EP4112781A1 - Cellule d'électrolyse destinée à l'électrolyse à membrane électrolytique polymère et son procédé de fabrication - Google Patents

Cellule d'électrolyse destinée à l'électrolyse à membrane électrolytique polymère et son procédé de fabrication Download PDF

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EP4112781A1
EP4112781A1 EP21182692.0A EP21182692A EP4112781A1 EP 4112781 A1 EP4112781 A1 EP 4112781A1 EP 21182692 A EP21182692 A EP 21182692A EP 4112781 A1 EP4112781 A1 EP 4112781A1
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cell
catalyst
electrolytic cell
polymer electrolyte
electrolyte membrane
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English (en)
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Heinz Neubert
Andre KLINGER
Yashar Musayev
Günter Schmid
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Siemens Energy Global GmbH and Co KG
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Siemens Energy Global GmbH and Co KG
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Priority to EP21182692.0A priority Critical patent/EP4112781A1/fr
Priority to PCT/EP2022/061776 priority patent/WO2023274601A1/fr
Priority to CA3225562A priority patent/CA3225562A1/fr
Priority to EP22727778.7A priority patent/EP4330445A1/fr
Priority to CN202280046156.6A priority patent/CN117651789A/zh
Publication of EP4112781A1 publication Critical patent/EP4112781A1/fr
Withdrawn legal-status Critical Current

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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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
    • 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
    • C25B11/061—Metal or alloy
    • 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
    • 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
    • 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
    • C25B11/089—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
    • 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

