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WO2025214608A1 - Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse - Google Patents

Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse

Info

Publication number
WO2025214608A1
WO2025214608A1 PCT/EP2024/059932 EP2024059932W WO2025214608A1 WO 2025214608 A1 WO2025214608 A1 WO 2025214608A1 EP 2024059932 W EP2024059932 W EP 2024059932W WO 2025214608 A1 WO2025214608 A1 WO 2025214608A1
Authority
WO
WIPO (PCT)
Prior art keywords
stack
water
electrolysis
conditioning
electrolysis stack
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/EP2024/059932
Other languages
English (en)
Inventor
Walter Goorts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Robert Bosch GmbH
Original Assignee
Robert Bosch GmbH
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
Application filed by Robert Bosch GmbH filed Critical Robert Bosch GmbH
Priority to PCT/EP2024/059932 priority Critical patent/WO2025214608A1/fr
Publication of WO2025214608A1 publication Critical patent/WO2025214608A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • 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
    • 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
    • C25B15/00—Operating or servicing cells
    • 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
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • C25B9/77—Assemblies comprising two or more cells of the filter-press type having diaphragms

Definitions

  • the present invention relates to a method for conditioning an electrolysis stack and an electrolysis stack according to the attached claims.
  • Electrolysis stacks are well known. Each electrolysis cell in an electrolysis stack has a layered construction, typically comprising an electrically insulating, but ion conducting composite polymer membrane with a respective cathode and anode, electrode layers provided on either side thereof, at which electrodes the actual electrochemical reaction takes place, such as H2O oxidation or oxygen evolution reaction at the anode and IT reduction or hydrogen evolution reaction at the cathode in case of electrolysis of water.
  • the anode and cathode catalyst layers comprise catalyst nano particles mixed with binder and support materials, typically an ionomer.
  • This layered assembly of the membrane and the electrodes is often referred to as membrane electrode assembly (MEA) or catalyst coated membrane (CCM), which latter naming refers to the conventional MEA production process of coating the membrane with the electrode catalyst mixture dissolved in a volatile solvent.
  • An electrolysis cell further comprises a porous transport or gas diffusion layer (PTL/GDL) on either side of the CCM for carrying electric current to or away from the electrodes, while allowing electrolyte and/or the electrochemical reactants/products to be supplied to or carried away from a respective electrode side of the CCM.
  • PTL/GDL porous transport or gas diffusion layer
  • the MEA is defined to include the PTL/GDL.
  • the PTL/GDL can be provided as a metal foam, sintered metal fibres/whiskers, woven or non-woven carbon fibres and the like. Effective porosity, average pore size, tortuosity, as well as electric conductance are all relevant characteristics of the PTL/GDL.
  • An electrolysis stack also comprises metal “bipolar” plates (BPP) shared between and mutually chemically separating adjacent cells for coupling electric current out-of, or into these cells, which plate can be corrugated such that it defines a fluid supply and distribution area and a fluid flow field for the transport of the electrolyte, the reactants/products and/or a cooling medium across the active area of the cell.
  • BPP metal “bipolar” plates
  • the MEA could be designed as a PTE (Porous Transport Electrode) or CCS (Catalyst Coated Substrate) which is a solution claimed to enable lower precious metal catalyst loadings, such as Iridium, or Ruthenium, for example.
  • PTE Porous Transport Electrode
  • CCS Catalyst Coated Substrate
  • a stack comprising multiple cells is normally taken into operation by flushing it with water of low conductivity, to remove substances and adsorbed species to the different components after which it is brought to operating temperature.
  • this is a process that takes some time to allow the membrane to hydrate and build the water-soaked clusters to promote the proton conductance.
  • the membrane swells in all directions, of which the swelling perpendicular to the in-plane direction allows for creating more contact positions between the membrane and the porous transport layers (PTL, GDL) on both sides.
  • PTL porous transport layers
  • the present invention relates to a method for treatment of an electrolysis stack.
  • the method disclosed herein comprises conditioning the electrolysis stack by flushing it with water for a predetermined time, wherein the water has a temperature higher than 75°C.
  • the method disclosed herein is based on the principle that during the process of conditioning, also called “activation” of the stack, which is carried out only once, in particular during or shortly after manufacturing of the stack, in particular between 100 and 500 hours of operation, in particular, before running the stack under regular operation conditions, the stack is flushed with water, in particular water with low conductivity, such as demineralized water, having a temperature higher than 75°C.
  • the water has a temperature greater than a temperature of the water under regular operating conditions of the stack.
  • conditioning comprises swelling of membranes in electrolysis cells of the stack, thereby maximizing contact positions between the membrane and porous transport layers on both sides of each cell. Especially on the anodic side this is crucial due to the usually slower OER (oxygen evolution reaction) being a limiting factor in the cell performance.
  • OER oxygen evolution reaction
  • flushing the stack with water having a temperature higher than 75°C enhances the contact between the CCM and PTL permanently, to improve the overall performance of the stack by reducing the interfacial contact resistance between CCM and PTL and by increasing the catalyst utilization.
  • the catalyst utilization is enhanced because more contact points are developed leading to a higher ratio of active so-called triple-phase-boundaries, which specifies contacts between the electron conducting PTL, the active catalyst and the proton conducting membrane.
  • the interfacial contact resistance is improved by an improved in-plane conduction of electrons through the improved number and size of the contact areas and an overall better distribution thereof.
  • the water has a temperature between 75°C and 100°C.
  • the water vapor is used with temperatures higher than 100°C.
  • the predetermined time is greater than 1 minute, in particular greater than 1 hour.
  • the time for flushing may be chosen between 1 minute and several hours. In particular, the time may be chosen the shorter, the greater the temperature of the water and vice versa.
  • the stack is operated at, despite from the water temperature, regular operating conditions.
  • a pressurized cathode i.e. a cathode operated under pressurized hydrogen conditions, has been found to maximize the beneficial effects of the method disclosed herein.
  • the stack after flushing the stack with water, the stack is operated under regular operating conditions with a water temperature lower than 75°C.
  • the present invention relates to an electrolysis stack, wherein the electrolysis stack comprises a number of electrolysis cells, and wherein the electrolysis stack has been conditioned by the method disclosed herein.
  • the method disclosed is preferably used for conditioning the stack disclosed herein, which may include a stack with improved surface morphology of the PTL, such as a fiber type MPL, for example.
  • a stack with improved surface morphology of the PTL such as a fiber type MPL, for example.
  • MPL enhances the conductivity by limiting macroscopic deformation while still allowing microscopic protrusion into the PTL pores and provides an interconnected, electrically conductive structure that allows a limited number of cracks in the catalyst layers and/or membrane due to lowered mechanical stress on these components to occur.
  • the method disclosed herein enables the use of a stack with extreme low catalyst loadings.
  • Such catalyst layers can be flexible enough to follow the shape of a deformed membrane and as such, form additional triple-phase-boundaries once the membrane deforms towards the inner fibres or particles of a PTL that otherwise would not be available as a reaction site.
  • each of the electrolysis cells comprise a porous transport electrode.
  • an electrochemical activity HER, OER
  • the electrolysis cells comprise non-PFSA membranes.
  • Non-PFSA membranes such as Hydro-carbon based membranes, of which some have less water absorption capability and a different swelling behavior and are therefore less effective in creating a balanced contact to the PTL may be favourably treated by the method disclosed herein.
  • non-PFSA membranes can be overcome by the method disclosed herein using a flushing of these membranes with water having a temperature greater than 75°C, thereby making use of changed properties, such as a modulus of elasticity of the base material.
  • FIG 1 shows schematically an embodiment of the method disclosed herein
  • FIG. 2 shows schematically an embodiment of the electrolysis stack disclosed herein.
  • Figure 3 shows a potential profile of a temperature of water used for conditioning in the method according to Figure 1.
  • a method 100 for treatment of an electrolysis stack comprises a conditioning step, in which the stack is conditioned during manufacturing, before being operated for the first time under normal operating conditions, by flushing it with water for a predetermined time, wherein the water has a temperature greater than 75°C.
  • an electrolysis stack 200 is shown.
  • the electrolysis stack 200 comprises a plurality of electrolysis cells 201 , which have been treated by the method 100.
  • the stack 200 shows a maximized overall performance, since the electrolysis cells show a minimal interfacial contact resistance between CCM and PTL and a maximized catalyst utilization.
  • a diagram 300 is shown, which shows time on its x-axis and temperature of water used for flushing the stack on its y-axis.
  • the temperature is elevated over 75 °C.
  • the temperature sinks to an ambient temperature for an installation period 303 in which the flushing of the stack is paused.
  • an operation period 305 starts, in which the temperature of the water is elevated to an operating temperature lower than 75 °C, as indicated by the delta 307.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention concerne un procédé (100) de traitement d'un empilement d'électrolyse (200). Le procédé (100) comprend la régulation des conditions (101) de l'empilement d'électrolyse (200) par rinçage avec de l'eau pendant un temps prédéterminé, l'eau ayant une température supérieure à 75°C. En outre, l'invention concerne un empilement d'électrolyse (200).
PCT/EP2024/059932 2024-04-12 2024-04-12 Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse Pending WO2025214608A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2024/059932 WO2025214608A1 (fr) 2024-04-12 2024-04-12 Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2024/059932 WO2025214608A1 (fr) 2024-04-12 2024-04-12 Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse

