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EP3728698B1 - Électrode de diffusion gazeuse, installation d'électrolyse et procédé de fonctionnement d'une installation d'électrolyse - Google Patents

Électrode de diffusion gazeuse, installation d'électrolyse et procédé de fonctionnement d'une installation d'électrolyse Download PDF

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EP3728698B1
EP3728698B1 EP19714106.2A EP19714106A EP3728698B1 EP 3728698 B1 EP3728698 B1 EP 3728698B1 EP 19714106 A EP19714106 A EP 19714106A EP 3728698 B1 EP3728698 B1 EP 3728698B1
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Prior art keywords
layer
gas diffusion
diffusion electrode
electrolyte
gas
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German (de)
English (en)
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EP3728698A1 (fr
Inventor
Harald Landes
Christian Reller
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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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    • 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
    • C25B1/23—Carbon monoxide or syngas
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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
    • 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
    • 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
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • 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

Definitions

  • the invention relates to a gas diffusion electrode according to claim 1, an electrolysis system for converting carbon dioxide according to claim 9 and a method for operating an electrolysis system according to claim 12.
  • organic valuable substances can be synthesized, which are obtained from the carbon dioxide-containing exhaust gases from industry and fossil power plant processes on the basis of aqueous CO 2 electrolysis.
  • One process step here is to reduce carbon dioxide to carbon monoxide with the help of electrical energy, whereby the carbon monoxide serves as a diverse valuable material and as a starting material for the further synthesis of organic substances.
  • electrolysis systems in the form of electrolysers are used, which have a so-called gas diffusion electrode (GDE) as a central component.
  • GDE gas diffusion electrode
  • These gas diffusion electrodes are usually produced on the basis of a silver catalyst bonded in a polymer matrix.
  • B. a metal mesh is introduced for mechanical stabilization.
  • the object of the invention is to provide a gas diffusion electrode and an electrolysis system with a gas diffusion electrode and a method for operating an electrolysis system that has a longer service life than the conventional structure.
  • the object is achieved in a gas diffusion electrode according to claim 1 and in an electrolysis system according to claim 9 and in the method for operating an electrolysis system according to claim 12.
  • the gas diffusion electrode according to claim 1 has at least two layers, of which a first layer has an electrically conductive fabric which is at least partially embedded in a hydrophobic polymer matrix. Furthermore, the gas diffusion electrode has a second layer with an open porosity, which comprises catalytically active particles and which has a thickness between 1 ⁇ m and 50 ⁇ m.
  • the first layer which has the electrically conductive fabric, essentially serves to mechanically stabilize the gas diffusion electrode and to make electrical contact. This is a feature that is already known for the GDEs from the prior art. Unlike in the prior art, however, this fabric is surrounded by a hydrophobic polymer matrix that has a wetting angle compared to water or to the adjacent liquid electrolyte, which is greater than 90 °.
  • the fabric consists of or comprises silver-containing or titanium-containing fibers. If the fabric is protected from wetting by the electrolyte by the polymer matrix except for the contact points with the second layer, it can also comprise nickel. A fabric made of silver fibers is particularly preferred. In further, not claimed embodiments, it is also possible that the fibers contain carbon.
  • a suitable matrix material for the polymer matrix of the first layer is polytetrafluoroethylene. This is sufficiently hydrophobic and it is suitable for enclosing the tissue as well as possible.
  • polymer matrix is not to be understood as a closed, dense matrix, but rather a, as already mentioned, porous matrix that allows gaseous starting materials to diffuse through this polymer matrix and reach an interface between the first layer and the second layer for reactive conversion .
  • the first layer of the GDE preferably has a thickness which is between 50 ⁇ m and 1000 ⁇ m.
  • the thickness of the first layer is essentially determined by the strength of the individual fabric fibers. Fibers with a diameter of 100 ⁇ m are quite common, the mesh size is usually 0.3 mm. Larger fiber thicknesses and thus greater layer thicknesses of the first layer are quite possible; they serve to increase the stability of the GDE, but mean that the educts, in particular gaseous educts, have to diffuse through a thicker layer, which in turn increases the electrochemical conversion between the first and the second Layer reduced.
  • the thickness of the first layer is between 100 ⁇ m and 400 ⁇ m.
  • the polymer matrix of the first layer prefferably has a porosity in which 95% of the pores have a diameter which is between 0.1 ⁇ m and 2 ⁇ m, preferably between 0.6 ⁇ m and 0.9 ⁇ m. Pores of this size allow gaseous educts to diffuse, but due to their hydrophobic character they do not allow any or hardly any liquid electrolytes to penetrate, even if this has an overpressure of 0.2 compared to the gas phase in the first layer bar as it can occur in larger cells and stacks.
  • the catalytically active particles of the second layer have a diameter which is between 0.05 ⁇ m and 1 ⁇ m, preferably between 0.1 ⁇ m and 0.5 ⁇ m.