Definitions

  • the invention relates to an electrolytic cell for polymer electrolyte membrane electrolysis, a method for producing such an electrolytic cell, the use of such an electrolytic cell and the use of a catalyst material.
  • PEM electrolysis polymer electrolyte membrane electrolysis
  • the two partial reactions according to equations (I) and (II) are carried out spatially separately from one another.
  • the reaction spaces are separated by means of a proton-conducting membrane, the polymer electrolyte membrane (PEM), also known as the proton exchange membrane.
  • PEM ensures extensive separation of the product gases hydrogen and oxygen, the electrical insulation of the electrodes and the conduction of the hydrogen ions as positively charged particles.
  • a PEM electrolysis plant is, for example, from EP 3 489 394 A1 famous.
  • figure 1 shows schematically the structure of a PEM electrolytic cell according to
  • the mentioned cell reactions according to the equations (I) and (II) are taking into account the increase in entropy when changing from liquid water to gaseous hydrogen or oxygen at a cell voltage of 1.48 V with their reverse reactions in equilibrium.
  • a higher voltage, the overvoltage is necessary.
  • the PEM electrolysis is therefore carried out at a cell voltage of approx. 1.8 - 2.1 V.
  • the prior art PEM electrolytic cell see e.g. B. Kumar, S, et al., Hydrogen production by PEM water electrolysis - A review, Materials Science for Energy Technologies, 2 (3) 2019, 442-454. https://doi.org/10.1016/j.mset.2019.03.002 , consists of two bipolar plates, gas diffusion layers, catalyst layers and the PEM viewed from the outside in. Due to the oxygen formation reaction, there are high oxidative potentials at the anode, which is why materials with rapid passivation kinetics, e.g. As titanium, for example, be used for the gas diffusion layer.
  • materials with rapid passivation kinetics e.g. As titanium, for example, be used for the gas diffusion layer.
  • the cathodic potential is less oxidative, so that gas diffusion layers can be made of stainless steel.
  • these corrode due to the acidic environment of the PEM electrolysis. This corrosion process is called acid corrosion.
  • the presence of elemental oxygen is not necessary here, as this is provided by the dissociation of the surrounding water.
  • the metal ions at the interface of the metal surface are oxidized by the hydroxide anion to form the respective hydroxide salt. This leads to degradation of the cell, which manifests itself in increased internal resistance and in foreign ions entering the PEM.
  • oxygen in the cathode compartment thus leads to increased corrosion rates and low hydrogen purity.
  • the transport of oxygen from the anode to the cathode can take place through two effects: the concentration-driven diffusion and the "electroosmotic drag".
  • the first effect relates to a solution-diffusion model of the PEM, in which the oxygen first dissolves at the interface in the polymer and then migrates to the cathode side, driven by the concentration gradient.
  • electroosmotic drags the oxygen molecules are entrained by the ions moving through the PEM and thus reach the cathode side. The latter effect can usually be neglected due to the lack of a dipole moment of oxygen.
  • the corrosion described above increases the impedance of the overall system, which means that the efficiency of the electrolysis process can be expected to be lower.
  • the introduction of the dissolved ions from the metal into the PEM can permanently damage its structure, which can have a negative effect on the mechanical stability, among other things.
  • the gas diffusion layer with its large surface is predestined for a corrosive attack.
  • Chromium-nickel base steels with a mass fraction of nickel of > 8% and high chromium contents due to their rapid passivation kinetics. Chromium forms thick CrO 3 passivation layers, through which oxygen can penetrate only with difficulty.
  • a further object of the invention is to specify a method for producing such an electrolytic cell.
  • a first aspect of the invention relates to an electrolytic cell for polymer electrolyte membrane electrolysis with a cathodic half-cell and an anodic half-cell, the cathodic half-cell and the anodic half-cell being separated from one another by means of a polymer electrolyte membrane.
  • the cathodic half-cell has a first catalyst material designed to catalyze a reduction of molecular oxygen.
  • the polymer electrolyte membrane can be formed, for example, from a tetrafluoroethylene-based polymer with sulfonated side groups.
  • the cathodic half-cell forms the reaction space in which the cathode reaction(s), e.g. B. run according to equation (II).
  • the anodic half-cell forms the reaction space in which the anode reaction(s), e.g. B. run according to equation (I).
