EP4229687A1 - Membrane à revêtement catalytique et cellule d'électrolyse de l'eau - Google Patents

Membrane à revêtement catalytique et cellule d'électrolyse de l'eau

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Publication number
EP4229687A1
EP4229687A1 EP21789703.2A EP21789703A EP4229687A1 EP 4229687 A1 EP4229687 A1 EP 4229687A1 EP 21789703 A EP21789703 A EP 21789703A EP 4229687 A1 EP4229687 A1 EP 4229687A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
membrane
noble metal
coated membrane
coated
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
EP21789703.2A
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German (de)
English (en)
Inventor
Alessandro Ghielmi
Dominik Gehrig
Jan Byrknes
Jens-Peter SUCHSLAND
Christian Eickes
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.)
Greenerity GmbH
Original Assignee
Greenerity GmbH
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Filing date
Publication date
Application filed by Greenerity GmbH filed Critical Greenerity GmbH
Publication of EP4229687A1 publication Critical patent/EP4229687A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/067—Inorganic compound e.g. ITO, silica or titania
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a catalyst-coated membrane with high power density at low catalyst loading and a water electrolysis cell comprising this catalyst-coated membrane.
  • Catalyst-coated membranes with a proton exchange membrane which are coated on one side with an anode and on the opposite side with a cathode, are known from the prior art under the term CCM (English: catalyst coated membrane). If the CCM is used in water electrolysis, the term PEM-WE (proton-exchange membrane water electrolysis) is common.
  • Protenene exchange membranes for use in PEM-WE are typically extruded perfluorosulfonic acid-based (PFSA) polymer membranes.
  • PFSA perfluorosulfonic acid-based
  • the most established examples of PEM are National® N115 and National® N117 from Chemours.
  • a catalyst for the oxidation of water is used in the anode electrode layer (abbreviated: anode).
  • This catalyst is often referred to as an OER (oxygen evolution reaction) catalyst.
  • OER catalysts are usually based on noble metals and comprise noble metal oxides that exhibit high catalytic activity for water splitting.
  • a proton-conducting polymer a so-called ionomer of the PFSA type, is usually used as a binder in the anode and is mixed with the OER catalyst.
  • the weight per unit area (mg) relates to the mass of the catalyst metal and the area (cm 2 ) to the geometric surface area of the CCM on which the catalyst is present. This area is also referred to as the active area.
  • a high basis weight, as indicated above, has hitherto been necessary in order to prevent losses in efficiency. Studies (see, for example, M. Bernt et al., The Electrochemical Society, 165 (5) F305-F314 (2018)) have shown that these losses are particularly pronounced at an iridium loading of less than 0.4 mg/cm 2 .
  • the above publication suggests making thicker electrodes as a solution, but does not teach how to make thicker electrodes without increasing the iridium loading at the same time.
  • the object of the invention is therefore to provide a catalyst-coated membrane which, with a low anode noble metal loading, has a good degree of efficiency, which is characterized by a low voltage at a given current density. It is also an object of the present invention to specify a water electrolysis cell which is also characterized by good efficiency and thus also by low operating costs due to reduced power consumption.
  • a catalyst-coated membrane which comprises a proton exchange membrane (membrane for short), an anode applied to a first side of the membrane and a cathode applied to a second side of the membrane.
  • the anode is characterized by a low catalyst loading and for this purpose comprises at least one noble metal-containing catalyst, the weight per unit area of the noble metal-containing catalyst, based on the noble metal content in the noble metal-containing catalyst, being less than or equal to 0.6 mg/cm 2 .
  • this low loading of noble metal-containing catalyst in the catalyst-coated membrane according to the invention is sufficient to achieve a low voltage at a given current density and thus a high efficiency.
  • Such a low loading is made possible by the fact that the surface area of the catalyst-coated membrane is less than 20% after storage for two hours in warm water at 100° C. at an air pressure of 1013 hPa.
  • the high dimensional stability of the invention The catalyst-coated membrane described is largely due to the high dimensional stability of the proton exchange membrane used, since the catalyst layers to be provided are generally essentially none when used according to the invention (and also in 100° C. warm water at an air pressure of 1013 hPa when stored in it for two hours). subject to dimensional change.