  • Such fine particles, in particular silver particles in turn have a large catalytic surface on which the desired reaction can take place.
  • the catalytically active particles are, in particular, silver particles which, on the one hand, have a hydrophilic surface that favors the absorption of the liquid electrolyte.
  • the surface of the silver particles has a particularly catalytic effect for many desired reactions, for example for the conversion of carbon dioxide to carbon monoxide, the disruptive reduction of the water to hydrogen being suppressed.
  • the catalytically active particles are mixed with binders that also have a hydrophilic effect, so that a specific porosity can be set in this way and a certain bond takes place between the catalytically active particles. It is useful here if the wetting angle of these hydrophilically acting binders is less than 90 °.
  • the pores of the second layer it is again expedient for 95% of the pores of the second layer to have a diameter which is between 0.1 ⁇ m and 5 ⁇ m or preferably between 0.1 ⁇ m and 1 ⁇ m.
  • image-evaluating methods are used. Here, a cross-section or a top view is photographed microscopically and the pore frequency or their diameter at the largest point of the diameter is evaluated.
  • Another component of the invention is an electrolysis system for the electrolytic conversion of carbon dioxide with a gas diffusion electrode according to one of the preceding claims.
  • Such an electrolysis system has a Gas space and an electrolyte chamber.
  • the gas diffusion electrode is installed between the gas space and the electrolyte chamber and separates them from one another at least in certain areas.
  • the second layer of the GDE is directed towards the electrolyte chamber, the first layer is in contact with the gas space.
  • the described effect of the gas diffusion electrode can be technically implemented. It is also useful if a contact web makes electronic contact with the gas diffusion electrode and is in direct contact with uncoated parts of the tissue.
  • Another component of the invention is a method for operating the electrolysis system, a carbon dioxide-containing educt being introduced into the gas space, the educt being fed to the gas diffusion electrode and diffusing through the first layer of the gas diffusion electrode. It hits a boundary layer of the first layer and the second layer of the gas diffusion electrode and is chemically converted there. The second layer is soaked in a liquid electrolyte.
  • the same modes of action and advantages already described for the gas diffusion electrode exist. This applies in particular with regard to the structure mentioned between the first and the second layer, the first layer being hydrophobic and the second layer preferably being hydrophilic and also having catalytically active particles.
  • the desired conversion occurs at an interface between the hydrophilic layer and the hydrophobic layer, in particular the reduction of carbon dioxide to carbon monoxide.
  • FIG. 1 a schematic representation of a section from an electrolysis system 20 is shown.
  • An electrolyser can also be referred to as an electrolysis system 20, in which case carbon dioxide is introduced as an educt and carbon monoxide is formed as a product.
  • the electrolysis system 20 has a gas space 22 and an electrolyte chamber 24.
  • the educt gas carbon dioxide is brought into the gas space 22 via an educt feed device (not shown here) and is guided through the gas space 22 to a gas diffusion electrode (GDE) 2.
  • GDE gas diffusion electrode
  • the gas diffusion electrode 2 essentially comprises two layers, a first layer 4 and a second layer 6.
  • the first layer 4 is characterized in that it takes on a load-bearing function for the entire GDE 2; consists of silver threads, embedded.
  • the fabric 8 is in turn surrounded by a polymer matrix 10 which, however, is designed to be porous, so that starting materials 28 in the form of carbon dioxide can diffuse in gaseous form through the first layer 4 up to an interface 30 of the GDE 2.
  • the interface 30 marks the boundary between the first layer 4 and the second layer 6.
  • the second layer 6 has a functional character compared to the first layer 4. It is characterized in that it is also porous and catalytically active particles 9 in the form of silver particles 9 are present on the surface of the pores.
  • it is an open porosity, but with a liquid electrolyte 32 is infiltrated, the liquid electrolyte 32 being present in particular in the electrolyte space 24.
  • contacting webs 26 are provided, which rest positively on the GDE 2 and press it against a counter web 27 through which electrical current is conducted to the tissue 8 and thus into the gas diffusion electrode 2.
  • FIG 2 an enlarged schematic section from the border area between the first layer 4 and the second layer 6 is shown, which is intended to explain the microstructure of the GDE 2 schematically. This is a representation that is not true to scale, in particular the second layer is drawn relatively densely.
  • the first layer 4 is shown with the fabric 8, the second layer 6 can be seen on the left-hand side. Both layers 4, 6 meet at the interface 30.
  • the in Figure 2 The section shown shows on the right side again a section from two fibers of the fabric 8, which in this case are silver fibers.
  • the lower fiber of the fabric 8 is in a form-fitting connection with the contact web 26.
  • the fabric 8 is protected by an inert matrix or coating.
  • this is the polymer matrix 10, the particles of the polymer matrix 10 being shown here by way of example and for better differentiation as triangles.
  • a material other than that used for the porous matrix between the individual fibers of the fabric 8 can also be used to coat the fabric 8.
