CN-122007634-A - Laser-induced proton exchange membrane multistage patterning method

CN122007634ACN 122007634 ACN122007634 ACN 122007634ACN-122007634-A

Abstract

A laser-induced proton exchange membrane multi-stage patterning method belongs to the fields of laser and substance interaction and proton exchange membrane processing. Under the conditions of no template, no external material and no chemical modification, the local transient heating and melting effect generated when the pulse laser acts on the surface of the proton exchange membrane is utilized, the membrane material is guided to undergo physical rearrangement and solidification in the cooling process, and a patterned structure with multi-scale and multi-level characteristics is directly formed on the surface of the membrane. The controllable construction of the multi-stage pattern is realized by regulating and controlling parameters such as laser wavelength, pulse width, scanning speed, point engraving time, repetition frequency, scanning path and the like, constructing a micron-scale primary structure on the surface of the proton exchange membrane, and forming a nano-scale or submicron-scale secondary structure in a local area of the primary structure. The invention is suitable for various proton exchange membrane materials, has the advantages of simple process, strong structural designability, high digitization degree in the processing process and the like, effectively improves the surface morphology of the membrane and the interface state of the membrane and the electrode, and has good engineering application prospect.

Inventors

JIN YUQI
Wen Tianzhuo
NI WEIWEI
XIA ZHANGXUN
WANG SULI
Yu Xinhou
LI GANG
TENG FEI
LUAN SHIYI

Assignees

中国科学院大连化学物理研究所

Dates

Publication Date: 20260512
Application Date: 20260326

Claims (10)

1. A laser-induced proton exchange membrane multistage patterning method is characterized in that laser is applied to the surface of a proton exchange membrane in a one-time or multiple-time action mode through regulating and controlling laser energy in time and/or space, a proton exchange membrane material is subjected to transient temperature rise in a local area without a solid template, heat-induced surface softening, melting and physical rearrangement behaviors are sequentially or superpositionedly generated in the gasification and recrystallization processes, a multistage patterning morphology formed by superposition of structures with different scales is formed on the surface of the membrane, and the chemical composition of the proton exchange membrane is kept unchanged before and after patterning, and the method specifically comprises the following steps: step 1, selecting a proton exchange membrane to be processed; step 2, determining laser processing parameters according to the material characteristics and the expected pattern structure of the proton exchange membrane; step 3, adjusting the laser focus to the surface of the proton exchange membrane, and carrying out laser scanning on the surface of the proton exchange membrane according to a preset scanning path; and 4, after the laser processing is finished, cooling the film by 5 s-10 s at room temperature, and finally forming a multi-stage patterning morphology formed by overlapping structures with different scales on the surface of the film.
2. The method according to claim 1, wherein in the step 2, the proton exchange membrane is selected from perfluorosulfonic acid proton exchange membrane, aromatic heterocyclic proton exchange membrane or aromatic heterocyclic proton exchange membrane doped with acid.
3. The multistage patterning method of a proton exchange membrane induced by laser according to claim 1, wherein the laser processing parameters in the step 2 include laser wavelength, laser pulse width, laser scanning speed, point engraving time and laser repetition frequency, the above laser processing parameters are matched with each other, and the selection principle of the laser processing parameters is specifically as follows: The laser wavelength is in the wavelength range of 200 nm-2000 nm; The laser pulse width is selected according to the expected structural scale, and is 1 ns-10 ms; the laser scanning speed is adjusted according to the pattern period and the structure scale and is 10 mm/s-3000 mm/s; The point engraving time is 1 ns-10 ms; the laser repetition frequency is selected according to the required structural level, and is 1 kHz-500 kHz.
4. A method for multistage patterning of a laser-induced proton exchange membrane according to claim 3, wherein the selection principle of the laser processing parameters is as follows: The laser wavelength is preferably the wavelength with lower transmissivity of the proton exchange membrane in the wavelength range; The laser pulse width is preferably 200 ns-3000 ns; The laser scanning speed is preferably 200 mm/s-2000 mm/s; the point engraving time is preferably 0.01 ms-0.1 ms; The laser repetition frequency is preferably 100 kHz-300 kHz.
5. A method of multi-stage patterning a laser-induced proton exchange membrane according to claim 3, wherein the laser processing parameters further comprise a laser spot diameter of 0.1 um to 500 um.
6. The method of claim 5, wherein in step 3, the laser energy is applied to the surface of the proton exchange membrane by scanning, projection, point-by-point action, or a combination thereof.
7. The method of claim 6, wherein in the step 3, the scanning path is used to determine the morphology of the primary structure of the pattern, and the remaining laser processing parameters are used to control the secondary structure characteristics formed on the surface of the primary structure.
8. The method of claim 1, wherein in step 4, the patterned structure has at least one micro-scale and/or nano-scale topographical feature, wherein the feature size is 100 nm-1 mm.
9. The method for multistage patterning of a proton exchange membrane induced by laser according to claim 1, wherein multistage patterning structures stacked by different dimensions are formed on the surface of the proton exchange membrane by adjusting and controlling time intervals, space intervals, scanning paths or repetition frequencies of laser action.
10. A patterned proton exchange membrane, characterized in that the patterned proton exchange membrane is obtained by adopting the preparation method of any one of claims 1-9, is applied to an electrochemical energy conversion or energy storage device, and can reduce activation polarization and/or mass transfer polarization by synergistically improving the interface state of a membrane and an electrode and the transmission condition of reactants through a multi-stage pattern structure.