  • a catalyst-coated membrane in the sense of measuring the surface area being understood to mean a membrane coated with a catalyst on one or both sides (depending on the production process).
  • membranes with high dimensional stability and thus also catalyst-coated membranes with high dimensional stability in the sense of the invention have clear advantages under high current densities, e.g. >1 A/cm 2 , where resistance becomes important, as soon as a low anode Precious metal loading is present.
  • the terms “load”, “noble metal load” or “weight per unit area” relate exclusively to the noble metal contained in the catalyst used.
  • the use of loading relative to the noble metal is advantageous because, in the case of noble metals, the metal contributes a particularly high proportion of the cost of the catalyst.
  • the dimensional stability of the membrane used according to the invention and thus of the catalyst-coated membrane according to the invention is understood to mean the dimensional stability during the transition from the dry state to the wet state.
  • the expansion that occurs in the membrane and thus also in the catalyst-coated membrane is referred to as the area expansion, which results from the expansion in two directions perpendicular to one another.
  • the directions perpendicular to one another are understood to be the planar expansion directions and not the expansion of the catalyst-coated membrane in the layer thickness direction or layer arrangement direction.
  • mutually perpendicular directions are understood to mean the direction of extension in the machine direction (MD) and in the transverse direction (TD), also known as the cross-machine direction, where the change in area can be expressed as a percentage extension of the area.
  • high dimensional stability always means a low surface area of less than 20%.
  • a membrane with a dry length of 100 mm (MD) and a dry width of 100 mm (TD) and whose length and width is soaked for two hours in water at 100 °C at an air pressure of 1013 hPa 115 mm (MD) and 125 mm (TD), have an area coverage of 43.75%, as explained in more detail below.
  • Membranes and consequently also catalyst-coated membranes with a high dimensional stability and thus with a surface area of less than 20% after storage for two hours in 100 ° C warm water at an air pressure of 1013 hPa in the sense of the present invention can be obtained in different ways and the method for producing them is not limited in detail.
  • one or more reinforcement structures are incorporated into a proton exchange membrane such that the reinforcement structure(s) limit the expansion of the membrane.
  • the reinforcement structure can be introduced during the manufacturing process of the membrane from an ionomer dispersion or ionomer solution.
  • a previously formed reinforcement structure such as (bi-)axially stretched PTFE (ePTFE, English: expanded PTFE)
  • ePTFE expanded PTFE
  • the membrane can then be annealed in a high-temperature step, e.g. at about 150 °C to 200 °C, in order to improve the stability of the membrane.
  • PFSA ionomers are preferably used as ionomers.
  • reinforced membranes can be obtained by lamination, for example in a pressing or calendering process, of one or more non-reinforced membranes with a reinforcement structure.
  • Membranes with several reinforcement structures can be obtained, for example, by lamination (e.g. pressing or calendering process) of two or more membranes, of which at least two membranes have a reinforcement structure.
  • lamination e.g. pressing or calendering process
  • membranes with two or more reinforcement structures can be obtained which have a very high dimensional stability, ie a surface expansion of less than 10% when the membrane is stored in warm water at 100° C. for 2 hours at an air pressure of 1013 hPa.
  • Suitable reinforcement structures are, for example, woven or non-woven polymer structures, porous ceramic thin films, perforated polymer films or perforated inorganic films or (bi-)axially stretched porous polymer films.
  • Preferred reinforcement structures are also porous thin films of expanded polytetrafluoroethylene (ePTFE) or polyolefin, which allow the fabrication of thin yet strong membranes with excellent electrochemical performance.
  • ePTFE expanded polytetrafluoroethylene
  • dimensionally stable membranes can be obtained by increasing the equivalent weight (EW) of the ionomer, thereby limiting the water uptake of the membrane.
  • EW indicates the mass of the polymer per mole of the ionic functional groups contained in the ionomer.
  • one skilled in the art can determine the appropriate minimum equivalent weight that does not exceed the desired areal area, for example less than 20%.