  • the matrix 10 has an open porosity 16 with individual pores 17, so that the educt 28, that is to say the carbon dioxide, can diffuse through the first layer 4 to the interface 30. This diffusion path is illustrated by the arrow 28, which is labeled with CO 2. It is also important that the material of the polymer matrix 10 is a hydrophobic material in order to prevent liquid electrolyte 32 from penetrating beyond the interface 30 into the first layer 4 of the GDE 2. It is thus avoided that an electrochemical reaction already takes place in the first layer 4, which in the reaction equations that apply to the conversion of carbon dioxide to carbon monoxide in connection with the electrolyte, leads to a salination of the GDE 2 in the essential areas of the first layer 4 would lead.
  • hydrophobic is understood to mean that the capillary forces that act on the liquid electrolyte 32 at the interfaces with the particles of the matrix 10 are sufficient to prevent this liquid electrolyte from penetrating the layer 4. It is usually assumed that a material surface 33 has a hydrophobic property when the wetting angle, which is in the Figure 3 is shown schematically, is greater than 90 °. However, the wetting angle is preferably> 95 °. This is in the Figure 3 shown on the left half of the illustration.
  • the matrix 10 in the first layer 4 is designed in such a way that it envelops the fibers of the fabric 8 as a protective layer, so that even when silver threads are used for the fabric 8, there is no catalytic effect between the Surface of the tissue 8 and the electrolyte or carbon dioxide can occur as educt 28.
  • the triangular matrix parts of the matrix 10 are therefore shown here schematically in such a way that they represent a protective surface layer on the tissue fibers 8. In principle, however, this can also be a separate coating for the fabric 8, which is different from the rest of the matrix 10 with regard to the material.
  • the layer on the silver fibers can also be porous as long as the pore radius is small enough to, in conjunction with the hydrophobic property of the matrix material, prevent wetting of the silver fibers with electrolyte.
  • first layer 4 Two important properties of the first layer 4, in addition to the load-bearing capacity provided by the fabric 8, also consist in the fact that it is as hydrophobic as possible and as unreactive as possible.
  • second layer 6 which is usually applied to the first layer 4 by a further coating process.
  • This layer comprises in particular catalytically active particles 9, which are designed in particular in the form of silver particles.
  • These particles 9 can preferably also be provided with a binding material, this being a hydrophilic binding agent 18, which is used in Figure 2 is shown schematically by oval particles.
  • the surface structure of this hydrophilic binder 18 is characterized in that it has the best possible wetting compared to the liquid electrolyte solution 32, so that the layer 6 can be infiltrated by the electrolyte 32, even if an overpressure in the range of 0.2 bar from the gas side prevails. This is achieved in particular when the surface of the hydrophilic binder has a surface tension which leads to the wetting angle in relation to water or a water droplet 15 or in relation to the liquid electrolyte according to FIG Figure 3 right side is less than 85 °. As the name suggests, these binders 18 have a binding effect between the individual catalytically active particles 9 and, depending on the structure and nature of the particles 9, are optional but advantageous for the production of the layer 6.
  • a specific porosity is set both in layer 4 and in layer 6, so that on the one hand the gas molecules can diffuse through the first layer 4 and the liquid electrolyte 32 can infiltrate into the second layer 6. It has been found here that it is expedient for the pore structure of the first layer 4 to be designed in such a way that 95% of the pores have a diameter which is between 0.6 ⁇ m and 0.9 ⁇ m. In terms of process technology, it is not always possible to set such an exact pore structure without increased technical effort. Therefore there are also larger pores up to 2 ⁇ m but also smaller pores up to 0.1 ⁇ m quite acceptable even to a lesser extent.
  • the layer thickness of the first layer 4 is determined in particular by the diameter of the fibers of the fabric 8.
  • the second layer 6 can be made significantly thinner than the first layer 4; ultimately, the second layer 6 is generally applied to the load-bearing first layer 4 using a specific coating process. Of the purely chemical processes, the second layer 6 could be very thin; strictly speaking, one layer of catalytically active particles 9 would be sufficient.
  • each individual particle 9 of the second layer 6 has a diameter which is between 0.05 ⁇ m and 3 ⁇ m, very particularly preferably between 0.1 ⁇ m and 0.5 ⁇ m.
  • the porosity of the second layer 6, here too 95% of the pores are between 0.1 ⁇ m and 5 ⁇ m, preferably between 0.1 ⁇ m and 1 ⁇ m.
  • Hollow particles 9, which are not shown here, which have an inner, externally accessible cavity with this pore size, are also expedient. With larger external dimensions, the pores between the particles inevitably also become larger and are then no longer suitable for holding the electrolyte in the pore against an existing gas pressure.
  • the starting material is then converted, usually carbon dioxide 28 to the product carbon monoxide 29.
  • the following reaction equations preferably or usually run : 2CO 2 + H 2 O + 2e - ⁇ CO + 2HCO 3 - Equation 1 CO 2 + H 2 O + 2e - ⁇ CO + 2OH - Equation 2
  • the electrons that are required for the reaction equations are guided to the interface 30 via the contact web 26 and the tissue 8.
  • the respective water is contained in a large excess in the electrolyte, which penetrates via the second layer 6 to the interface 30.
  • the carbon dioxide is generated according to path 28 in Figure 2
  • the carbon monoxide is likewise discharged through the first layer 4 via the same route.
