transfer, secondary coating or auxiliary fixing steps are still commonly adopted in the structure construction and catalytic layer deposition processes, so that the binding force between the catalytic layer and the substrate is insufficient, and stable output under alkaline environment, especially under the condition of high current density, is not facilitated; fourthly, the problems of processing cost, equipment matching and material system adaptation make engineering popularization difficult to realize in the prior art. Therefore, there is still a need to develop a method for preparing HER electrode with hierarchical structure, stable interface, direct processing on metal substrate, and high catalytic performance and structural stability. Disclosure of Invention In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a hydrogen evolution electrode based on femtosecond laser liquid phase processing, which constructs a micron-sized columnar array through femtosecond laser air and grows a nickel-copper composite nano-particle layer in situ in a CuCl 2 liquid phase, thereby improving mass transfer efficiency, reaction dynamics and electrode stability. In order to achieve the above object, the present invention provides the following solutions: A hydrogen evolution electrode preparation method based on femtosecond laser liquid phase processing comprises the following steps: Performing grid scanning processing on the surface of the conductive substrate in an air environment by using femtosecond laser so as to construct a micron-sized columnar microstructure array on the surface of the conductive substrate, thereby obtaining a columnar microstructure array substrate; immersing a columnar microstruct