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CN-121976218-A - Tubular integrated membrane electrode assembly for PEM (PEM) electrolytic tank and preparation method thereof

CN121976218ACN 121976218 ACN121976218 ACN 121976218ACN-121976218-A

Abstract

The invention discloses a tubular integrated membrane electrode assembly for a PEM (proton exchange membrane) electrolytic tank and a preparation method thereof, and relates to the technical field of membrane electrode preparation, comprising the following steps of placing a polyacrylonitrile fiber membrane in Nafion solution for dipping, adding palladium-loaded UiO-66-NH 2 , carrying out ultrasonic dipping and drying to obtain a composite proton exchange membrane; mixing ethanol, deionized water and Nafion solution, respectively adding supported platinum UiO-66-NH 2 and supported iridium UiO-66-NH 2 , performing ultrasonic treatment to obtain cathode and anode catalyst slurry, respectively spraying the cathode catalyst slurry and the anode catalyst slurry to two sides of the pretreated composite proton exchange membrane under negative pressure, placing the pretreated composite proton exchange membrane between two gas diffusion layers, and performing hot pressing on a tubular mold to obtain the tubular integrated membrane electrode.

Inventors

  • YE DEJUN
  • YE YONGQING
  • JIANG KUN
  • WU ZHAOHUI
  • LIU PENG
  • HUHETAOLI

Assignees

  • 永氢(江苏)能源科技有限公司

Dates

Publication Date
20260505
Application Date
20260310

Claims (10)

