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CN-121992436-A - Anode dehydrogenation catalyst slurry, preparation method thereof, membrane electrode and electrolytic water hydrogen production device

CN121992436ACN 121992436 ACN121992436 ACN 121992436ACN-121992436-A

Abstract

The application provides anode hydrogen-eliminating catalyst slurry and a preparation method thereof, a membrane electrode and a water electrolysis hydrogen production device. The anode dehydrogenation catalyst slurry comprises an anode catalyst, a dehydrogenation catalyst, electrolyte resin, alcohol and water, wherein the absolute value of the zeta potential value of the anode dehydrogenation catalyst slurry is more than or equal to 60mV. The anode dehydrogenation catalyst slurry contains a dehydrogenation catalyst, and is used for preparing an anode catalyst layer of a membrane electrode of a water electrolysis hydrogen production device, so that the purpose of anode side dehydrogenation can be achieved, the purity of oxygen at the anode side can be improved, the amount of oxygen at the anode side diffused to the cathode side can be reduced, and the purity of hydrogen at the cathode side can be improved. Further, the zeta potential value of the anode hydrogen eliminating catalyst slurry is controlled, so that the stability and uniformity of the slurry can be ensured, the action effect of the hydrogen eliminating catalyst and the anode catalyst is further improved, and the comprehensive performance of the membrane electrode prepared by the anode hydrogen eliminating catalyst slurry is obviously improved.

Inventors

  • CHAO WEI
  • FENG ZHIYANG

Assignees

  • 未势能源科技有限公司

Dates

Publication Date
20260508
Application Date
20241104

Claims (10)

  1. 1. An anode dehydrogenation catalyst slurry is characterized by comprising an anode catalyst, a dehydrogenation catalyst, electrolyte resin, alcohol and water; The absolute value of the zeta potential value of the anode dehydrogenation catalyst slurry is more than or equal to 60mV.
  2. 2. The anode dehydrogenation catalyst slurry of claim 1, wherein the anode catalyst comprises at least one of Ir, ru, oxides of Ir, and oxides of Ru, preferably the anode catalyst is an iridium oxide catalyst having an iridium content of 30-80wt%; The hydrogen eliminating catalyst comprises at least one of Pt and Pd, and is preferably a platinum-carbon catalyst; The electrolyte resin comprises one or more of perfluorosulfonic acid resin, sulfonated trifluorostyrene resin and polymethylphenylsulfonic acid siloxane resin; The alcohol comprises one or more of methanol, ethanol, propanol, n-propanol and isopropanol.
  3. 3. The anode dehydrogenation catalyst slurry according to claim 2, wherein the mass content of the electrolyte resin in the anode dehydrogenation catalyst slurry is 5 to 25wt%; The mass content of the anode catalyst in the anode dehydrogenation catalyst slurry is 2% -10%; the content of the dehydrogenation catalyst in the anode dehydrogenation catalyst slurry is 1% -10%; the mass content of water in the anode dehydrogenation catalyst slurry is 15% -35%; the mass content of alcohol in the anode dehydrogenation catalyst slurry is 40% -55%.
  4. 4. A method of preparing the anode dehydrogenation catalyst slurry of any of claims 1-3, comprising: Step S1, mixing an anode catalyst, a first electrolyte resin, a first alcohol and water, and performing first ultrasonic treatment to obtain anode catalyst pre-dispersion slurry; step S2, mixing a dehydrogenation catalyst, a second electrolyte resin, a second alcohol and water, and performing second ultrasonic treatment to obtain a dehydrogenation catalyst pre-dispersion slurry; And step S3, mixing the anode catalyst pre-dispersion slurry and the hydrogen eliminating catalyst pre-dispersion slurry, and performing ball milling to obtain the anode hydrogen eliminating catalyst slurry, wherein the ball milling speed is 150-300rpm, and the time is 3-8h.
  5. 5. The method for preparing an anode dehydrogenation catalyst slurry according to claim 4, wherein the temperature of the first ultrasonic treatment and/or the second ultrasonic treatment is 0-8 ℃; the time of the first ultrasonic treatment and/or the second ultrasonic treatment is 5-60min, preferably 30-40min; preferably, the first alcohol is mixed with the anode catalyst after being cooled to 0-5 ℃; preferably, the second alcohol is mixed with the dehydrogenation catalyst after being cooled to 0-5 ℃.
  6. 6. The method for preparing the anode hydrogen elimination catalyst slurry according to claim 4, wherein in the step S1, the first electrolyte resin is added in the form of a first electrolyte resin solution, the solid content of the electrolyte resin in the first electrolyte solution is 8% -30%, and the mass ratio of the anode catalyst, the first electrolyte resin solution, the first alcohol and the water is 1 (0.5-2): 0.2-1.0; In the step S2, the second electrolyte resin is added in the form of a second electrolyte resin solution, the solid content of the electrolyte resin in the second electrolyte solution is 8% -30%, and the mass ratio of the dehydrogenation catalyst to the second electrolyte resin solution to the second alcohol to the water is 1 (2-4): (6-12): (1-5); preferably, the first alcohol and/or the second alcohol are mixed with the anode catalyst after being cooled to 0-5 ℃.
  7. 7. The method for preparing an anode hydrogen elimination catalyst slurry according to claim 4, wherein in the step S3, a mass ratio of the anode catalyst pre-dispersion slurry to the hydrogen elimination catalyst pre-dispersion slurry is 1:4-1:8; The ratio of the mass of the ball-milled grinding balls to the sum of the mass of the anode catalyst pre-dispersion slurry and the mass of the dehydrogenation catalyst pre-dispersion slurry is 3:1-6:1; preferably, the size of the grinding balls is 1-5mm.
  8. 8. A membrane electrode comprising an anode catalyst layer, a proton exchange membrane and a cathode catalyst layer which are sequentially arranged, wherein the anode catalyst layer is prepared from the anode dehydrogenation catalyst slurry according to any one of claims 1 to 3 or the anode dehydrogenation catalyst slurry prepared by the preparation method according to any one of claims 4 to 7.
  9. 9. The membrane electrode according to claim 8, wherein the anode catalyst layer has an anode catalyst loading of 0.5 to 5mg cm -2 ; the loading amount of the dehydrogenation catalyst in the anode catalyst layer is 0.3-5 mg cm -2 ; The loading amount of the cathode catalyst in the cathode catalyst layer is 0.2-0.5 mg cm -2 .
  10. 10. An apparatus for producing hydrogen by electrolysis of water, comprising the membrane electrode according to claim 9.

