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WO-2026092038-A1 - PROTON EXCHANGE MEMBRANE ELECTROLYSIS WATER CATALYST SLURRY AND PREPARATION METHOD THEREFOR

WO2026092038A1WO 2026092038 A1WO2026092038 A1WO 2026092038A1WO-2026092038-A1

Abstract

A proton exchange membrane electrolysis water catalyst slurry, comprising 10-25% of iridium-based catalysts in different valence states, 2-10% of water, 35-65% of an organic alcohol, 15-35% of a perfluorosulfonic acid resin mixed solution and 0.05-0.5% of a surfactant, wherein the iridium-based catalysts in different valence states comprise a iridium-based non-noble metal doped catalyst and a ruthenium-iridium-terbium oxidation state catalyst. By means of a combination of two rhodium-based catalysts in different valence states, the use amount of rhodium used can be reduced, the agglomeration of two rhodium-based catalyst particles in different valence states is also effectively reduced, and the dispersibility of the catalyst, the suspension stability of the slurry and the porosity of a catalytic layer are improved.

Inventors

  • WANG, YANFEI
  • XIAO, Haicheng
  • YU, Yinglong
  • WANG, JINGJING
  • SHAO, Chenyi
  • XIA, Bowen
  • LONG, Chuan
  • WANG, ZIPENG
  • HE, Yeheng
  • LI, Qingxun

Assignees

  • 中国石油天然气股份有限公司

Dates

Publication Date
20260507
Application Date
20250928
Priority Date
20241030

Claims (14)

  1. A proton exchange membrane water electrolysis catalyst slurry, wherein, by mass percentage, the proton exchange membrane water electrolysis catalyst slurry comprises 10-25% iridium-based catalyst of different valence states, 2-10% water, 35-65% organic alcohol, 15-35% perfluorosulfonic acid resin mixed solution, and 0.05-0.5% surfactant, and the sum of the mass percentages of each component is 100%. The iridium-based catalysts with different valence states include a first iridium-based catalyst and a second iridium-based catalyst, wherein the first iridium-based catalyst is selected from iridium-based non-noble metal doped catalysts, and the second iridium-based catalyst is selected from ruthenium-iridium-terbium oxide catalysts. The iridium-based non-noble metal doped catalyst is selected from one or more combinations of Ir y Co 1-y and Ir z Ni 1-z , wherein 0 < y < 1 and 0 < z <1; The molecular formula of the ruthenium - iridium- terbium oxidized catalyst is Tb₂RuₓIr₂⁻⁴O₇ , where 0 < x < 2 ; The perfluorosulfonic acid resin mixed solution contains two or more perfluorosulfonic acid resin solutions with different molar mass values.
  2. According to claim 1, the proton exchange membrane electrolysis water catalyst slurry, wherein the mass ratio of the first iridium-based catalyst and the second iridium-based catalyst is 1:5-1:20.
  3. According to claim 1 or 2, the proton exchange membrane electrolysis water catalyst slurry comprises, by mass percentage, 15-20% iridium-based catalyst of different valence states, 4-8% water, 45-55% organic alcohol, 20-30% perfluorosulfonic acid resin mixed solution, and 0.2-1% surfactant, wherein the sum of the mass percentages of each component is 100%.
  4. The proton exchange membrane electrolysis water catalyst slurry according to claim 1 or 2, wherein 0.05 ≤ x ≤ 1.95.
  5. According to claim 4, the proton exchange membrane electrolysis water catalyst slurry, wherein 0.4 ≤ x ≤ 1.6.
  6. According to claim 1 or 5 , the proton exchange membrane water electrolysis catalyst slurry, wherein the ruthenium - iridium - terbium oxidized catalyst is selected from one or more combinations of Tb₂Ru₁.₆Ir₀.₄O₇ , Tb₂Ru₁.₀Ir₁.₀O₇ , and Tb₂Ru₀.₄Ir₁.₆O₇ .
  7. According to claim 1, the proton exchange membrane electrolysis water catalyst slurry, wherein the ruthenium-iridium-terbium oxidized catalyst is granular with a particle size of 40-180 nm.
  8. According to claim 1, the proton exchange membrane electrolysis water catalyst slurry, wherein the organic alcohol is one or a combination of two or more of ethylene glycol, glycerol, ethanol, n-propanol, and isopropanol.
  9. According to claim 1, the proton exchange membrane electrolysis water catalyst slurry, wherein the surfactant is selected from at least one anionic surfactant.
  10. According to claim 9, the proton exchange membrane electrolysis water catalyst slurry, wherein the anionic surfactant is one or a combination of two or more of the following: (perfluoro)alkyl or arylsulfonic acid surfactants, (perfluoro)alkyl or arylsulfonic acid surfactants, (perfluoro)alkyl or arylcarboxylic acid surfactants, and (perfluoro)alkyl or arylphosphoric acid surfactants.
  11. According to claim 1, the proton exchange membrane water electrolysis catalyst slurry, wherein the perfluorosulfonic acid resin mixed solution contains resin solution a and resin solution b, wherein the molar mass value of resin solution a is 600-900, and the molar mass value of resin solution b is 900-1200.
  12. According to claim 11, the mass ratio of resin solution a to resin solution b is 1:1 to 1:10, the concentration of resin solution a is 5% to 20%, and the concentration of resin solution b is 5% to 20%.
  13. A method for preparing a proton exchange membrane water electrolysis catalyst slurry according to any one of claims 1-12, comprising the following steps: The first iridium-based catalyst and the second iridium-based catalyst were mixed with water and a surfactant, and then a perfluorosulfonic acid resin mixture and an organic alcohol were added sequentially to obtain a mixed solution. The mixed solution was subjected to ultrasonic vibration and ball milling to obtain the proton exchange membrane water electrolysis catalyst slurry.
  14. According to the preparation method of claim 13, the ultrasonic oscillation time is 10-30 minutes and the ultrasonic power is 350-750W; The ball milling time is 30-120 minutes, and the rotation speed is 300-500 rpm.

