CN-121976247-A - Hydrogen elimination layer with composite structure and preparation method and application thereof

Abstract

The invention relates to a dehydrogenation layer with a composite structure, and a preparation method and application thereof. The technical problems of potential safety hazards caused by overhigh hydrogen in oxygen at the anode side and pressurization are mainly solved, and the technical scheme of the invention is as follows: the hydrogen eliminating layer with composite structure is formed through coating the surface of proton exchange film several times, and reinforcing material is added between the layers. The hydrogen elimination layer can effectively avoid the problems of rapid reduction of proton conduction and hydrogen elimination performance caused by chemical degradation of the ion polymer layer of the hydrogen elimination layer and loss of a hydrogen elimination catalyst, solves the safety problems caused by chemical durability and overhigh hydrogen in oxygen of a proton exchange membrane electrode in the operation process of a PEM (proton exchange membrane) water electrolysis device, and has wide application prospect.

Inventors

• WANG XINLEI
• ZHANG XIAN
• WU ZHEYU
• Qin Banggang

Assignees

• 上海升水新能源科技有限公司

Dates

Publication Date

20260505

Application Date

20260109

Claims (9)

1. 1. The hydrogen eliminating layer with the composite structure is characterized in that the hydrogen eliminating layer is coated on the surface of the proton exchange membrane for multiple times to form a multi-layer composite structure, and reinforcing materials are added between the layers of the hydrogen eliminating layer.
2. 2. The hydrogen-eliminating layer according to claim 1, wherein the reinforcing material is selected from one or more of expanded polytetrafluoroethylene, polyvinylidene fluoride, polypropylene, polyethylene.
3. 3. The hydrogen elimination layer according to claim 1, wherein said proton exchange membrane is a perfluorosulfonic acid resin dispersion.
4. 4. The hydrogen eliminating layer according to claim 1, wherein the thickness of the hydrogen eliminating layer is 4-10 μm.
5. 5. A method for preparing the hydrogen eliminating layer with the composite structure as defined in claim 1, which is characterized by comprising the following steps of ① preparing a film forming liquid by fully mixing perfluorinated sulfonic acid resin, a hydrogen eliminating catalyst and an aqueous alcohol solution; ② Preparing a dehydrogenation layer: coating a film-forming liquid on a substrate, and coating a reinforcing material on the surface of the film-forming liquid after each coating; step two, drying and annealing are carried out on the substrate and the wet film on the substrate; And thirdly, coating film forming liquid with a certain thickness on the film surface which is preliminarily dried and coated with the reinforcing material, and drying and annealing to obtain the final hydrogen eliminating layer.
6. 6. The method according to claim 5, wherein the hydrogen-eliminating catalyst is a noble metal platinum-based catalyst, the alcohol of the alcohol solution is a mixed solution of ethanol and isopropanol, the substrate is made of any one of release polyethylene terephthalate, release polyimide and release polytetrafluoroethylene film, and the reinforcing material is one or more selected from the group consisting of expanded polytetrafluoroethylene, polyvinylidene fluoride, polypropylene and polyethylene.
7. 7. The method of claim 5, wherein the coating is by solution casting.
8. 8. The method of claim 5, wherein the drying and annealing is performed by a combination of infrared baking and oven drying, the temperature of the infrared baking is 60 ℃, the drying time is 3min, the temperature of the oven drying is 50180 ℃, and the drying time is 6-10min.
9. 9. Use of a hydrogen-eliminating layer having a composite structure according to claim 1 on an electrolytic water membrane electrode.

Description

Hydrogen elimination layer with composite structure and preparation method and application thereof Technical Field The invention relates to the field of hydrogen production by water electrolysis, in particular to a preparation method and application of a hydrogen elimination material with a composite structure. Background The hydrogen energy has the advantages of high energy density, no pollution, abundant reserves, wide application and the like, and has wide application prospect in the fields of electric power, heat energy, industry and the like. Among them, the preparation of hydrogen as an upstream process of a hydrogen energy utilization chain is critical to the development of hydrogen energy. The proton exchange membrane electrolyzes water to prepare hydrogen (proton exchange membrane water electrolysis, PEMWE) has great application and development prospect in the aspects of renewable energy utilization and hydrogen energy storage due to the advantages of quick dynamic response, good fluctuation adaptability, high hydrogen purity, relatively simple process and the like. However, hydrogen and oxygen interpenetration is often accompanied during operation of proton exchange membrane (proton exchange membrane, PEM) electrolyzer, which on the one hand accelerates degradation of the membrane electrode, reduces electrolyzer operating efficiency, and may also cause "hydrogen embrittlement" of the electrolyzer clamps. More importantly, enrichment of hydrogen at the anode side can pose a significant safety hazard, particularly when the relative concentration of oxygen at the anode side is low under low current density operating conditions, the permeated hydrogen can exceed the lower explosion limit (lower explosive limited, LEL), and in commercial operation, the danger is further amplified by pressurized operation of the cathode or by thinner proton exchange membranes. There is therefore a need to develop new hydrogen elimination layers to eliminate the safety problems caused by too high hydrogen in the oxygen at the anode side and pressurization. Disclosure of Invention The invention mainly aims to provide a preparation method and application of a dehydrogenation layer with a composite structure, which can effectively avoid the mutual permeation of hydrogen and oxygen, eliminate the degradation of a membrane electrode, improve the running efficiency of an electrolytic cell and eliminate the danger caused by hydrogen embrittlement of an electrolytic cell clamp. The invention realizes the aim through the following technical scheme that the hydrogen elimination layer with the composite structure is formed into a multi-layer composite structure by coating the surface of the proton exchange membrane for multiple times, and reinforcing materials are added between the layers of the hydrogen elimination layer. The substrate is made of any one of release polyethylene terephthalate, release polyimide or release polytetrafluoroethylene film. The reinforcing material is selected from one or more of ePTFE (expanded polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PP (polypropylene) and PE (polyethylene), and preferably ePTFE (expanded polytetrafluoroethylene). The proton exchange membrane is a perfluorosulfonic acid resin dispersion liquid. The thickness of the hydrogen-eliminating layer is 4-10 μm, preferably 5-6 μm. A preparation method of a dehydrogenation layer with a composite structure comprises the following steps: ① Preparing a membrane preparation liquid, namely fully mixing perfluorinated sulfonic acid resin, a dehydrogenation catalyst and an aqueous alcohol solution to obtain the membrane preparation liquid; ② Preparing a dehydrogenation layer: Coating the film-forming liquid on a substrate, and coating a reinforcing material on the surface of the film-forming liquid after each coating. And step two, drying and annealing the substrate and the wet film on the substrate. And thirdly, coating film forming liquid with a certain thickness on the film surface which is preliminarily dried and coated with the reinforcing material, and drying and annealing to obtain the final hydrogen eliminating layer. The alcohol substance is a mixed solution of ethanol and isopropanol. The reinforcing material is selected from one or more of ePTFE, PVDF, PP, PE, preferably ePTFE. The dehydrogenation catalyst comprises a noble metal-based catalyst, preferably platinum black. The substrate is made of any one of release polyethylene terephthalate, release polyimide or release polytetrafluoroethylene, and release polyimide is preferred. The coating mode is solution casting coating. The gap of the solution casting coating is 50-300 μm, preferably 70-160 μm. The coating speed is 1-3m/min, preferably 2m/min. The drying and annealing modes are a mode of combining infrared baking and oven drying, the temperature of the infrared baking is 60 ℃, and the drying time is 3min. The temperature of the oven is 50180 ℃, preferably 80 ℃, and the