  • Non-reinforced membranes comprising ionomers with such an equivalent weight can be made, for example, by extrusion or solvent-based coating processes.
  • the method by which the introduction of one or more reinforcement structures into the membrane is provided can be preferred, since thin membranes, e.g. with a layer thickness in the range of 50 ⁇ m, with very good dimensional stability, good mechanical properties and low ionic resistance are obtained can, which is particularly advantageous for the use of the present invention in water electrolysis cells.
  • ionomers used in the polymer electrolyte membrane used according to the invention and in the catalyst layers are not restricted in detail and can be perfluorinated ionomers (PFSA), partially fluorinated or hydrocarbon-based (non-fluorinated) ionomers, with different ionomers being able to be used in the different layers of the catalyst-coated membrane .
  • PFSA perfluorinated ionomers
  • partially fluorinated or hydrocarbon-based (non-fluorinated) ionomers with different ionomers being able to be used in the different layers of the catalyst-coated membrane .
  • the membrane can be built up from sub-layers which can comprise different ionomers.
  • ionomers of the PFSA type are National® from Chemours, Aquivion® from Solvay Specialty Polymers, ionomers from 3M, Aciplex® from Asahi Kasei or Flemion® from Asahi Glass.
  • hydrocarbon-based ionomers examples include sulfonated poly ether ketones (sPEK), sulfonated poly ether ether ketones (sPEEK), sulfonated poly ketone ketones (sPKK), sulfonated poly sulfones (sPSU) and sulfonated poly ether sulfones (sPES).
  • sPEK sulfonated poly ether ketones
  • sPEEK sulfonated poly ether ether ketones
  • sPKK sulfonated poly ketone ketones
  • sPSU sulfonated poly sulfones
  • sPES sulfonated poly ether sulfones
  • the surface area of the catalyst-coated membrane is less than 15% and in particular less than 10% after storage for two hours in 100° C. warm water at an air pressure of 1013 hPa, as described further below.
  • the efficiency of the catalyst-coated membrane can be improved and a particularly low voltage can be achieved for a given current density.
  • the weight per unit area of the noble metal-containing catalyst based on the precious metal content, preferably less than or equal to 0.4 mg/cm 2 and in particular less than or equal to 0.35 mg/cm 2 .
  • the basis weight of the noble metal-containing catalyst is preferably greater than or equal to 0.02 mg/cm 2 and in particular greater than or equal to 0.05 mg / cm2 .
  • the noble metal of the at least one catalyst containing noble metal is selected in particular from iridium and ruthenium. This means that both iridium and ruthenium can be used individually as noble metal-containing catalysts, or in combination.
  • the noble metal-containing catalyst is selected from iridium oxide, ruthenium oxide, mixtures thereof and alloys thereof, which is particularly advantageous in the light of high catalyst stability combined with outstanding OER activity.
  • Other elements can be admixed to improve the activity and/or stability of the OER catalyst.
  • Any alloying metals can be selected in particular from tin (Sn), niobium (Nb), nickel (Ni), tantalum (Ta), titanium (Ti), cobalt (Co), zinc (Zn), platinum (Pt), iron (Fe). ), silicon (Si) and cerium (Ce), the alloying metals being contained in the alloy with a content of less than 50% by weight.
  • Iridium and ruthenium oxide can be present, for example, in the form of (nano)particles or as thin films coated on substrates.
  • the catalyst oxides can be free-standing, agglomerated or finely dispersed on a substrate, typically powders with a high specific surface area such as titanium oxide.
  • the catalysts are present as thin films, either inorganic, e.g., ceramic, or organic compounds, e.g., polyaromatic molecules such as perylenes, can be used as the substrate.
  • the OER catalyst oxides can be obtained by wet-chemical methods, such as precipitation of hydroxides from soluble salts with subsequent thermal treatment in air, or by thermal, dry processes (e.g. “Adam’s fusion method”) or by gas-phase processes.
  • J. Hansaem and L. Jaeyoung Journal of Energy Chemistry, Vol. 46, July 2020, pp. 152-172) summarize various methods for the synthesis of iridium oxide as examples.