  1. 1. A preparation method of a tubular integrated membrane electrode assembly for a PEM (PEM) electrolytic cell is characterized by comprising the following steps: S1, placing a polyacrylonitrile fiber membrane in Nafion solution, dipping, adding supported palladium UiO-66-NH 2 , carrying out ultrasonic dipping, and drying to obtain a composite proton exchange membrane; S2, mixing ethanol, deionized water and Nafion solution, respectively adding supported platinum UiO-66-NH 2 and supported iridium UiO-66-NH 2 , and carrying out ultrasonic treatment to obtain cathode and anode catalyst slurry; and S3, respectively spraying cathode catalyst slurry and anode catalyst slurry to two sides of the pretreated composite proton exchange membrane under negative pressure, placing the pretreated composite proton exchange membrane between two gas diffusion layers, and hot-pressing the pretreated composite proton exchange membrane on a tubular mold to obtain the tubular integrated membrane electrode.
  2. 2. The method for preparing the tubular integrated membrane electrode assembly for the PEM electrolytic tank, which is characterized in that in the step S1, the preparation method of the polyacrylonitrile fiber membrane comprises the steps of adding polyacrylonitrile and anhydrous zinc acetate into a mixed solution of acetone and N, N-dimethylacetamide, performing ultrasonic dispersion, standing and defoaming to obtain a spinning solution, performing electrostatic spinning with the spinning solution at 15-18kV, wherein the spinning speed is 0.8-2mL/h, the receiving distance is 15-20cm, and drying to obtain the polyacrylonitrile fiber membrane; In the preparation process of the polyacrylonitrile fiber membrane, the mass ratio of the polyacrylonitrile to the anhydrous zinc acetate is 1 (0.2-0.4).
  3. 3. The method for preparing a tubular integrated membrane electrode assembly for a PEM electrolyzer of claim 1, wherein in step S1, the preparation method of the supported palladium UiO-66-NH 2 solution comprises the steps of adding UiO-66-NH 2 into methanol solution, adding ammonium chloropalladate, stirring at room temperature, then adding methanol solution containing sodium borohydride at a speed of 0.2-0.5ml/min, stirring, centrifugally collecting solids, washing, and vacuum drying to obtain supported palladium UiO-66-NH 2 ; In the preparation process of the supported palladium UiO-66-NH 2 , the mass ratio of the UiO-66-NH 2 to the ammonium chloropalladate to the sodium borohydride is 1 (0.04-0.06) (0.15-0.22).
  4. 4. A process for preparing a tubular integrated membrane electrode assembly for a PEM electrolyzer as defined in claim 3, wherein said UiO-66-NH 2 is prepared by adding zirconium chloride and 2-amino terephthalic acid to N, N-dimethylformamide, ultrasonic dispersing, adding glacial acetic acid as regulator, heating at 80-120 ℃ for reaction for 6-24 hours, cooling to room temperature, centrifuging to collect solid, washing, and vacuum drying to obtain UiO-66-NH 2 ; In the preparation process of the UiO-66-NH 2 , the mass ratio of the zirconium chloride to the 2-amino terephthalic acid is1 (0.4-0.7).
  5. 5. The method of manufacturing a tubular integrated membrane electrode assembly for a PEM electrolyzer of claim 1 wherein in step S1, the mass ratio of the polyacrylonitrile fiber membrane, nafion solution, supported palladium UiO-66-NH 2 is 1 (10-20): 0.05-0.1.
  6. 6. The method of manufacturing a tubular integrated membrane electrode assembly for a PEM electrolyzer of claim 1 wherein in step S2 the volume ratio of ethanol, deionized water and Nafion solution is (8-9): 1-2): 0.045-0.065.
  7. 7. The method for preparing a tubular integrated membrane electrode assembly for a PEM electrolyzer of claim 1 wherein in step S2, the preparation method of the supported platinum UiO-66-NH 2 comprises the steps of adding UiO-66-NH 2 into methanol solution, adding potassium tetrachloroplatinate, stirring at room temperature, adding sodium borohydride solution at a speed of 0.2-0.5ml/min, stirring, centrifugally collecting solids, washing, and vacuum drying to obtain supported platinum UiO-66-NH 2 ; In the preparation process of the supported platinum UiO-66-NH 2 , the mass ratio of the UiO-66-NH 2 to the potassium tetrachloroplatinate to the sodium borohydride is 1 (0.4-0.6) to 0.2-0.3.
  8. 8. The method for preparing a tubular integrated membrane electrode assembly for a PEM electrolyzer of claim 1, wherein in step S2, the preparation method of the supported iridium UiO-66-NH 2 comprises the steps of adding UiO-66-NH 2 into methanol solution, stirring and mixing uniformly, adding potassium hexachloroiridate, adjusting pH to 7.5,80-100 ℃ by sodium hydroxide, heating for 6-24h, cooling to room temperature, boiling under oxygen bubbling, and drying to obtain supported iridium UiO-66-NH 2 ; In the preparation process of the iridium-loaded UiO-66-NH 2 , the mass ratio of the UiO-66-NH 2 to the potassium hexachloroiridate is 1 (0.4-0.6).
  9. 9. The method for preparing a tubular integrated membrane electrode assembly for a PEM electrolyzer of claim 1, wherein the preparation method of the pretreated composite proton exchange membrane comprises the steps of placing the composite proton exchange membrane in a hydrogen peroxide solution, heating and washing, placing the composite proton exchange membrane in a sulfuric acid solution, heating and washing, and placing the composite proton exchange membrane in deionized water to obtain the pretreated composite proton exchange membrane; the negative pressure spraying parameters are that the temperature is 60-80 ℃ and the pressure is 0-0.2MPa.
  10. 10. A tubular integrated membrane electrode assembly for a PEM electrolyser according to any of claims 1-9 prepared by the process of preparing a tubular integrated membrane electrode assembly.