Publications (1)

Publication Number Publication Date
WO2025214608A1 true WO2025214608A1 (fr) 2025-10-16

Family

ID=90825637

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/059932 Pending WO2025214608A1 (fr) 2024-04-12 2024-04-12 Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse

Country Status (1)

Country Link
WO (1) WO2025214608A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6500217B1 (en) * 1999-03-11 2002-12-31 Degussa-Huls Aktiengesellschaft Process for applying electrode layers to a polymer electrolyte membrane strip for fuel cells
US20230374679A1 (en) * 2020-10-13 2023-11-23 Greenerity Gmbh Catalyst-coated membrane and water electrolysis cell
WO2024123960A1 (fr) * 2022-12-09 2024-06-13 Uop Llc Composition d'encre de catalyseur et membranes revêtues d'un catalyseur à des fins d'électrolyse

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6500217B1 (en) * 1999-03-11 2002-12-31 Degussa-Huls Aktiengesellschaft Process for applying electrode layers to a polymer electrolyte membrane strip for fuel cells
US20230374679A1 (en) * 2020-10-13 2023-11-23 Greenerity Gmbh Catalyst-coated membrane and water electrolysis cell
WO2024123960A1 (fr) * 2022-12-09 2024-06-13 Uop Llc Composition d'encre de catalyseur et membranes revêtues d'un catalyseur à des fins d'électrolyse

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