  • the hydrogen carbonate ions or the hydroxide ions are returned in aqueous solution through the layer 6 to the liquid electrolyte, which is exchanged by a volume flow so that a constant concentration is present in each case. Because the second layer is thin, the transport of all electrolyte components is promoted, so that the precipitation of hydrogen carbonate is counteracted.
  • the hydrophobic effect of the matrix 10 of the first layer 4 prevents the electrolyte 32 from reaching the first layer 4 and where salts precipitate after the reaction.
  • the thickness of the second layer is comparatively small at 1 ⁇ m to 50 ⁇ m. This ensures, on the one hand, that sufficient electronic conductivity is available within the catalyst layer in order to ensure the supply of the GDE within the meshes of the conductive network 8. On the other hand, there is enough catalytically active surface of the particles 9 within a range of the diffusing and dissolved carbon dioxide is available to a Carry current density in the desired form to reduce the carbon dioxide. Consequently, the second layer 6 can in principle be produced from a few monolayers of particles 9 with a diameter of 0.1 ⁇ m. Particles 9, in particular silver particles with a diameter of approx. 1 ⁇ m, are still in the range of what leads to successful catalysis, but they are not so well suited.
  • Electrochemically active are essentially only the surfaces within a region from the interface into the layer 6 which is in the order of magnitude of a diffusion length of the dissolved carbon dioxide, that is to say in the 0.1 to 1 ⁇ m range.
  • the areas of the second layer 6 which extend further into the electrolyte space contribute insignificantly to the CO 2 reduction compared with those areas of the layer 6 which are close to the interface 30. Due to a small voltage drop in the electrolyte of the GDE 2, the development of hydrogen is only possible to a small extent, if at all, since hardly any concentration gradient is established in the porous second layer 6 on this small extent.
  • the thickness of the second layer 6 can be greater than the few particle layers mentioned is due to the fact that an electrical path resistance that is present in the layer 6 must also be low enough to provide the electronic power supply between the individual contact webs 26 to ensure.
  • the pore diameter is actually smaller than the already described upper limit of 1 ⁇ m.
  • the pores Preferably only the pores have a diameter of 0.1 ⁇ m to 0.5 ⁇ m, so that it is ensured that these pores 13 are filled with electrolyte 32 due to the hydrophilic surface of the catalytically active particles 9, which results in a diffusion barrier for the carbon dioxide leads.
  • the catalytically active particles 9 should therefore accordingly be anchored on the hydrophobic structure of the first layer 4 at the interface 30, if possible by an additional binder.
  • the pore systems in both the first layer 4, which has a supporting function, and the second layer 6, which has a catalytic function to have the highest possible porosity. It has been found that porosities over 25% are well suited so that, on the one hand, the gas transport of carbon dioxide and carbon monoxide can take place through the first layer 4 and, on the other hand, the infiltration of the second layer 6 by the liquid electrolyte 32 can take place.
  • the path that the liquid electrolyte 32 has to travel into the gas diffusion electrode 2 is shortened; on the other hand, the path 28 that the carbon dioxide has to travel through the first layer 4 is barely increased significantly, which results in the polarization of the gas diffusion electrode described 2 decreases compared to conventional GDEs.
  • a layer of Dyneon TF 2021 is sieved onto a silver fabric 8 with a wire diameter of 180 ⁇ m and a mesh size of 250 ⁇ m using 500 ⁇ m thick stencils (with an opening of 60 mm x 120 mm) and then pulled off with a squeegee.
  • the layer is rolled using a 2-roll calender with a roll gap of 0.3 ⁇ m so that the crests of the wire mesh protrude from the membrane.
  • a 1 ⁇ m to 20 ⁇ m thick second layer 6, which serves as a catalyst layer, made of silver nanoparticles with a primary particle diameter of 0.1 ⁇ m is sprayed on with the aid of an airbrush.
  • the particle suspension is prepared as follows: 60 mg of silver nanoparticles (purity> 99.9%) and 30 mg of a hydrophilic binder (anion exchange ionomer) are dispersed in 3 ml of n-propanol in an ultrasonic bath for 10 to 15 minutes. It becomes a load aimed at from 0.5 mg to 3 mg catalyst / cm 2.
  • the electrode is dried under a continuous stream of argon for 12 hours. The electrical contacting of the nanoparticles takes place through percolation or through the protruding tips of the silver fabric 8.
  • the electrode has a sheet resistance of 0.001 ⁇ and can advantageously be contacted from the gas side.
  • a particular advantage of this electrode structure is that the reaction site at the interface between the first and second layer is fixed within certain limits regardless of the pressure difference between the gas and liquid sides. This is ensured by the fact that the pressure required to press the electrolyte out of the preferably hydrophilic second layer is in the range of preferably more than 0.2 bar and, conversely, an excess pressure of this amount on the electrolyte side is not sufficient to transfer the electrolyte into the first To allow layer to penetrate. In this way, well-suited operating conditions are established in the reaction zone without having to carefully adjust the pressure between the gas and electrolyte side.
  • the GDE described is robust against pressure fluctuations, such as those that occur as a result of the weight pressure in larger cells and cell stacks, or when there is a flow through the cells during operation.
  • the penetration depth of the electrolyte differs locally and depends on the pressure difference in the mbar range.
  • the electrolyte or gas-filled pores up to the reaction site are of different lengths and thus there are places at which the undesired water reduction is favored.