Description

Anode dehydrogenation catalyst slurry, preparation method thereof, membrane electrode and electrolytic water hydrogen production device Technical Field The invention relates to the technical field of hydrogen production by proton exchange membrane water electrolysis, in particular to anode hydrogen removal catalyst slurry and a preparation method thereof, a membrane electrode and a water electrolysis hydrogen production device. Background The proton exchange membrane electrolyzed water hydrogen production is concerned at home and abroad due to the characteristics of large current density, small occupied area, high hydrogen production purity, good dynamic response to renewable energy sources with fluctuation characteristics and the like, and is considered as the development direction of the water electrolysis hydrogen production in the future 5-10 years. The hydrogen production membrane electrode by water electrolysis is an important component of a polyelectrolyte membrane (PEM) water electrolysis device, and comprises a proton exchange membrane, an anode catalyst layer on the anode side of the proton exchange membrane and a cathode catalyst layer on the cathode side of the proton exchange membrane. The anode side of the proton exchange membrane has oxygen and the cathode side has hydrogen, which can permeate through the proton exchange membrane, and the mixing of hydrogen and oxygen not only increases the risk of gas explosion, but also reduces the efficiency of the conversion from providing charge (electrons) to generating gas quantities. To solve this safety problem, an effective method is to use a hydrogen oxidation catalyst having activity and stability. By means of this catalyst, H 2 which has permeated the membrane can be "recombined" back into water by reaction with oxygen generated at the anode side, i.e. to act as hydrogen elimination. For example, CN104726891B indicates that the dehydrogenation catalysts are loaded on the surfaces of the current collector and the bipolar plate, which not only can increase the purity of the gas product and improve the safety, but also can simplify the gas treatment device and reduce the system cost. The hydrogen eliminating catalyst supported on the surfaces of the current collector and the bipolar plate is far from the anode side of the proton exchange membrane, i.e., far from the forefront of hydrogen permeation, and thus an effective hydrogen eliminating effect cannot be formed. For another example, CN113337844B indicates a cathode catalyst layer, a proton exchange membrane, a hydrogen elimination catalyst layer, and an anode catalyst layer, which are sequentially stacked in the electrolytic water membrane electrode. The hydrogen elimination catalyst layer can achieve the purpose of eliminating hydrogen at the anode side, so that the purity of oxygen at the anode side is improved, the amount of oxygen at the anode side diffused to the cathode side can be reduced, and the purity of hydrogen at the cathode side is improved. Disclosure of Invention The invention mainly aims to provide an anode hydrogen elimination catalyst slurry, a preparation method thereof, a membrane electrode and an electrolytic water hydrogen production device, so as to solve the problems of potential safety hazard and gas yield reduction caused by hydrogen entering an anode side in electrolytic water hydrogen production in the prior art. In order to achieve the above object, according to one aspect of the present invention, there is provided an anode catalyst slurry comprising an anode catalyst, a dehydrogenation catalyst, an electrolyte resin, an alcohol, and water, wherein the anode catalyst slurry has a zeta potential value of 60mV or more in absolute value. Further, the anode catalyst comprises at least one of Ir, ru, an oxide of Ir and an oxide of Ru, preferably, the anode catalyst is an iridium oxide catalyst, and the iridium content of the iridium oxide catalyst is 30-80wt%; the dehydrogenation catalyst comprises at least one of Pt and Pd, and is preferably a platinum-carbon catalyst; The electrolyte resin comprises one or more of perfluorosulfonic acid resin, sulfonated trifluorostyrene resin and polymethylphenylsulfonic acid siloxane resin; the alcohol comprises one or more of methanol, ethanol, propanol, n-propanol and isopropanol. Further, the mass content of the electrolyte resin in the anode dehydrogenation catalyst slurry is 5-25wt%; The mass content of the anode catalyst in the anode dehydrogenation catalyst slurry is 2-10%; The content of the dehydrogenation catalyst in the anode dehydrogenation catalyst slurry is 1-10%; The mass content of water in the anode dehydrogenation catalyst slurry is 15% -35%; the mass content of alcohol in the anode dehydrogenation catalyst slurry is 40% -55%. According to another aspect of the application, a preparation method of the anode hydrogen elimination catalyst slurry is provided, and the preparation method comprises the steps of S1, mixin