WO2023052749A1 - Membranes échangeuses de protons revêtues de catalyseur pour électrolyseurs d'eau produisant de l'hydrogène - Google Patents

Membranes échangeuses de protons revêtues de catalyseur pour électrolyseurs d'eau produisant de l'hydrogène Download PDF

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Publication number
WO2023052749A1
WO2023052749A1 PCT/GB2022/052436 GB2022052436W WO2023052749A1 WO 2023052749 A1 WO2023052749 A1 WO 2023052749A1 GB 2022052436 W GB2022052436 W GB 2022052436W WO 2023052749 A1 WO2023052749 A1 WO 2023052749A1
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WIPO (PCT)
Prior art keywords
polymer
membrane
membranes
catalyst
layer
Prior art date
Application number
PCT/GB2022/052436
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English (en)
Inventor
Peter Richard Ellis
Monica GONZALEZ HERRERA
Katie M RIGG
Chris ZALITIS
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB2113807.8A external-priority patent/GB202113807D0/en
Priority claimed from GBGB2113808.6A external-priority patent/GB202113808D0/en
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO2023052749A1 publication Critical patent/WO2023052749A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/881—Electrolytic membranes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04197—Preventing means for fuel crossover
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes

Definitions

  • electrolyser configuration which can be used to produce green hydrogen. Electrolysis of water to produce high purity hydrogen and oxygen can be carried out in both alkaline and acidic electrolyte systems and practical devices using both types of electrolyte systems exist as commercial products.
  • Those electrolysers that are acid electrolyte-based typically employ a solid proton-conducting polymer electrolyte membrane or proton exchange membrane (PEM) and are known as polymer electrolyte membrane water electrolysers or proton exchange membrane water electrolysers (PEMWEs).
  • a catalyst-coated membrane (CCM) is employed within the cell of a PEMWE, which comprises the proton exchange membrane with two catalyst layers (for the anode and cathode reactions) applied on either face of the proton exchange membrane.
  • the present specification is focused on proton exchange membrane water electrolysers (PEMWEs) based on a catalyst coated proton exchange membrane.
  • the catalyst coated membrane comprises a proton conducting polymer membrane coated on one side by a cathode catalyst for catalysing a hydrogen evolution reaction and coated on the other side by an anode catalyst for catalysing an oxygen evolution reaction.
  • cathode catalyst materials comprise platinum.
  • Anode catalysts typically comprise iridium or iridium oxide (IrOx) materials or oxides containing both iridium and ruthenium.
  • membranes have been 125 microns or thicker because of the need to limit such hydrogen crossover.
  • the use of thicker membranes increases electronic and ionic resistances within the CCM. Since hydrogen crossover is exacerbated by the use of thinner membranes in PEMWEs it is quite typical to employ membranes with thicknesses of over 125 pm, and typically close to 200pm, or thicker.
  • PEM thicknesses in PEMWEs are 125 pm or greater to reduce the level of hydrogen crossover, but the concomitant increase in ionic resistance severely limits PEMWE performance.
  • Examples of currently used membranes include NationalTM N115 (thickness 125 pm) or NationalTM N117 (thickness 175 pm).
  • the recombination catalyst layer will lie closer to the plane in which the levels of H2 and O2 are suitable for most effective recombination. This is because of the faster diffusion rate of H2 relative to O2 through the CCM such that the optimal plane is closer to the oxygen producing side of the CCM than the hydrogen producing side.
