EP3307924B1 - Präparationstechnik von kohlenwasserstoffselektiven gasdiffusionselektroden basierend auf cu-haltigen-katalysatoren - Google Patents

Präparationstechnik von kohlenwasserstoffselektiven gasdiffusionselektroden basierend auf cu-haltigen-katalysatoren Download PDF

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EP3307924B1
EP3307924B1 EP16741915.9A EP16741915A EP3307924B1 EP 3307924 B1 EP3307924 B1 EP 3307924B1 EP 16741915 A EP16741915 A EP 16741915A EP 3307924 B1 EP3307924 B1 EP 3307924B1
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copper
layer
binder
mixture
weight
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German (de)
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French (fr)
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EP3307924A1 (de
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Ralf Krause
Anna Maltenberger
Christian Reller
Bernhard Schmid
Günter Schmid
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Siemens AG
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Siemens AG
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—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
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound

Definitions

  • the present invention relates to a gas diffusion electrode comprising a preferably copper-containing carrier and a first layer comprising at least copper and at least one binder, the (first) layer comprising hydrophilic and hydrophobic pores and / or channels, further comprising a second layer comprising copper and at least a binder, wherein the second layer is on the carrier and the first layer on the second layer, wherein the content of binder in the first layer is smaller than in the second layer, a method for producing such a gas diffusion electrode and an electrolytic cell comprising a such gas diffusion electrode.
  • CO 2 is converted into carbohydrates by photosynthesis. This temporally and on a molecular level spatially divided into many sub-steps process is very difficult to copy on an industrial scale.
  • the currently more efficient route compared to pure photocatalysis is the electrochemical reduction of CO 2 s, as in photosynthesis
  • electrical energy which is preferably obtained from regenerative energy sources such as wind or sun
  • CO 2 is converted into a higher energy product (such as CO, CH 4 , C 2 H 4 , C 1 -C 4 alcohols, etc.).
  • the amount of energy required in this reduction ideally corresponds to the combustion energy of the fuel and should come only from renewable sources or use electricity that just can not be removed from the grid.
  • an overproduction of renewable energies is not continuously available, but currently only at times with strong sunlight and / or strong wind.
  • this will be further strengthened or remedied in the near future as the installations are located in different locations.
  • Table 1 shows the typical Faraday efficiencies (FE) on different metal cathodes.
  • FE Faraday efficiencies
  • CO 2 is reduced almost exclusively to CO, for example on Ag, Au, Zn, and with restrictions on Pd, Ga
  • copper has a large number of hydrocarbons as reduction products.
  • metal alloys as well as mixtures of metal and metal oxide, which is co-catalytically active, are of interest because they can increase the selectivity of a particular hydrocarbon.
  • this is the state of the art is not very pronounced.
  • Table 1 Faraday efficiencies for carbon dioxide on various metal electrodes electrode CH 4 C 2 H 4 C 2 H 5 OH C 3 H 7 OH CO HCOO - H 2 Total Cu 33.3 25.5 5.7 3.0 1.3 9.4 20.5 103.5 Au 0.0 0.0 0.0 0.0 87.1 0.7 10.2 98.0 Ag 0.0 0.0 0.0 0.0 81.5 0.8 12.4 94.6 Zn 0.0 0.0 0.0 0.0 79.4 6.1 9.9 95.4 Pd 2.9 0.0 0.0 0.0 28.3 2.8 26.2 60.2 ga 0.0 0.0 0.0 0.0 23.2 0.0 79.0 102.0 pb 0.0 0.0 0.0 0.0 0.0 0.0 97.4 5.0 102.4 hg 0.0 0.0 0.0 0.0 99.5 0.0 99.5 In 0.0 0.0 0.0 0.0 2.1 94.
  • the single-electrode equations show that very complex, previously unexplained processes with, for example, CO or format intermediates take place here.
  • a particularly preferred site on and / or on the copper cathodes should be necessary.