Description

A proton exchange membrane water electrolysis catalyst slurry and its preparation method Cross-reference information This application claims priority to Chinese Patent Application No. 202411537599.2, filed on October 30, 2024, entitled "A Proton Exchange Membrane Electrolysis Water Catalyst Slurry and Its Preparation Method", the entire contents of which are incorporated herein by reference. Technical Field This invention relates to the field of proton exchange membrane electrolysis for hydrogen production technology, and more specifically, to a proton exchange membrane electrolysis catalyst slurry and its preparation method. Background Technology Proton exchange membrane (PEM) electrolysis for hydrogen production is one of the effective methods for large-scale hydrogen production in the future. It boasts advantages such as high efficiency, high hydrogen purity, compact electrolyzer and system structure, inherent safety, wide adjustable range of load fluctuations, and suitability for rapid start-up and shutdown. The anode reaction is the rate-controlling step, and the activity, efficiency, and cost of the anode catalyst are currently key factors restricting the large-scale development of PEM electrolysis for hydrogen production. Currently, the main commercial anode catalysts are IrO₂ or iridium black elemental catalysts. Ir is scarce and expensive; therefore, the urgent task is to develop efficient methods for preparing membrane electrode slurries that reduce the amount of iridium-based catalyst used, thereby improving the utilization rate of iridium-based catalysts and reducing the amount of iridium catalyst used to lower costs. The membrane electrode assembly (MEA), as the core component of PEM water electrolysis, is not only a crucial site for electron generation and separation but also plays a role in water transport and gas expulsion. The MEA mainly consists of a proton exchange membrane, a catalyst layer, and a diffusion layer. The microstructure of the catalyst layer in the MEA is determined by the slurry coated on the proton exchange membrane, and the composition and dispersion of the slurry significantly affect the catalyst active area and the migration rates of protons and electrons. The preparation of the catalyst slurry is critical, as its performance directly affects the catalytic performance of the prepared MEA and ultimately the performance of PEM water electrolysis. Commonly used oxygen evolution catalysts include iridium black and iridium dioxide. Metallic iridium is scarce and expensive. The form in which the iridium-based catalyst exists is the main factor affecting the oxygen evolution performance of iridium oxide catalysts. Industrially used iridium-based catalysts can generally be divided into elemental iridium black, IrO₂ , and IrOₓ catalysts. IrOₓ has a bulk structure rich in oxygen vacancies and a large number of hydroxyl groups on its surface. In terms of oxygen evolution performance, elemental iridium black is less stable than IrO₂ and IrOₓ , but its activity is superior . This difference in activity and stability stems from the different oxygen evolution mechanisms of the two catalysts. Lower-cost RuO₂ can be used as an anode electrode to replace commercial IrO₂ , but under harsh corrosive conditions, such as high oxidation potential, low pH, and high oxygen concentration, RuO₂ is unstable and eventually decomposes into soluble RuO₄ or H₂RuO₅ . It is difficult to simultaneously achieve both high activity and stability with simple elemental iridium black or iridium-based oxidized catalysts. Given the significant application value of iridium-based nanomaterials in PEM water electrolysis technology, there is an urgent need to develop efficient and low-cost methods for preparing iridium-based catalyst membrane electrode slurries in order to promote the large-scale application of PEM water electrolysis technology. Summary of the Invention To achieve the above objectives, the present invention aims to provide a proton exchange membrane water electrolysis catalyst slurry and its preparation method. The catalyst slurry uses a combination of two iridium-based catalysts and is formulated with two perfluorosulfonic acid resins and a surfactant, which can reduce the cost of the catalyst while ensuring the suspension stability of the catalyst material. To achieve the above objectives, the present invention provides a proton exchange membrane water electrolysis catalyst slurry, wherein, by mass percentage, the proton exchange membrane water electrolysis catalyst slurry comprises 10-25% iridium-based catalyst of different valence states, 2-10% water, 35-65% organic alcohol, 15-35% perfluorosulfonic acid resin mixed solution, and 0.1-1.2% surfactant, and the sum of the mass percentages of each component is 100%. The iridium-based catalysts with different valence states include a first iridium-based catalyst and a second iridium-based catalyst, wherein the first iridium-based catalyst is selected