  • molecular oxygen can be reduced to molecular water, for example, in accordance with equation (X) below.
  • equation (X) O 2 + 2 H + + 2 e- ⁇ H 2 O (X)
  • the proportion of oxygen in the cathodic half-cell can be reduced, so that the processes of oxygen corrosion explained in the introduction take place to a lesser extent or can even be avoided entirely.
  • oxygen corrosion can be actively reduced or even avoided by combating the cause, namely the presence of oxygen in the cathodic half-cell.
  • the measures described above and known from the prior art only increase the Resistance to this type of corrosion, but not affecting its cause.
  • the life of the electrolytic cell can be extended and the cost of maintenance and repairs and replacement parts reduced.
  • reaction product of the electrolysis formed in the cathodic half-cell e.g. B. hydrogen
  • the reaction product of the electrolysis formed in the cathodic half-cell e.g. B. hydrogen
  • oxygen contaminated to a lesser extent with oxygen.
  • a time-consuming and energy-intensive purification of the desired reaction product of the electrolysis can consequently be largely avoided.
  • the electrolysis cell can have a second catalyst material designed to catalyze a reduction of hydrogen ions.
  • the second catalyst material can bring about a catalytic reduction of hydrogen ions to molecular hydrogen according to equation (II) in the cathodic half-cell, so that hydrogen is formed to a sufficient extent as the desired reaction product of the electrolysis.
  • Possible materials for the second catalyst material are, for example, noble metal compounds such. As platinum, platinum-ruthenium or transition metal compounds. Other suitable materials are described in Yu, J. et al. A mini-review of noble-metal-free electrocatalysts for overall water splitting in non-alkaline electrolytes, Mat. Rep.: Energy, 1 (2) 2021, 100024. https://doi.org/10.1016/j.matre. 2021.100024
  • the second catalyst material contributes to an increase in the reaction rate of the cathode reaction(s), so that the economy of electrolysis can be improved.
  • the first catalyst material can be introduced into a first catalyst layer and/or the second catalyst material can be introduced into a second catalyst layer.
  • a layer can be understood to mean a flat structure whose dimensions in the layer plane, length and width, are significantly greater than the dimension in the third dimension, the layer thickness.
  • the introduction of the catalyst materials in layers makes it possible in a simple manner to implement a predeterminable distribution of the catalyst materials in the cathodic half-cell. In addition, the handling of the catalyst materials can be facilitated.
  • the first catalyst material and the second catalyst material can also be present together in one layer. This can have the advantage of simpler manufacture, since only one layer has to be manufactured instead of two.
  • the first catalyst layer can be arranged adjacent to, preferably directly adjacent to, ie in direct contact with, the second catalyst layer.
  • planar first and second catalyst layers can directly adjoin one another, forming an interface that is arranged parallel to the respective layer planes, e.g. B. be arranged directly on top of each other.
  • the second catalyst layer can be arranged adjacent to, preferably directly adjacent to, ie in direct contact with, the polymer electrolyte membrane.
  • the polymer electrolyte membrane which is also flat, and the second catalyst layer can directly adjoin one another, forming an interface that is arranged parallel to the plane of the layer, e.g. B. be arranged directly on top of each other.
  • first catalyst layer is also arranged adjacent to the second catalyst layer, an arrangement results in which the second catalyst layer is adjacent to the first catalyst layer on one side and to the polymer electrolyte membrane on the opposite side.
  • ionic contacting of the first catalyst layer can be dispensed with without the catalytic reaction in the first catalyst layer, e.g. B. according to equation (X), is negatively influenced to a greater extent, so the first catalyst material can fulfill the function explained above.
  • a non-binding and non-limiting attempt at explanation by the inventors of the present invention for this is seen in the presence of acidic process water. In other words, direct contact between the first catalyst layer and the polyelectrolyte membrane is not required.
  • the cathodic half cell of the electrolytic cell can have a gas diffusion layer.
  • the gas diffusion layer can be arranged adjacent, preferably directly adjacent, to the first catalyst layer.
  • the gas diffusion layer serves to transport the gaseous reaction products of the catalytic reaction(s) away from the catalyst material(s) and to make electrical contact. It can therefore also be referred to as a current collector layer or gas diffusion electrode.