Description

Tubular integrated membrane electrode assembly for PEM (PEM) electrolytic tank and preparation method thereof Technical Field The invention relates to the technical field of membrane electrode preparation for PEM (proton exchange membrane) electrolytic cells, in particular to a tubular integrated membrane electrode assembly for PEM electrolytic cells and a preparation method thereof. Background Hydrogen energy is a green secondary energy source with rich sources and is widely applied in the fields of traffic, energy, industry and the like. The hydrogen production by water electrolysis is an efficient and clean hydrogen production process due to simple process and high product purity. Currently, the processes for producing hydrogen from electrolyzed water are mainly alkaline electrolysis, proton Exchange Membrane (PEM) electrolysis, solid oxide electrolysis and anion exchange membrane electrolysis. The PEM electrolysis technology has the advantages of high purity of hydrogen production, high response speed, capability of coping with fluctuation of renewable energy sources and the like, and has great development potential in commercial application. However, in the current PEM electrolytic hydrogen production process, a flat membrane electrode structure is mostly adopted, and the structure faces the problems of high bipolar plate ratio, increased cost, difficult sealing, high noble metal load and the like. In addition, the mechanical property and chemical stability of the proton exchange membrane in the membrane electrode are difficult to balance, and the interface compatibility of each component is poor. Therefore, the development of a tubular integrated membrane electrode assembly for a PEM electrolyzer is of great importance. Disclosure of Invention The invention aims to provide a tubular integrated membrane electrode assembly for a PEM (proton exchange membrane) electrolytic tank and a preparation method thereof, so as to solve the problems in the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions: a method for preparing a tubular integrated membrane electrode assembly for a PEM electrolyzer, comprising the steps of: S1, placing a polyacrylonitrile fiber membrane in Nafion solution, dipping, adding supported palladium UiO-66-NH 2, carrying out ultrasonic dipping, and drying to obtain a composite proton exchange membrane; S2, mixing ethanol, deionized water and Nafion solution, respectively adding supported platinum UiO-66-NH 2 and supported iridium UiO-66-NH 2, and carrying out ultrasonic treatment to obtain cathode and anode catalyst slurry; and S3, respectively spraying cathode catalyst slurry and anode catalyst slurry to two sides of the pretreated composite proton exchange membrane under negative pressure, placing the pretreated composite proton exchange membrane between two gas diffusion layers, and hot-pressing the pretreated composite proton exchange membrane on a tubular mold to obtain the tubular integrated membrane electrode. In the step S1, the preparation method of the polyacrylonitrile fiber membrane comprises the steps of adding polyacrylonitrile and anhydrous zinc acetate into a mixed solution of acetone and N, N-dimethylacetamide, performing ultrasonic dispersion, standing and defoaming to obtain a spinning solution, performing electrostatic spinning with the spinning solution at 15-18kV, wherein the spinning speed is 0.8-2mL/h, the receiving distance is 15-20cm, and drying to obtain the polyacrylonitrile fiber membrane; In the preparation process of the polyacrylonitrile fiber membrane, the mass ratio of the polyacrylonitrile to the anhydrous zinc acetate is 1 (0.2-0.4). Further, in the step S1, the preparation method of the supported palladium UiO-66-NH 2 solution comprises the steps of adding UiO-66-NH 2 into a methanol solution, adding ammonium chloropalladate, stirring at room temperature, adding a methanol solution containing sodium borohydride at a speed of 0.2-0.5ml/min, stirring, centrifugally collecting solids, washing, and vacuum drying to obtain supported palladium UiO-66-NH 2; In the preparation process of the supported palladium UiO-66-NH 2, the mass ratio of the UiO-66-NH 2 to the ammonium chloropalladate to the sodium borohydride is 1 (0.04-0.06) (0.15-0.22). Further, the preparation method of the UiO-66-NH 2 comprises the steps of adding zirconium chloride and 2-amino terephthalic acid into N, N-dimethylformamide, performing ultrasonic dispersion, adding glacial acetic acid as a regulator, heating at 80-120 ℃ for reaction for 6-24 hours, cooling to room temperature, centrifugally collecting solids, washing, and performing vacuum drying to obtain the UiO-66-NH 2; In the preparation process of the UiO-66-NH 2, the mass ratio of the zirconium chloride to the 2-amino terephthalic acid is1 (0.4-0.7). Further, in the step S1, the mass ratio of the polyacrylonitrile fiber membrane, the Nafion solution and the supporte