Description

Laser-induced proton exchange membrane multistage patterning method Technical Field The invention belongs to the fields of interaction of laser and substances and proton exchange membrane processing, and relates to a laser-induced proton exchange membrane multistage patterning method, in particular to a method for constructing a multistage pattern structure on the surface of a proton exchange membrane under the template-free condition by utilizing physical rearrangement of a laser-induced material. Background Electrochemical devices such as fuel cells, water electrolysis hydrogen production and the like provide a key technical path for the efficient utilization and conversion of hydrogen energy. The proton exchange membrane is used as a key functional component in the device and plays important roles in proton conduction, reactant isolation, reaction occurrence and the like, and the performance of the proton exchange membrane directly influences the overall efficiency and stability of the electrochemical device. During electrochemical operation, the performance loss associated with proton exchange membranes is generally expressed as an increase in activation polarization, ohmic polarization, and mass transfer polarization, corresponding to the reaction kinetic resistance of the reaction interface, the resistance of the membrane body itself, and the resistance of the reactant in the process of transporting the reactant to the reaction interface, respectively. As the device operates for a long period of time, the membrane material may undergo structural and morphological changes, which may result in the above-mentioned increase in polarization behavior, thereby limiting the improvement in the performance of the electrochemical device. The proton exchange membrane surface is subjected to patterning treatment, and a micrometer or nanometer scale structure is introduced into the membrane surface, so that the method is an effective means for improving the interface state of the membrane and the electrode and improving the effective area of an electrochemical reaction interface. Related researches show that compared with a single-scale structure, the multi-level pattern formed by stacking different-scale structures is constructed on the surface of the membrane, so that the mass transfer condition of reactants is improved while the interface reaction area is improved, and the limitation of activation polarization and mass transfer polarization on performance is synergistically relieved in different working current density intervals. Therefore, the construction of the multi-stage and multi-scale pattern structure on the surface of the proton exchange membrane has important application value. However, the existing technical schemes for constructing the multi-stage structure are mostly dependent on modes such as template imprinting, multiple transfer printing or multilayer superposition processing, and the like, so that the process flow is complex, the processing flexibility is limited, and foreign matters or defects are easily introduced on the surface of the membrane in the processes of template processing and using, so that the intrinsic performance of the membrane material is influenced. Such template-dependent methods also have limitations in terms of process scale-up and continuous production. Therefore, there is a need for a proton exchange membrane surface multi-stage patterning method that has simplified process flow, flexible structure control, and no introduction of exogenous substances. Disclosure of Invention Aiming at the problems in the prior art, the invention provides a laser-induced proton exchange membrane multi-stage patterning method. The method utilizes the instantaneous temperature rise, melting and subsequent physical rearrangement process of the proton exchange membrane material in a local area under the action of laser, and directly forms a multi-scale and multi-level patterning structure on the surface of the membrane under the template-free condition without introducing any additional materials or chemical modification steps. In order to achieve the above purpose, the following technical scheme is adopted: a laser-induced multistage patterning method for proton exchange membrane features that the laser energy is regulated in time and/or space to make the laser be applied to the surface of proton exchange membrane in one or more modes, so the temp of proton exchange membrane is raised in local area without solid template, and the surface softening, fusing and physical rearrangement actions induced by heat are sequentially or overlapped in gasifying and recrystallizing process. The method specifically comprises the following steps: step 1, selecting a proton exchange membrane to be processed; Step 2, determining laser processing parameters including, but not limited to, laser wavelength, laser pulse width, laser scanning speed, point engraving time and laser repetition frequency according to