  • the gas diffusion layer of the cathodic half-cell has a porous material to ensure gas permeability. It can be made of stainless steel, for example.
  • the corrosion accelerated by oxygen and the associated degradation of the gas diffusion layer can be reduced or even avoided.
  • the service life of the gas diffusion layer can be increased.
  • a channel structure can be arranged adjacent, preferably directly adjacent, to the gas diffusion layer.
  • the channel structure is used to collect and discharge the gaseous reaction product of the electrolysis in the cathodic half-cell, ie z. B. hydrogen according to equation (II).
  • the channel structure can be designed as a bipolar plate, for example. Bipolar plates allow several electrolytic cells to be stacked to form an electrolytic cell module by electrically conductively connecting the anode of one electrolytic cell to the cathode of an adjacent electrolytic cell. In addition, the bipolar plate enables gas separation between adjacent electrolytic cells.
  • the first catalyst material can be selected from a group formed by platinum/palladium, platinum/ruthenium, platinum/nickel, platinum/lead/platinum, core-shell catalyst materials, base metal catalyst materials, metal oxides and mixtures thereof.
  • the notation metal A/metal B means that it is a mixed metal catalyst of metals A and B.
  • the first catalyst material can have one or more of the materials mentioned or consist of one or more of the materials mentioned.
  • Core-shell catalysts can be designed, for example, as PtPb/Pt catalysts.
  • Base metal catalysts can be formed, for example, as M-N-C compounds, where M stands for transition metal, N for nitrogen and C for carbon.
  • the required amount of the first catalyst material can be reduced, so that the production costs of the electrolytic cell can also be reduced.
  • the first catalyst layer can have at least one carrier material selected from a group formed by soot particles, carbon fiber fleece, carbon fiber fabric, stainless steel fleece, stainless steel fabric and stainless steel grids.
  • the first catalyst layer can have one or more of the materials mentioned or consist of one or more of the materials mentioned.
  • the term “grid” designates a fine-meshed network.
  • the carrier materials mentioned are characterized by high corrosion resistance.
  • the terms “grid” and “fabric” describe a directional structure, the term “fleece” a non-directional structure.
  • the first catalyst material can be applied to the support material. This advantageously enables a uniform distribution of the first catalyst material.
  • the first catalyst material can have the largest possible surface area be provided, so that the catalytic effect can be improved with the same amount of first catalyst material or less first catalyst material is required for the same catalytic effect.
  • one advantage of a support material is that a higher specific surface area can be generated, as a result of which the activity of the corresponding catalyst material increases accordingly.
  • Another advantage is the contact points with the second catalyst layer that are created by the higher surface area, which increases the contact resistance with the second catalyst layer and improves the transverse conductivity.
  • Another aspect of the invention relates to a method for producing an electrolytic cell for polymer electrolyte membrane electrolysis.
  • the method comprises: providing a polymer electrolyte membrane, forming an anodic half-cell adjacent to the polymer electrolyte membrane and forming a cathodic half-cell adjacent to the polymer electrolyte membrane, wherein the cathodic half-cell and the anodic half-cell are arranged separately from one another by means of the polymer electrolyte membrane and a first catalyst material is formed for catalyzing a Reduction of molecular oxygen, placed in the cathodic half-cell.
  • one of the electrolytic cells for polymer electrolyte membrane electrolysis described above can be produced. Accordingly, reference is made to the above explanations and advantages of these electrolytic cells.
  • the first catalyst material can be introduced into a first catalyst layer.
  • the first catalyst material can be applied to a carrier material.
  • the carrier material with the applied first catalyst material can form the first catalyst layer.
  • the first catalyst material can be applied to the support material, for example by means of chemical vapor deposition (CVD) and/or physical vapor deposition (PVD).
  • CVD chemical vapor deposition
  • PVD physical vapor deposition
  • Chemical vapor deposition may be preferred for porous structures and substrates, while physical vapor deposition may be preferred for non-porous structures. Both chemical vapor deposition and physical vapor deposition advantageously enable the production of thin layers with a layer thickness in the range from a few nanometers to a few micrometers. As a result, catalyst material can be saved.