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Claims (12)

  1. Electrode (2) à diffusion de gaz comprenant au moins deux couches (4,6), dont une première couche (4) a un tissu (8) conducteur de l 'électricité, qui est incorporé, au moins en partie, dans une matrice (10) polymère à effet hydrophobe, la matrice (10) polymère étant conformée de manière hydrophobe et ayant un angle (14) de mouillage vis -à -vis de l'eau de plus de 90° et dans lequel une deuxième couche (6) a une porosité (12) ouverte, qui comprend des particules (9) à effet catalytique et qui a une épaisseur comprise entre 1 µm and 50 µm, caractérisée en ce que le tissu (8) comprend une fibre contenant de l 'argent, du titane ou du nickel.
  2. Electrode à diffusion de gaz suivant la revendication 1, caractérisée en ce que la matrice (10) polymère comprend du polithetrafluoroéthylène.
  3. Electrode à diffusion de gaz suivant l'une des revendications précédentes, caractérisée en ce que la première couche (4) a une épaisseur, qui est comprise entre 50 µm et 1 000 µm, en étant comprise notamment entre 100 µm et 400 µm.
  4. Electrode à diffusion de gaz suivant l'une des revendications précédentes, caractérisée en ce que la matrice (10) polymère a une porosité (16) et en ce que 95 % des pores (17) ont un diamètre, qui est compris entre 0,1 µm et 2 µm, en étant de préférence compris entre 0,6 µm et 0,9 µm.
  5. Electrode à diffusion de gaz suivant l'une des revendications précédentes, caractérisée en ce que les particules (9) à effet catalytique de la deuxième couche (6) ont un diamètre, qui est compris entre 0,05 µm et 1 µm, en étant de préférence compris entre 0,1 µm et 0,5 µm.
  6. Electrode à diffusion de gaz suivant l'une des revendications précédentes, caractérisée en ce que la deuxième couche (6) comprend des particules d 'argent, comme particules (9) à effet catalytique.
  7. Electrode à diffusion de gaz suivant l'une des revendications précédentes, caractérisée en ce que les particules (9) de la deuxième couche (6) sont mélangées à un liant (18) hydrophile, qui a un angle (14) de mouillage par rapport à l'eau de moins de 90°.
  8. Electrode à diffusion de gaz suivant l'une des revendications précédentes, caractérisée en ce que au moins 95 % des pores (13) de la deuxième couche (6) ont un diamètre, qui est compris entre 0,1 µm et 5 µm, en étant de préférence compris entre 0,1 µm et 1 µm.
  9. Installation d 'électrolyse pour la transformation électrolytique du dioxyde de carbone, ayant une électrode à diffusion de gaz suivant l'une des revendications précédentes.
  10. Installation d 'électrolyse suivant la revendication 9, caractérisée en ce que l 'installation d 'électrolyse a un compartiment (22) pour du gaz et une chambre (24) d 'électrolyte, la deuxième couche (6) de l 'électrode (2) à diffusion de gaz étant dirigée vers la chambre (24) d "électrolyte.
  11. Installation d 'électrolyse suivant l'une des revendications 9 ou 10, caractérisée en ce qu'une barrette (26) de contact est en contact électriquement avec l 'électrode (2) à diffusion de gaz.
  12. Procédé pour faire fonctionner une installation d 'électrolyse suivant l'une des revendications 9 à 11, dans lequel on introduit dans le compartiment (22) pour du gaz un éduit (28) contenant du dioxyde de carbone, on envoie l 'éduit (28) à l 'électrode à diffusion de gaz (2), et on le fait diffuser dans la première couche (4) de l 'électrode à diffusion de gaz (2), grâce à quoi il atteint une surface (30) limite de la première couche (4) avec la deuxième couche (6) de l 'électrode (2) à diffusion de gaz et il y est réduit, la deuxième couche (6) étant imprégnée d'un électrolyte liquide.
EP19714106.2A 2018-03-29 2019-03-08 Électrode de diffusion gazeuse, installation d'électrolyse et procédé de fonctionnement d'une installation d'électrolyse Active EP3728698B1 (fr)