  • the noble metal-containing catalyst is preferably supported on inorganic and/or ceramic supports, in particular on Titanium oxide and/or niobium oxide and/or antimony-doped niobium oxide and/or tin oxide and/or antimony-doped tin oxide.
  • the cathode comprises a platinum-containing and/or palladium-containing cathode catalyst, the platinum-containing and/or palladium-containing cathode catalyst being supported in particular on a carbon-containing material.
  • cathode catalysts containing platinum and/or palladium have a particularly high HER activity, which contributes to the power density of the catalyst-coated membrane according to the invention.
  • the cathode does not essentially affect the dimensional stability of the catalyst-coated membrane, so that it also applies to a catalyst-coated membrane with anode and cathode that the surface area of the catalyst-coated membrane is less than 20% after storage for two hours in 100 °C warm water at an air pressure of 1013 hPa.
  • the proton exchange membrane also advantageously has a layer thickness of from 5 to 120 ⁇ m, in particular from 15 to 90 ⁇ m and in particular from 35 to 75 ⁇ m. This achieves an optimal balance between efficiency and dimensional stability.
  • membranes with a greater thickness e.g. up to 200 ⁇ m
  • membranes with a greater thickness e.g. up to 200 ⁇ m
  • a hydrocarbon-based ionomer is preferably included in at least a sublayer of the membrane in order to reduce the gas permeability from one side of the catalyst-coated membrane to the other side of the catalyst-coated membrane.
  • Hydrocarbon-based ionomers have intrinsically lower gas permeability than PFSA ionomers.
  • the proton exchange membrane comprises at least one recombination catalyst, including in particular platinum particles.
  • the platinum particles are preferably finely dispersed within the membrane.
  • the recombination catalyst catalyzes the reaction of hydrogen passing from the cathode to the anode with oxygen from the anode side to prevent the formation of explosive mixtures on the anode side of a cell.
  • Anodes and cathodes of the catalyst coated membrane of the present invention can be prepared by conventional methods. For this purpose, for example, a powdered noble metal-containing catalyst is dispersed together with an ionomeric binder in an organic solvent or in a mixture of water and one or more organic solvents.
  • This dispersion is then stirred, optionally in a high-energy mixer, to allow good dispersion and reduce catalyst aggregate size.
  • the ink or paste thus obtained is then coated or printed directly onto the membrane surface (the first or second side of the proton exchange membrane) or first onto an inert substrate, a so-called decal, using a coating or printing device.
  • the liquid medium is then evaporated and a thin electrode layer is obtained. If one or both electrodes are coated on an inert substrate, the dried electrode is then transferred to the membrane surface by the application of heat and pressure, i.e. by a so-called decal transfer method.
  • the ink or paste for producing the cathode can be coated or printed directly onto a porous transport layer, in particular a gas diffusion layer.
  • a gas diffusion layer in particular a gas diffusion layer.
  • GDE gas diffusion electrode
  • the anode is applied to the membrane via a decal process or via direct membrane coating, resulting in a one-sided catalyst-coated membrane or a so-called half-CCM.
  • the (both sides) catalyst-coated membrane is then obtained during installation in the electrolytic cell, with a connection between the cathode catalyst layer and the membrane being obtained under the operating conditions of the cell.
  • a water electrolysis cell comprising a catalyst coated membrane as disclosed above. Due to the use of the catalyst-coated membrane according to the invention, the water electrolysis cell according to the invention is also distinguished by a high power density and a high level of efficiency with relatively low production costs.
  • the square piece (membrane, half-CCM or CCM) was then kept in water at 100 °C at an air pressure of 1013 hPa for 2 h. The piece was then removed from the water, excess water drops quickly dabbed off, and the edge lengths of the square were measured with calipers to a resolution of 0.01 mm, yielding edge lengths Li, wet and L2, wet.