  • the membrane configuration comprises: a first polymer membrane which is conductive to protons; a recombination catalyst layer for catalysing a recombination reaction of molecular oxygen and hydrogen; and a second polymer membrane which is conductive to protons, wherein the recombination catalyst layer is disposed between the first and second polymer membranes, wherein the first polymer membrane is thicker than the second polymer membrane, the first polymer membrane having a thickness in a range 60 micrometres to 100 micrometres and the second polymer membrane having a thickness in a range 5 micrometres to 30 micrometres, wherein the first polymer membrane comprises at least two reinforcement polymer layers and the second polymer membrane comprises at least one reinforcement polymer layer, the first polymer membrane having more reinforcement polymer layers than the second polymer membrane, wherein one or both of the first and second polymer membranes comprise a radical reducing additive, and wherein the first polymer membrane is a single coherent non-laminated polymer film comprising a plurality of proto
  • FIG 4 shows a schematic illustration (10) of such a membrane configuration (referred to herein as JM Membrane Plus) including an 80 micrometre thick membrane (11) with two reinforcement layers (12), a 15 micrometre thick membrane (13) with a single reinforcement layer (12), and a recombination catalyst layer (14) disposed between the two membranes (11, 13).
  • the 15 micrometre thick single reinforced membrane (13) can be fabricated in a similar manner to the 80 micrometre thick double reinforced membrane (11) as described previously.
  • the recombination catalyst layer (14) can be formed on either the 80 micrometre thick membrane (11) or the 15 micrometre thick membrane (13) and then the two membranes (11,13) laminated together with the recombination catalyst layer (14) disposed therebetween.
  • the two membranes can be hot-pressed at 170 °C, 800 PSI for 2-3 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une membrane revêtue de catalyseur destinée à un électrolyseur d'eau, la membrane revêtue de catalyseur comprenant : une couche de catalyseur de cathode permettant de catalyser une réaction d'évolution d'hydrogène ; une première membrane polymère qui est conductrice vis-à-vis des protons ; une couche de catalyseur de recombinaison permettant de catalyser une réaction de recombinaison de l'oxygène moléculaire et de l'hydrogène ; une seconde membrane polymère qui est conductrice vis-à-vis des protons ; et une couche de catalyseur d'anode permettant de catalyser une réaction d'évolution d'oxygène, la couche de catalyseur de recombinaison étant disposée entre la première et la seconde membrane polymère avec la couche de catalyseur de cathode disposée sur un côté opposé de la première membrane polymère par rapport à la couche de catalyseur de recombinaison et la couche de catalyseur d'anode disposée sur un côté opposé de la seconde membrane polymère par rapport à la couche de catalyseur de recombinaison. Les deux membranes polymères sont des films polymères non stratifiés cohérents uniques comprenant une pluralité de couches polymères.
PCT/GB2022/052436 2021-09-28 2022-09-27 Membranes échangeuses de protons revêtues de catalyseur pour électrolyseurs d'eau produisant de l'hydrogène WO2023052749A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB2113807.8 2021-09-28
GBGB2113807.8A GB202113807D0 (en) 2021-09-28 2021-09-28 Catalyst coated proton exchange membranes for green hydrogen producing water electrolysers
GBGB2113808.6A GB202113808D0 (en) 2021-09-28 2021-09-28 Catalyst coated proton exchange membranes for green hydrogen producing water electrolysers
GB2113808.6 2021-09-28

Publications (1)

Publication Number Publication Date
WO2023052749A1 true WO2023052749A1 (fr) 2023-04-06

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PCT/GB2022/052436 WO2023052749A1 (fr) 2021-09-28 2022-09-27 Membranes échangeuses de protons revêtues de catalyseur pour électrolyseurs d'eau produisant de l'hydrogène

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018115821A1 (fr) 2016-12-22 2018-06-28 Johnson Matthey Fuel Cells Limited Membrane revêtue de catalyseur dotée d'une structure stratifiée

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018115821A1 (fr) 2016-12-22 2018-06-28 Johnson Matthey Fuel Cells Limited Membrane revêtue de catalyseur dotée d'une structure stratifiée

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C. KLOSE ET AL: "Membrane Interlayer with Pt Recombination Particles for Reduction of the Anodic Hydrogen Content in PEM Water Electrolysis", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 165, no. 16, 21 November 2018 (2018-11-21), pages F1271 - F1277, XP055669989, ISSN: 0013-4651, DOI: 10.1149/2.1241814jes *

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