Priority Applications (1)

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PL19714106T PL3728698T3 (pl) 2018-03-29 2019-03-08 Elektroda dyfuzyjna gazowa, instalacja elektrolityczna oraz sposób eksploatacji instalacji elektrolitycznej

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DE102018204890 2018-03-29
DE102018205571.8A DE102018205571A1 (de) 2018-03-29 2018-04-12 Gasdiffusionselektrode, eine Elektrolyseanordnung sowie ein Verfahren zum Betreiben einer Elektrolyseanlage
PCT/EP2019/055839 WO2019185328A1 (fr) 2018-03-29 2019-03-08 Électrode de diffusion gazeuse, installation d'électrolyse et procédé de fonctionnement d'une installation d'électrolyse

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US (1) US20210002776A1 (fr)
EP (1) EP3728698B1 (fr)
DE (1) DE102018205571A1 (fr)
DK (1) DK3728698T3 (fr)
ES (1) ES2908010T3 (fr)
PL (1) PL3728698T3 (fr)
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DE102022127150A1 (de) * 2022-10-17 2024-04-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Gasdiffusionssubstrat aus einem porösen Metallsubstrat und einer gasdurchlässigen Polymerschicht, Verfahren zu dessen Herstellung sowie Gasdiffusionselektrode und elektrochemische Zelle mit einem Gasdiffusionssubstrat
DE102024201239A1 (de) * 2024-02-12 2025-08-14 Siemens Energy Global GmbH & Co. KG Elektrolysezelle mit optimierter Kontaktierung einer Katalysatorschicht

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US3444004A (en) * 1965-09-30 1969-05-13 Leesona Corp Electrochemical cell having at least one non-consumable electrode comprising a porous metal support having internal voids sealed with a hydrophobic polymer
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JP3628756B2 (ja) * 1995-04-28 2005-03-16 ペルメレック電極株式会社 ガス拡散電極
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PL3728698T3 (pl) 2022-04-04
EP3728698A1 (fr) 2020-10-28
DE102018205571A1 (de) 2019-10-02
ES2908010T3 (es) 2022-04-27
DK3728698T3 (da) 2022-02-07
WO2019185328A1 (fr) 2019-10-03
US20210002776A1 (en) 2021-01-07

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