CN-121976217-A - Preparation method of high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by femtosecond laser

CN121976217ACN 121976217 ACN121976217 ACN 121976217ACN-121976217-A

Abstract

The invention provides a preparation method of an efficient mass transfer anti-precipitation seawater hydrogen electrode constructed by femtosecond laser, and relates to the technical field of seawater electrolysis hydrogen production. The invention comprises the steps of carrying out substrate pretreatment on a conductive substrate, periodically preparing a hump microstructure on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology, and loading a catalytic active layer on the surface of the hump microstructure substrate to form an integrated electrode. The integrated electrode can improve catalytic activity and mass transfer efficiency under the seawater electrolysis condition, inhibit magnesium-calcium precipitation coverage, and realize the synergistic optimization of high-efficiency hydrogen production and electrode stability.

Inventors

TAO HAIYAN
SUN YING
HE YAOWEN
YANG YING
SONG LIN

Assignees

长春理工大学

Dates

Publication Date: 20260505
Application Date: 20260311

Claims (10)

1. A preparation method of an efficient mass transfer anti-precipitation seawater hydrogen electrode constructed by femtosecond laser is characterized by comprising the following steps: performing substrate pretreatment on a conductive substrate to obtain a conductive substrate pretreated by the substrate; Periodically preparing a hump microstructure on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface and obtain the hump microstructure substrate; And loading a catalytic active layer on the surface of the hump microstructure substrate by adopting one or more of electrochemical deposition, a hydrothermal method and chemical vapor deposition to form an integrated electrode, thereby obtaining the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode.
2. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein the method for preparing the conductive substrate is characterized by comprising the following steps of: Providing the conductive substrate, wherein the conductive substrate is a nickel sheet, foam nickel or stainless steel mesh; and performing the substrate pretreatment on the conductive substrate to obtain a conductive substrate pretreated by the substrate.
3. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein the substrate pretreatment is performed on the conductive substrate to obtain the conductive substrate pretreated by the substrate, comprising: And cleaning the conductive substrate to obtain the conductive substrate pretreated by the substrate.
4. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein a hump microstructure is periodically prepared on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface, and the hump microstructure substrate is obtained, and the method comprises the following steps: setting the laser wavelength of the femtosecond laser direct writing technology to 1030 nanometers; setting the pulse width of the femtosecond laser direct writing technology to 500 femtoseconds; setting the power of the femtosecond laser direct writing technology to 10-20 watts; setting a repetition frequency of the femtosecond laser direct writing technology to 500 kilohertz to 1 megahertz; The scanning speed of the femtosecond laser direct writing technique is set to 0.2 meters per second to 1 meter per second.
5. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein a hump microstructure is periodically prepared on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface, and the hump microstructure substrate is obtained, and the method comprises the following steps: setting the column diameter of the hump microstructure to be 50-100 microns; Setting the height of the hump microstructure to be 50-300 microns; the pillar spacing of the hump microstructure is set to 20 micrometers to 150 micrometers.
6. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein a hump microstructure is periodically prepared on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface, and the hump microstructure substrate is obtained, and the method comprises the following steps: Preparing the hump microstructure forming a transverse and longitudinal cross channel on the surface of the conductive substrate; After the hump microstructure is formed, ultrasonic cleaning is carried out on the conductive substrate, so that the hump microstructure substrate with transverse and longitudinal crossed channels on the surface is obtained.
7. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 6, wherein a hump microstructure is periodically prepared on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface, so as to obtain the hump microstructure substrate, which comprises the following steps: Setting the power of the femtosecond laser direct writing technology to 7.5 watts; setting the repetition frequency of the femtosecond laser direct writing technology to 500 kilohertz; Setting a scanning speed of the femtosecond laser direct writing technology to be 0.2 meters per second; Setting the scanning interval of the femtosecond laser direct writing technology to be 60 microns; Setting the scanning times of the femtosecond laser direct writing technology to be 50 times; after the hump microstructure is formed, the width of the transverse and longitudinal intersecting channels is made to be 50 micrometers.
8. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein one or more of electrochemical deposition, a hydrothermal method and chemical vapor deposition are adopted to load a catalytic active layer on the surface of the hump microstructure substrate so as to form an integrated electrode, and the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode is obtained, and the method comprises the following steps: growing and forming the catalytic active layer on the surface of the hump microstructure substrate; the thickness of the catalytically active layer is set to 10 nm to 2 μm.
9. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 1, wherein one or more of electrochemical deposition, a hydrothermal method and chemical vapor deposition are adopted to load a catalytic active layer on the surface of the hump microstructure substrate so as to form an integrated electrode, and the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode is obtained, and the method comprises the following steps: generating a precursor on the surface of the hump microstructure substrate by a hydrothermal method to obtain the hump microstructure substrate carrying the precursor; And heating the hump microstructure substrate carrying the precursor to 350 ℃ under the protection atmosphere of inert gas, and preserving heat for 2 hours to complete the phosphating reaction and generate the catalytic active layer formed by the CoNiP nano catalyst, thereby obtaining the integrated electrode.
10. The method for preparing the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser according to claim 9, wherein a precursor is generated on the surface of the hump microstructure substrate by a hydrothermal method to obtain the hump microstructure substrate carrying the precursor, comprising the following steps: adding cobalt nitrate, nickel nitrate, urea and ammonium fluoride into deionized water, and stirring until the cobalt nitrate, the nickel nitrate, the urea and the ammonium fluoride are completely dissolved to obtain a mixed precursor solution; transferring the mixed precursor liquid into a hydrothermal kettle, putting the mixed precursor liquid into the hump microstructure substrate, sealing the hydrothermal kettle, and then performing constant-temperature reaction for 6 hours at 120 ℃ to generate the precursor on the surface of the hump microstructure substrate; And naturally cooling the hydrothermal kettle to room temperature after the reaction is finished, taking out the hump microstructure substrate, washing the hump microstructure substrate with deionized water, and drying to obtain the hump microstructure substrate loaded with the precursor.

