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CN-121992421-A - Sandwich membrane electrode for realizing function gradient regulation and control by carbon carrier morphology control and preparation method thereof

CN121992421ACN 121992421 ACN121992421 ACN 121992421ACN-121992421-A

Abstract

The invention belongs to the field of electrolyzed water, and particularly relates to a sandwich membrane electrode capable of realizing functional gradient regulation and control through morphology control of a carbon carrier and a preparation method thereof. The sandwich membrane electrode comprises a proton exchange membrane and catalytic layers attached to two sides of the proton exchange membrane, and the sandwich membrane electrode is designed by adopting effective regulation and control of carbon carriers with different sizes, wherein an anode and a cathode respectively comprise at least two catalytic layers. Wherein, the catalytic layer is respectively optimized in noble metal loading, resin content, catalyst particle size and dispersion process. This optimization ensures uniformity of the catalyst slurry and good spray results. Thereby improving mass transfer rate and gas transmission efficiency, increasing noble metal utilization rate and enhancing durability.

Inventors

  • FU FUHUA

Assignees

  • 华燚新能源材料(上海)有限公司

Dates

Publication Date
20260508
Application Date
20260212
Priority Date
20241218

Claims (9)

  1. 1. A sandwich membrane electrode is characterized in that the function gradient regulation and control are realized through the shape control of a carbon carrier; The sandwich membrane electrode comprises a proton exchange membrane and catalytic layers attached to two sides of the proton exchange membrane; The catalytic layer is attached to each side of the proton exchange membrane and comprises at least two layers and at most five layers, wherein the size of the carbon carrier of the catalytic layer is gradually reduced, or is gradually increased, or is staggered in size in the direction away from the proton exchange membrane; The catalytic layer comprises a noble metal catalyst and perfluorinated sulfonic acid resin, wherein the noble metal catalyst is synthesized by loading noble metal nano particles on a carbon carrier.
  2. 2. The sandwich membrane electrode according to claim 1, wherein the carbon support is of a regular hexagonal three-dimensional structure.
  3. 3. The sandwich membrane electrode according to claim 2, characterized in that the specific preparation method of the carbon carrier is as follows: S1, dissolving aluminum nitrate hexahydrate (Al (NO 3 ) 3 ·6H 2 O) and 1,3, 5-benzene tricarboxylic acid in a mixed solution of N-N-Dimethylformamide (DMF) and deionized water (DI), taking out after the hydrothermal reaction is finished, washing and drying to obtain a preparation material; S2, fully mixing the preparation material with metal salt, carrying out high-temperature treatment under inert atmosphere, after the reaction is finished, uniformly mixing and placing a reaction product and an acid solution, and then washing and drying to obtain the controllable membrane electrode carbon carrier; In S1, the mol ratio of the aluminum nitrate hexahydrate to the 1,3, 5-benzene tricarboxylic acid is 1:1-3:1, and the volume ratio of the N-N-dimethylformamide in the mixed solution is 10% -90%; In S2, the metal salt comprises potassium salt, zinc salt and magnesium salt, the mass ratio of the preparation material to the metal salt is 1:1-3:1, and the high-temperature treatment condition is 700-900 ℃; in S2, the acid solution is hydrochloric acid aqueous solution or sulfuric acid aqueous solution, and the molar concentration of hydrogen ions of the acid solution is 6-12 mol/L.
  4. 4. The sandwich membrane electrode of claim 2, wherein the carbon support is 5um to 100nm um in size.
  5. 5. The sandwich membrane electrode according to claim 1, characterized in that the noble metal is Pt nanoparticles.
  6. 6. The sandwich membrane electrode of claim 1 wherein the loading of noble metal nanoparticles is 550%.
  7. 7. The method for preparing the sandwich membrane electrode according to any one of claims 1 to 6, which comprises the following steps: (1) Preparing catalyst slurry by adopting a catalyst synthesized by loading noble metal nano particles on a carbon carrier, wherein the raw materials comprise, by mass, 5% -10% of noble metal catalyst, 0.1% -10% of perfluorosulfonic acid resin, and the balance of the catalyst slurry by using isopropanol and deionized water, wherein the ratio of the isopropanol to the deionized water is 0.5-16; The raw materials are placed in a low-temperature water domain environment for shearing at a high speed of 0.5-1.5 h, and then are placed in a low-temperature water domain environment for ultrasonic treatment of 0.5-1.5 h, so that catalyst slurry is obtained; (2) Spraying the catalyst slurry obtained in the step (1) on the cathode side of a Proton Exchange Membrane (PEM) by using a spraying machine, wherein the spraying load is 0.6-2.0 mg/cm 2 , and drying to obtain a catalytic layer; (3) Repeating steps (1) - (2) by increasing the number of catalytic layers on the cathode side of the Proton Exchange Membrane (PEM); (4) And (3) preparing a Proton Exchange Membrane (PEM) anode side catalytic layer, and repeating the steps (1) - (3).
  8. 8. The method according to claim 7, wherein the anode side catalytic layer of the proton exchange membrane is prepared from commercial grace Ir75-0480 catalyst with a spray loading of 0.75 mg/cm 2 .
  9. 9. Use of the sandwich membrane electrode according to any of claims 1-6 as an electrolytic water membrane electrode.