  • the area change (%) was calculated using the following formula:
  • the measurement of the swelling behavior and thus the area expansion of the membrane, the half-CCM or the CCM, at 100 °C (this corresponds to the temperature of 100 °C warm water at an air pressure of 1013 hPa at an air pressure of 1013 hPa) is one established condition in the prior art and also correlates with the swelling behavior of the membrane and thus also the swelling behavior of the half-CCM or CCM in water under other conditions, for example at room temperature and in particular in warm water, in which the membrane or the half- CCM or CCM, normally operated.
  • the membranes/semi-CCMs/CCMs with greater swelling behavior at 100 °C and thus a high surface area also show greater swelling behavior at lower temperatures.
  • measuring the swelling behavior at 100° C. offers the advantage that this temperature is very controlled by the boiling point of the water and is therefore used according to the invention.
  • the efficiency of the CCM was measured in a single cell with an active area of 25 cm 2 .
  • the cell consisted of platinized titanium plates with a column bar flow field design on the anode side and the cathode side.
  • the flux field plate on the cathode side was additionally gold-plated.
  • a titanium sinter (1 mm thickness) and carbon paper (Toray TGP-H-120) were used as the porous transport layer and gas diffusion layer on the anode side and the cathode side, respectively.
  • the cell was closed with six M8 screws with a torque of 10 Nm. Deionized water with a conductivity less than 1 pS/cm was circulated on the anode side.
  • the cell was heated within 20 minutes by heating pads applied to the end plates Room temperature heated to 60 °C. The temperature was then increased to 80° C. within 20 min. Conditioning was performed by cycling ten times between 0 and 1 A/cm 2 with a hold time of 5 min for each step. At the end of the conditioning, the cell was kept at 1 A/cm 2 for 10 min.
  • Anode inks were coated onto a glass fiber reinforced PTFE substrate, in other words a decal, using a wire bar.
  • the wet film thickness was gradually increased by selecting different spiral applicators, each with increasing wire gauge, to achieve an iridium metal loading (area weight) of 0.15 mg/cm 2 , 0.25 mg/cm 2 , 0.5 mg/cm 2 , 1 .0 mg/cm 2 and 2.25 mg/cm 2 .
  • the wet layer thickness was varied between 10 ⁇ m and 285 ⁇ m by selecting spiral applicators with the appropriate wire diameters. After coating, the wet layers were dried in an oven at 110°C for 5 min.
  • Example 1 Production of catalyst-coated membranes (CCMs) with high dimensional stability (low surface area) and different catalyst loading of the anode
  • a membrane with high dimensional stability and a thickness of 41 ⁇ m comprising two expanded PTFE (ePTFE) reinforcement structures was obtained by laminating an unreinforced PFSA membrane with a thickness of 25 ⁇ m between two reinforced PFSA membranes with a thickness of 8 ⁇ m each.
  • the lamination was carried out in a press at a temperature of 160° C. and a pressure of 1.5 MPa for 1 min.
  • the machine directions of the three membranes were each aligned parallel to one another.
  • the linear expansion of the membrane due to the uptake of water (100° C.) was measured according to the method described and gave 2.0% and 3.3%, respectively.
  • the resulting area expansion was 5.4%.
  • the membranes were arranged between anode and cathode decals (5 cm ⁇ 5 cm) and pressed at a temperature of 180° C. and a pressure of 1.5 MPa for 1 min, so that the electrode layers were transferred from the decal substrate to the membranes became.
  • the cathode was identical for all CCMs and consisted of a catalyst with platinum supported on carbon and a National® ionomer binder.
  • the catalyst to ionomer weight ratio in the cathode was 3:1 and the platinum loading was 0.3 mg/cm 2 .
  • the cathode was also applied to glass fiber reinforced PTFE.
  • the anode loading of the different CCMs was varied by using anode decals with different loadings as described in the section "Preparation of anodes with different iridium loadings on a decal" to produce the CCMs.
  • the actual anode loading was determined gravimetrically by determining the weight of the anode decais before transfer (anode electrode on PTFE substrate) and the anode decais after transfer (pure PTFE substrate).
  • the basis weight (loading) of the iridium was calculated by taking the difference (anode decal minus pure PTFE substrate) and incorporating the known composition of the dry electrode layer.