  • the formation of the cathodic half-cell can have the following steps: applying a second catalyst layer with a second catalyst material, designed to catalyze a reduction of hydrogen ions, to the polymer electrolyte membrane, applying the first catalyst layer to the second catalyst layer, and applying a gas diffusion layer to the first catalyst layer.
  • forming the cathodic half-cell can also include applying a channel structure to the gas diffusion layer.
  • the term “apply on” does not necessarily refer to a concrete spatial arrangement in the sense of “above”. Rather, it is intended merely as an expression be brought that said layers are arranged adjacent to each other.
  • the sequence of the method steps can also be reversed or changed, ie the formation of the cathodic half-cell can alternatively be based on the gas diffusion layer or the channel structure.
  • one of the middle layers e.g. B. the gas diffusion layer or the first catalyst layer can be chosen as a starting point, are applied to both sides, the respective adjacent layers.
  • the structure of the anodic half-cell can be done in an analogous manner, i. H. a catalytic layer for catalyzing the anode reaction, e.g. B. according to equation (I), then a gas diffusion layer and optionally a channel structure, z. B. in the form of a bipolar plate applied.
  • the materials used for this can preferably be adapted to the conditions prevailing in the anodic half-cell, e.g. B. in terms of their corrosion resistance.
  • a further aspect of the invention relates to the use of an electrolytic cell as described above for the electrolytic production of hydrogen.
  • the reactions according to equations (I) and (II) can be carried out in the cathodic or anodic half-cell when an electric current flows through the electrolytic cell.
  • a further aspect of the invention relates to the use of a catalyst material for catalyzing a reduction of molecular oxygen in a cathodic half-cell of an electrolytic cell.
  • the catalyst material can be, for example, the first catalyst material described above, so that reference is made to the relevant explanations and advantages.
  • the electrolytic cell 1 shows an electrolytic cell 1 for polymer electrolyte membrane electrolysis according to the prior art in a schematic representation.
  • the electrolytic cell 1 is used for the electrolytic generation of hydrogen.
  • the electrolytic cell 1 has a polymer electrolyte membrane 4 .
  • the cathodic half-cell 2 of the electrolytic cell 1 is arranged on the other side of the polymer electrolyte membrane 4, in the illustration according to figure 1 on the right, the anodic half-cell 3 of the electrolytic cell 1 is arranged.
  • the anodic half-cell 3 comprises an anodic catalyst layer 12 arranged directly adjacent to the polymer electrolyte membrane 4, one directly adjacent to the anodic catalyst layer 12 arranged gas diffusion layer 9b and a directly adjacent to the gas diffusion layer 9b arranged channel structure 11b.
  • the anodic catalyst layer 12 catalyzes the anode reaction according to Equation (I).
  • the gas diffusion layer 9b is made of a material on the surface of which a passivation layer is easily formed, e.g. B. made of titanium.
  • the channel structure 11b is designed as a bipolar plate, so that a stacking of several electrolytic cells 1 is made possible.
  • the cathodic half cell 2 comprises a catalyst layer 8 with a catalyst material 6 which is arranged directly adjacent to the polymer electrolyte membrane 4 .
  • the catalyst material 6 is designed to catalyze a reduction of hydrogen ions, in particular according to equation (II) to form molecular hydrogen.
  • a gas diffusion layer 9a is also arranged on the catalyst layer 8 .
  • the gas diffusion layer 9a of the cathodic half-cell 2 is made of stainless steel. This is possible due to the lower oxidation potential in the cathodic half-cell 2 compared to the anodic half-cell 3 and reduces the costs of the electrolytic cell 2.
  • a channel structure 11a is also arranged directly adjacent to the gas diffusion layer 9a, which, analogously to the anodic half-cell 3, is designed as a bipolar plate .
  • a disadvantage of this electrolytic cell 1 known from the prior art, as explained above, is the susceptibility to corrosion of the materials in the cathodic half-cell 2 with regard to acid corrosion promoted by elemental oxygen.
  • the hydrogen generated in the cathodic half-cell 2 is contaminated by oxygen.
  • a first catalyst material 5 into the cathodic half-cell, which is used to catalyze a reduction of molecular oxygen, in particular according to equation (X), ie with formation of water.
  • a modified electrolytic cell 1 is an example in figure 2 shown schematically.