Description

Sandwich membrane electrode for realizing function gradient regulation and control by carbon carrier morphology control and preparation method thereof Technical Field The invention belongs to the field of electrolyzed water, and particularly relates to a sandwich membrane electrode capable of realizing functional gradient regulation and control through morphology control of a carbon carrier and a preparation method thereof. Background The hydrogen production by water electrolysis is the technology with the most potential for producing green energy at present, has a very wide application range and is mainly applied to the fields of energy, chemical industry, traffic and the like. In the field of energy, the energy source can be used as an important storage and conversion mode of renewable energy sources, and stable and adjustable energy source output is provided for an electric power system. The method can be used for producing chemicals such as hydrogen, ammonia and the like in the chemical industry field, and has the advantages of environmental protection, high efficiency and the like. In the traffic field, the energy source can be used as an important energy source of a fuel cell automobile, and a travel mode with zero emission and high efficiency is realized. The membrane electrode technology plays a vital role in the field of electrochemical energy conversion, and the development and optimization of the technology have important significance for improving the energy conversion efficiency, reducing the cost and promoting the application of clean energy technology. In the technology of hydrogen production by water electrolysis, a membrane electrode is an important part of the membrane electrode, and relates to three-phase interface reaction and a complex mass and heat transfer process. The components mainly comprise a proton exchange membrane, a catalytic layer and a diffusion layer. Wherein the catalytic layer as a place where the electrochemical reaction takes place has a decisive influence on the performance of the membrane electrode. Besides reducing the loading of the catalyst, optimizing and designing the structure of the catalyst becomes an effective strategy for improving the overall performance of the membrane electrode. The traditional membrane electrode in the field of electrolytic water has the problems of low mass transfer rate, low gas transmission efficiency and the like in the reaction process due to the distribution of a single catalytic layer, so that the catalyst utilization rate is low, the reaction rate is low, the durability is poor, the proton conductivity of the prepared catalytic layer is poor, and the transmission resistance of the multilayer catalytic layer prepared by superposition is also greatly increased. Therefore, it is very necessary to develop a novel functionally graded membrane electrode. Disclosure of Invention In order to solve the technical problems, the structure of the catalytic layer is optimized and designed on the basis of the single-layer membrane electrode, and a series of problems of low catalyst utilization rate, poor durability and the like caused by low mass transfer rate and low gas transmission efficiency in the reaction process of the single catalytic layer distribution of the conventional membrane electrode are solved. The invention provides a sandwich membrane electrode for realizing functional gradient regulation by controlling the morphology of a carbon carrier and a preparation method thereof. The sandwich membrane electrode prepared by the method improves the mass transfer rate and the gas transmission efficiency between the proton exchange membrane and the catalytic layer, and enhances the electrical stability of the sandwich membrane electrode. In order to achieve the above purpose, the first aspect of the present invention discloses a sandwich membrane electrode, wherein the function gradient regulation and control are realized through the shape control of a carbon carrier; The sandwich membrane electrode comprises a proton exchange membrane and catalytic layers attached to two sides of the proton exchange membrane; The catalytic layer is attached to each side of the proton exchange membrane and comprises at least two layers and at most five layers, wherein the size of the carbon carrier of the catalytic layer is gradually reduced, or is gradually increased, or is staggered in size in the direction away from the proton exchange membrane; The catalytic layer comprises a noble metal catalyst and perfluorinated sulfonic acid resin, wherein the noble metal catalyst is synthesized by loading noble metal nano particles on a carbon carrier. Preferably, the carbon support has a regular hexagonal three-dimensional structure. Preferably, the specific preparation method of the carbon carrier is as follows: S1, dissolving aluminum nitrate hexahydrate (Al (NO 3)3·6H2 O) and 1,3, 5-benzene tricarboxylic acid in a mixed solution of N-N-Dimethylformamide (DMF