  • the following anode iridium loadings were obtained for the five CCMs: 0.162 mg/cm 2 , 0.261 mg/cm 2 , 0.474 mg/cm 2 , 1.029 mg/cm 2 and 2.072 mg/cm 2 .
  • the CCM with an anode iridium loading of 0.261 mg/cm 2 was also used for
  • the prior art CCM was prepared analogously to the procedure of Example 1, except that the membrane used was National® NR212 (Chemours, USA). This membrane, which has a thickness of about 50 pm, is an established membrane in PEM-WE publications.
  • the anodes and cathodes used corresponded to those from example 1.
  • the following anode iridium loadings were obtained for the following five CCMs as well: 0.155 mg/cm 2 , 0.303 mg/cm 2 , 0.504 mg/cm 2 , 1.068 mg/cm 2 and 2.102 mg/cm 2 .
  • the CCM with NR212 with an anode iridium loading of 0.303 mg/cm 2 was also investigated to measure the dimensional stability under water absorption (100 °C, see method description).
  • the CCM showed a dimensional change of 15.7% in length and 15.9% in width. This corresponds to an area expansion of 34.1%.
  • the swelling behavior in 100 °C warm water at an air pressure of 1013 hPa also correlates with the swelling behavior at lower temperatures.
  • the CCMs from Example 1 and Comparative Example 1 were electrochemically characterized in a water electrolysis cell according to the method described above (see section “Performance/Efficiency in the Water Electrolysis Cell”).
  • the results, ie the cell voltage at a given current density as a function of the anode catalyst loading (anode noble metal loading), are shown in FIGS. 1 to 4. From the data it can be seen that CCMs with high dimensional stability have better efficiency than CCMs with a membrane with low dimensional stability at an anode catalyst loading equal to or less than 0.6 mg/cm 2 and current densities above 1 A/cm 2 between the two examined temperatures. It should be mentioned that the current density of interest for the application is at higher current densities (> 1 A/cm 2 ) so as to produce a large amount of hydrogen per unit area of the electrolyser and time.
  • Fig. 3 The cell voltage at a current density of 0.05 A / cm 2 as a function of
  • Fig. 4 The cell voltage at a current density of 3.0 A / cm 2 as a function of
  • FIG. 1 shows the cell voltage of water electrolysis cells of Example 1 and Comparative Example 1 at a current density of 3.0 A/cm 2 and a cell temperature of 80° C. for different anode iridium loadings.
  • a comparison between a CCM with a membrane with high dimensional stability and thus low surface area according to the present invention (triangles; Example 1) and a CCM with a membrane with low dimensional stability and thus high surface area (circles; Comparative Example 1) shows the advantage of using the Dimensionally stable membrane at an anode loading below 0.6 mg / cm 2 significantly, the improvement in cell voltage is 40 mV and more.
  • FIG. 2 shows the cell voltage of water electrolysis cells of Example 1 and Comparative Example 1 at a current density of 1.2 A/cm 2 and a cell temperature of 80° C. for different anode iridium loadings.
  • a comparison between a CCM with a membrane with high dimensional stability and thus low surface area according to the present invention (triangles; Example 1) and a CCM with a membrane with low dimensional stability and thus high surface area (circles; Comparative Example 1) shows the advantage of using the Dimensionally stable membrane at an anode loading below 0.6 mg / cm 2 significantly.
  • FIG. 3 shows the cell voltage of water electrolysis cells of Example 1 and Comparative Example 1 at a current density of 0.05 A/cm 2 and a cell temperature of 80° C. for different anode iridium loadings.
  • the performance/efficiency in the region of this low current density is similar for both membrane types over the entire anode loading range.
  • the voltage difference between the loading at 2 mg/cm 2 and 0.2 mg/cm 2 is in the range of 45 to 50 mV, which corresponds to a slope of 45-50 mV/decade and thus the theoretical expectation for an iridium oxide OER Catalyst corresponds.
  • the slope should be calculated using the resistance-corrected cell voltage, but the correction, which is only a few mV, is negligible at such low current densities, and since the correction is neglected for both loadings, the slope and hence the conclusions drawn from it do not change .