  • the anodic half-cell 3 of the in figure 2 shown embodiment of an electrolytic cell 1 is analogous to the electrolytic cell according to figure 1 constructed so that reference can be made to the relevant statements.
  • the cathodic half-cell 2 has, also in analogy to the electrolytic cell according to figure 1 , a gas diffusion layer 9a and a channel structure 11a.
  • a second catalyst layer 8 with a second catalyst material 6 is also arranged directly adjacent to the polymer electrolyte membrane 4, the second catalyst material 6 being designed to catalyze the reduction of hydrogen ions, in particular according to equation (II) to form molecular hydrogen.
  • a first catalyst layer 7 is additionally arranged directly adjacent to the first catalyst layer 8 .
  • the first catalyst layer 7 consists of a fine mesh of a highly corrosion-resistant support material 10, z. B. a stainless steel grid on which the first catalyst material 5, z. B. Pt / Pd, is applied.
  • the first catalyst material 5 is designed to catalyze the reduction of molecular oxygen according to equation (X), ie water is formed from molecular oxygen.
  • equation (X) molecular oxygen
  • the oxygen concentration in the cathodic half-cell 2 decreases and the corrosion promoted by oxygen, in particular of the gas diffusion layer 9a, can be reduced.
  • the result is a longer service life, especially for the gas diffusion layer.
  • the reduced corrosion may allow the use of less expensive materials in the cathodic half-cell 2.
  • the electrolytically generated hydrogen is also less contaminated with oxygen, i. H. the purity of the product hydrogen is increased. A low proportion of oxygen in the hydrogen produced reduces the effort required for subsequent purification for various applications. The hydrogen produced is thus upgraded.
  • the hydrogen therefore reaches the gas diffusion layer 9a, which is arranged directly adjacent to the first catalyst layer 7, with a significantly lower oxygen content, and then leaves the electrolytic cell 2 with high purity via the channel structure 11a arranged directly adjacent to the gas diffusion layer 9a. This occurs during the catalytic reaction of the first catalyst material 5 water formed according to equation (X) is discharged together with the gas stream.
  • figure 3 shows a flowchart of an exemplary method 100 for producing an electrolytic cell 1, for example the one in figure 2 shown electrolytic cell 1.
  • a polymer electrolyte membrane 4 is provided in step S1. Then, in step S2, an anodic half-cell 3 adjoining the polymer electrolyte membrane 4 is formed.
  • the anodic catalyst layer 12, the gas diffusion layer 9b and the channel structure 11b can be arranged one on top of the other, e.g. B. are deposited on each other.
  • step S3 the cathodic half-cell 2, also adjacent to the polymer electrolyte membrane 4, but opposite to the anodic half-cell 3, is formed.
  • the first catalyst material 5 which is designed to catalyze a reduction of molecular oxygen, is arranged in the cathodic half-cell 2. Steps S2 and S3 can also be carried out at the same time or in reverse order.
  • the step S3 comprises the sub-steps S4 to S7, i. H.
  • the cathodic half-cell 2 is formed by means of steps S4 to S7.
  • a second catalyst layer 8 with a second catalyst material 6, which is designed to catalyze a reduction of hydrogen ions to molecular hydrogen, is first applied to the side of the polymer electrolyte membrane 4 opposite the anodic half-cell 2.
  • a first catalyst layer 7 is then applied to the second catalyst layer 8 in step S5.
  • the second catalyst layer 8 contains the first catalyst material 5.
  • first a support material 10 is provided, on the surface of which the first catalyst material 5 is applied by means of chemical vapor deposition and/or physical vapor deposition.
  • step S6 a gas diffusion layer 9a is applied to the first catalyst layer 7 before a channel structure 11a in the form of a bipolar plate is applied to the gas diffusion layer 9a in step S7.
  • the cathodic half-cell 2 can also be formed starting from the channel structure 11a. i.e.
  • the channel structure 11a can be chosen as the starting point, onto which first the gas diffusion layer 9a, then the first catalyst layer 7, then the second catalyst layer 8 and finally the polymer electrolyte membrane 4 are applied.
  • a corresponding procedure is possible for the anodic half-cell 3 . Consequently, the layers and structures of the electrolytic cell 1 can alternatively also starting from the channel structure 11a of the cathodic Half-cell 2 or starting from the channel structure 11b of the anodic half-cell 3 are constructed.
  • the term "and/or" when used in a set of two or more items means that each of the listed items can be used alone, or any combination of two or more of the listed items can be used.