Description

Preparation method of high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by femtosecond laser Technical Field The invention relates to the technical field of seawater electrolysis hydrogen production, in particular to a preparation method of an efficient mass transfer anti-precipitation seawater hydrogen electrode constructed by femtosecond laser. Background The seawater electrolysis hydrogen production has important application prospect because of the convenience in acquiring water resources, but the continuous generation and accumulation of solid phase precipitation on the electrode surface caused by complex ion environment cover electrode catalytic active sites, so that the gas release and electrochemical reaction interface updating are seriously hindered, and the method becomes a key bottleneck for limiting the seawater hydrogen production efficiency and long-term stable operation. The existing research focuses on improving the intrinsic activity or corrosion resistance design of electrode materials, and the regulation and control effect of the electrode interface two-phase flow behavior in the deposition adhesion and desorption processes still lacks systematic knowledge, so that the problem of electrode failure caused by deposition is difficult to effectively alleviate from the dynamic aspect. Disclosure of Invention In order to overcome the defects of the prior art, the invention aims to provide the preparation method of the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode constructed by the femtosecond laser, which can simultaneously improve the catalytic activity, the mass transfer efficiency and the electrode stability under the seawater electrolysis condition and realize the collaborative optimization of the high-efficiency hydrogen production and the anti-precipitation performance. In order to achieve the above object, the present invention provides the following solutions: a preparation method of an efficient mass transfer anti-precipitation seawater hydrogen electrode constructed by femtosecond laser comprises the following steps: Performing substrate pretreatment on the conductive substrate to obtain a conductive substrate subjected to substrate pretreatment; Periodically preparing a hump microstructure on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface and obtain the hump microstructure substrate; and (3) loading a catalytic active layer on the surface of the hump microstructure substrate by adopting one or more of electrochemical deposition, a hydrothermal method and chemical vapor deposition to form an integrated electrode, thereby obtaining the high-efficiency mass transfer anti-precipitation seawater hydrogen electrode. Preferably, the pretreatment of the conductive substrate to obtain a pretreated conductive substrate comprises: Providing a conductive substrate, wherein the conductive substrate is a nickel sheet, foam nickel or stainless steel mesh; a substrate pretreatment is performed on the conductive substrate to obtain a substrate pretreated conductive substrate. Preferably, the substrate pretreatment is performed on the conductive substrate to obtain a substrate pretreated conductive substrate, including: And cleaning the conductive substrate to obtain the conductive substrate pretreated by the substrate. Preferably, a hump microstructure is periodically prepared on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface, thereby obtaining the hump microstructure substrate, which comprises the following steps: setting the laser wavelength of the femtosecond laser direct writing technology to 1030 nanometers; Setting the pulse width of the femtosecond laser direct writing technology to 500 femtoseconds; setting the power of the femtosecond laser direct writing technology to 10-20 watts; Setting the repetition frequency of the femtosecond laser direct writing technology to 500 kilohertz to 1 megahertz; The scanning speed of the femtosecond laser direct writing technique is set to 0.2 meters per second to 1 meter per second. Preferably, a hump microstructure is periodically prepared on the surface of the conductive substrate pretreated by the substrate by adopting a femtosecond laser direct writing technology so as to regulate and control the gas-liquid two-phase flow characteristic of a hydrogen production interface, thereby obtaining the hump microstructure substrate, which comprises the following steps: setting the pillar diameter of the hump microstructure to be 50-100 microns; setting the height of the hump microstructure to be 50-300 microns; The pillar