  • FIG. 4 shows the cell voltage of water electrolysis cells of Example 1 and Comparative Example 1 at a current density of 3.0 A/cm 2 and a cell temperature of 65° C. for different anode iridium loadings.
  • a comparison between a CCM with a membrane with high dimensional stability and thus low surface area according to the present invention (triangles; Example 1) and a CCM with a membrane with low dimensional stability and thus high surface area (circles; Comparative Example 1) shows the advantage of using the dimensionally stable membrane with an anode loading significantly below 0.6 mg/cm 2 , with the improvement in cell voltage being 40 mV and more.

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Abstract

L'invention concerne une membrane à revêtement catalytique qui comprend une membrane échangeuse de protons, une anode appliquée sur un premier côté de la membrane et une cathode appliquée sur un second côté de la membrane, l'anode comprenant au moins un catalyseur contenant du métal noble, la masse surfacique du catalyseur contenant du métal noble, rapportée à la teneur en métal noble, étant inférieure ou égale à 0,6 mg/cm2, et la surface occupée par la membrane à revêtement catalytique représentant moins de 20 % après un séjour de deux heures dans de l'eau à 100 °C à une pression de 1013 hPa.
EP21789703.2A 2020-10-13 2021-10-07 Membrane à revêtement catalytique et cellule d'électrolyse de l'eau Pending EP4229687A1 (fr)

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DE102020126797.5A DE102020126797A1 (de) 2020-10-13 2020-10-13 Katalysatorbeschichtete Membran und Wasserelektrolysezelle
PCT/EP2021/077749 WO2022078872A1 (fr) 2020-10-13 2021-10-07 Membrane à revêtement catalytique et cellule d'électrolyse de l'eau

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CA (1) CA3194898A1 (fr)
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CN114525521B (zh) * 2022-04-08 2024-06-21 北京化工大学 一种贵金属单原子分散于非贵金属基底表面的纳米材料及其制备方法和用途
DE102022213725A1 (de) 2022-12-15 2024-06-20 Robert Bosch Gesellschaft mit beschränkter Haftung Verfahren zur Herstellung einer elektrochemischen Zelle, elektrochemische Zelle
DE102023107646A1 (de) * 2023-03-27 2024-10-02 Greenerity Gmbh Membranelektrodenanordnung und verfahren zur herstellung derselben, brennstoffzelle und elektrolysezelle
WO2025048510A1 (fr) * 2023-09-01 2025-03-06 주식회사 엘지화학 Séparateur et cellule électrochimique le comprenant
CN117418205B (zh) * 2023-10-20 2025-11-14 北京亿华通科技股份有限公司 多孔催化剂气体扩散电极磁控溅射制备方法及电极
WO2025143612A1 (fr) * 2023-12-29 2025-07-03 코오롱인더스트리 주식회사 Ensemble membrane-électrode pour une cellule d'électrolyse de l'eau, et cellule d'électrolyse de l'eau comprenant celui-ci
GB2640128A (en) 2024-04-02 2025-10-15 Johnson Matthey Hydrogen Technologies Ltd Catalyst-coated membranes for water electrolysis
WO2025214608A1 (fr) * 2024-04-12 2025-10-16 Robert Bosch Gmbh Procédé pour réguler les conditions d'un empilement d'électrolyse et empilement d'électrolyse
KR20260000299A (ko) 2024-06-25 2026-01-02 국립창원대학교 산학협력단 공기극 계면 안정성이 향상된 고체산화물 수전해 전지

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ITMI20050446A1 (it) * 2005-03-17 2006-09-18 Solvay Solexis Spa Composito ccm
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CN116325242B (zh) 2026-02-06
US20230374679A1 (en) 2023-11-23
JP7665020B2 (ja) 2025-04-18
KR20230121999A (ko) 2023-08-22
CA3194898A1 (en) 2022-04-21
CN116325242A (zh) 2023-06-23
JP2023546077A (ja) 2023-11-01
DE102020126797A1 (de) 2022-04-14
WO2022078872A1 (fr) 2022-04-21

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