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  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP21182692.0A 2021-06-30 2021-06-30 Cellule d'électrolyse destinée à l'électrolyse à membrane électrolytique polymère et son procédé de fabrication Withdrawn EP4112781A1 (fr)

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EP21182692.0A EP4112781A1 (fr) 2021-06-30 2021-06-30 Cellule d'électrolyse destinée à l'électrolyse à membrane électrolytique polymère et son procédé de fabrication
PCT/EP2022/061776 WO2023274601A1 (fr) 2021-06-30 2022-05-03 Cellule électrolytique pour électrolyse à membrane électrolytique polymère et son procédé de production
CA3225562A CA3225562A1 (fr) 2021-06-30 2022-05-03 Cellule electrolytique pour electrolyse a membrane electrolytique polymere et son procede de production
EP22727778.7A EP4330445A1 (fr) 2021-06-30 2022-05-03 Cellule électrolytique pour électrolyse à membrane électrolytique polymère et son procédé de production
CN202280046156.6A CN117651789A (zh) 2021-06-30 2022-05-03 用于聚合物电解质膜电解的电解池及其制造方法

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EP22727778.7A Pending EP4330445A1 (fr) 2021-06-30 2022-05-03 Cellule électrolytique pour électrolyse à membrane électrolytique polymère et son procédé de production

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US20190071783A1 (en) * 2016-03-17 2019-03-07 Hpnow Aps Electrochemical cell for gas-phase reactant in liquid environment
EP3453785A1 (fr) * 2017-09-07 2019-03-13 Kabushiki Kaisha Toshiba Ensemble électrode à membrane, cellule électrochimique et dispositif électrochimique
EP3489394A1 (fr) 2017-11-24 2019-05-29 Siemens Aktiengesellschaft Électrolyseur pour électrolyse pem à basse pression
EP3553866A1 (fr) * 2018-04-13 2019-10-16 Technische Universität Berlin Matériau catalyseur pour une pile à combustible ainsi que son procédé de fabrication
US20210066741A1 (en) * 2019-09-03 2021-03-04 Korea Institute Of Science And Technology High temperature-type unitized regenerative fuel cell using water vapor and method of operating the same

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DE102013019341A1 (de) * 2013-11-20 2015-05-21 Forschungszentrum Jülich GmbH Elektrochemische Elektrolysezelle sowie Verfahren zum Betreiben derselben
US20190071783A1 (en) * 2016-03-17 2019-03-07 Hpnow Aps Electrochemical cell for gas-phase reactant in liquid environment
EP3453785A1 (fr) * 2017-09-07 2019-03-13 Kabushiki Kaisha Toshiba Ensemble électrode à membrane, cellule électrochimique et dispositif électrochimique
EP3489394A1 (fr) 2017-11-24 2019-05-29 Siemens Aktiengesellschaft Électrolyseur pour électrolyse pem à basse pression
EP3553866A1 (fr) * 2018-04-13 2019-10-16 Technische Universität Berlin Matériau catalyseur pour une pile à combustible ainsi que son procédé de fabrication
US20210066741A1 (en) * 2019-09-03 2021-03-04 Korea Institute Of Science And Technology High temperature-type unitized regenerative fuel cell using water vapor and method of operating the same

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KUMAR, S ET AL.: "Hydrogen production by PEM water electrolysis - A review", MATERIALS SCIENCE FOR ENERGY TECHNOLOGIES, vol. 2, no. 3, 2019, pages 442 - 454, Retrieved from the Internet <URL:https://doi.org/10.1016/j.mset.2019.03.002>
SCHALENBACH, M. ET AL.: "Pressurized PEM water electrolysis: Efficiency and gas crossover", INTERN. J. HYDR. ENER., vol. 38, no. 35, 2013, pages 14921 - 14933, XP028762381, Retrieved from the Internet <URL:https://doi.org/10.1016/j.ijhydene.2013.09.013> DOI: 10.1016/j.ijhydene.2013.09.013
YU, J. ET AL.: "A mini-review of noble-metal-free electrocatalysts for overall water splitting in non-alkaline electrolytes", MAT. REP.: ENERGY, vol. 1, no. 2, 2021, pages 100024, Retrieved from the Internet <URL:https://doi.org/10.1016/j.matre.2021.100024>

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CN117651789A (zh) 2024-03-05
CA3225562A1 (fr) 2023-01-05
WO2023274601A1 (fr) 2023-01-05

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