  • the catalytic activity depends on the crystallographic Orientation of the copper surface, as in for example Y. Hori, I. Takahashi, O. Koga, N. Hoshi, "Electrochemical reduction of carbon dioxide at various series of copper single crystal electrodes"; Journal of Molecular Catalysis A: Chemical 199 (2003) 39-47 ; or M. Gattrell, N. Gupta, A. Co, "A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper”; Journal of Electroanalytical Chemistry 594 (2006) 1-19 shown, changes.
  • the electrode In order to be able to provide all these crystallographic surfaces for a high ethylene-forming efficiency at high current density, the electrode must not consist of a smooth metal sheet, but should be micro- to nanostructured.
  • GDE gas diffusion electrodes
  • Silver / silver oxide / PTFE (polytetrafluoroethylene) -based gas diffusion electrodes have recently been used industrially for the production of caustic soda in the existing chloralkali electrolysis process (oxygen-consuming electrodes).
  • the efficiency of the chloralkali electrolysis process could be increased by 30-40% unlike conventional electrodes.
  • the method of catalyst embedding with PTFE is known from a variety of publications and patents.
  • the mentioned wet process 1 can have the following disadvantages, apart from the fact that literature-known examples of gas diffusion electrodes contain the catalyst only as an additive and consist mainly of bound conductive carbon (for high conversions the catalyst loading should be high):
  • the suspensions or pastes usually applied by spraying or knife application generally have long drying times, which means that continuous production with larger (technically relevant) electrode surfaces is not economically possible. Too fast drying leads to cracking, so-called "mud cracking", within the applied layers, rendering the electrode unusable.
  • the porosity of the applied layer is determined (generated) in the wet-chemical method almost exclusively by the evaporation of the solvent.
  • This process is highly solvent or boiling point dependent and can lead to a high rejection rate of the electrodes thus produced since evaporation can not be ensured uniformly over the entire area.
  • Another central disadvantage is the use of surface-active substances (surfactants) or thickeners, to name plasticizing, which are used to stabilize the particle suspensions, since they can not be removed without residue through the corresponding drying phases or the thermal crosslinking process.
  • Nafion® perfluorosulfonic acid, PFSA
  • PFSA perfluorosulfonic acid
  • Nafion® itself is a hydrophilic ionomer that contains strongly acidic R-HSO 3 groups, which in some catalysts can lead to undesirable acid corrosion or partial dissolution of the metal.
  • Nafion® bonded layers have a much lower porosity than PTFE bonded layers.
  • Nafion® is not suitable for the formation of hydrophobic channels, which are advantageous for gas transport within a gas diffusion electrode due to the hydrophilic properties.
  • Applicable electrodes comprising Nafion® should therefore consist of several layers in order to realize the essential properties of a GDE. Multi-layer coating processes, however, are less attractive from an economic point of view. Nafion®-based compounds can also lead to the undesirable formation of hydrogen.
  • the dry process 3. is based on a roll calendering process, for example of PTFE / catalyst powder.
  • the appropriate technique is on the EP 0297377 A2 according to the Mn 2 O 3 -based electrodes were made for batteries.
  • DE 3710168A1 For the first time, attention is drawn to the use of the drying process with regard to the preparation of metallic electrocatalyst electrodes.
  • the technique has also been used in patents for producing silver-based (silver (I) or silver (II) oxide) gas diffusion electrodes (oxygen-consuming electrodes).
  • EP 2444526 A2 or in DE 10 2005 023615 A1 mixtures which have a binder content of 0.5-7%.
  • the carriers used were Ag or nickel nets with a wire diameter of 0.1-0.3 mm and a mesh width of 0.2-1.2 mm.
  • the task of the powder takes place directly on the net before it is fed to the roll calender.
  • the DE 10148599 A1 or EP 0115845 B1 describe a similar process in which the powder mixture is first made into a fur or Film is extruded, which is pressed in a further step on the net.
  • the EP 2410079 A2 describes the one-step process for preparing a silver-based oxygen-consuming electrode with the addition of metal oxide additives such as TiO 2 , Fe 3 O 4 , Fe 2 O 3 , NiO 2 , Y 2 O 3 , Mn 2 O 3 , Mn 5 O 8 , WO 3 , CeO 2 and spinels such as CoAl 2 O 4 , Co (AlCr) 2 O 4 and inverse spinels such as (Co, Ni, Zn) 2 (Ti, Al) O 4 , perovskites such as LaNiO 3 , ZnFe 2 O 4 .
  • metal oxide additives such as TiO 2 , Fe 3 O 4 , Fe 2 O 3 , NiO 2 , Y 2 O 3 , Mn 2 O 3 , Mn 5 O 8 , WO 3 , CeO 2 and spinels such as CoAl 2 O 4 , Co (AlCr) 2 O 4 and inverse spinels such as (Co, Ni, Zn)
  • catalysts which can alternatively be used for oxygen-consuming electrodes: noble metals, eg Pt, Rh, Ir, Re, Pd, noble metal alloys, eg Pt-Ru, compounds containing noble metals, eg noble metal-containing sulfides and oxides, and Chevrel phases, eg MO 4 Ru 2 Se 8 or MO 4 Ru 2 S 8 , which may also contain Pt, Rh, Re, Pd etc.
  • noble metals eg Pt, Rh, Ir, Re, Pd
  • noble metal alloys eg Pt-Ru
  • Chevrel phases eg MO 4 Ru 2 Se 8 or MO 4 Ru 2 S 8 , which may also contain Pt, Rh, Re, Pd etc.
  • the DE 101 30 441 A1 discloses a biporous pore system in a gas diffusion electrode, but not a two-layered construction. For such a single-layer structure, a flood of the electrode was observed in our own preliminary experiments. A single-layer structure can also be used, for example DE 10 2010 031 571 A1 be removed. According to the DE 101 30 441 A1 a metallic scaffold is rolled into a catalyst film made there.
  • the US 2013/0280625 A1 discloses a two-layered structure of a gas diffusion electrode which, however, does not disclose hydrophobic pores but only pores in the diffusion layer as a hydrophilic layer. Therein a sacrificial material is necessarily used, which is required for the formation of pores. However, our own preliminary tests have shown that this is not expedient.
  • cathodes for carbon dioxide electrolysis in which carbon dioxide can be effectively converted to hydrocarbons. Furthermore, it is an object of the invention to provide a catalyst concept that not based on in-situ Cu deposition, but provides a Cu gas diffusion electrode that can be processed into an electrode. Furthermore, the development of long-term stable selective electrocatalysts and their embedding in electrically contactable gas diffusion electrodes is an object of the present invention.
  • the present invention relates to a gas diffusion electrode, comprising a, preferably copper-containing, carrier, preferably in the form of a sheet, and a first layer comprising at least copper and optionally at least one binder, wherein the first layer hydrophilic and hydrophobic pores and / or channels comprising, further comprising a second layer comprising copper and at least one binder, wherein the second layer is on the carrier and the first layer on the second layer, wherein the content of binder in the first layer is smaller than in the second layer, wherein the second layer 3 to 30% by weight of binder, preferably 10 to 30% by weight of binder, more preferably 10 to 20% by weight of binder, based on the second layer, and the first layer 0 to 10% by weight of binder, more preferably 0.1 to 10% by weight of binder, even more preferably 1 to 10% by weight of binder, particularly preferably 1 to 7% by weight of binder, particularly preferably 3 to 7% by weight of binder, based on the first layer.
  • the present invention relates to an electrolytic cell comprising the gas diffusion electrode according to the invention.
  • hydrophobic is understood as meaning water-repellent. Hydrophobic pores and / or channels according to the invention are therefore those which repel water. In particular, hydrophobic properties are associated according to the invention with substances or molecules with nonpolar groups.
  • hydrophilic is understood as the ability to interact with water and other polar substances.
  • the present invention relates to a gas diffusion electrode, comprising a, preferably copper-containing, carrier, preferably in the form of a sheet, and a first layer comprising at least copper and at least one binder, the (first) layer comprising hydrophilic and hydrophobic pores and / or channels, further comprising a second layer comprising copper and at least one binder, the second layer being on the support and the first layer on the second layer, wherein the content of binder in the first layer is smaller than in the second layer, wherein the second layer 3 - 30 wt.% Binder, preferably 10 - 30 wt.% Binder, more preferably 10 - 20 % By weight binder, based on the second layer, and the first layer 0-10% by weight of binder, more preferably 0.1-10% by weight of binder, even more preferably 1-10% by weight of binder, particularly preferably 1% 7% by weight of binder, particularly preferably 3-7% by weight of binder, based on the first layer.
  • the second layer may comprise hydrophilic and / or hydrophobic pores and / or channels.
  • gas diffusion electrode comprising a, preferably copper-containing, carrier, preferably in the form of a sheet, and a first layer comprising at least copper and at least one binder, the layer comprising hydrophilic and hydrophobic pores and / or channels.
  • FIG. 1 illustrates the relationships between hydrophilic and hydrophobic regions of a GDE, which can achieve a good three-phase relationship liquid, solid, gaseous.
  • hydrophobic channels or regions 1 and hydrophilic channels or regions 2 are found in the electrode on the electrolyte side, with catalyst sites 3 having low activity in the hydrophilic regions.
  • inactive catalyst centers 5 are located on the gas side.
  • Particularly active catalyst centers 4 are liquid, solid, gaseous in the three-phase region.
  • An ideal GDE thus has a maximum penetration of the bulk material with hydrophilic and hydrophobic channels in order to obtain as many as possible three-phase areas for active catalyst centers.
  • the first layer comprises hydrophilic and hydrophobic pores and / or channels.
  • the support here is not particularly limited insofar as it is suitable for a gas diffusion electrode and is preferably copper-containing.
  • parallel wires can form a carrier in extreme cases.
  • the support is a sheet, more preferably a mesh, most preferably a copper mesh.
  • the support may also be suitably adjusted with regard to the electrical conductivity of the first layer.
  • the use of copper in the carrier can provide suitable conductivity and reduce the risk of introducing unwanted foreign metals.
  • the carrier is therefore made of copper.
  • a preferred copper-containing carrier is, according to certain embodiments, a copper mesh with a mesh size w of 0.3 mm ⁇ w ⁇ 2.0 mm, preferably 0.5 mm ⁇ w ⁇ 1.4 mm and a wire diameter x of 0.05 mm ⁇ x ⁇ 0.5 mm, preferably 0.1 mm ⁇ x ⁇ 0 , 25 mm.
  • the fact that the first layer comprises copper also ensures a high electrical conductivity of the catalyst and, in particular in conjunction with a copper network, a homogeneous potential distribution over the entire electrode area (potential-dependent product selectivity).
  • a preferably copper-containing mesh preferably the copper mesh used as the backing, has a mesh size of the backing between 0.3 and 2.0 mm, preferably between 0.5-1.4 mm, to a good To achieve conductivity and stability.
  • the binder comprises a polymer, for example a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE.
  • a polymer for example a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE.
  • PTFE particles with a particle diameter of between 5 and 95 ⁇ m, preferably between 8 and 70 ⁇ m, are used to produce the first layer.
  • Suitable PTFE powders include, for example, Dyneon® TF 9205 and Dyneon TF 1750.
  • Suitable binder particles, for example, PTFE particles may for example be approximately spherical, for example spherical, and may be prepared, for example, by emulsion polymerization.
  • the binder particles are free of surfactants.
  • the particle size can be determined, for example, in accordance with ISO 13321 or D4894-98a and can correspond, for example, to the manufacturer's instructions (eg TF 9205: average particle size 8 ⁇ m according to ISO 13321, TF 1750: average particle size 25 ⁇ m according to ASTM D4894-98a).
  • the first layer comprises at least copper, which may be present for example in the form of metallic copper and / or copper oxide and which acts as a catalyst center.
  • the first layer contains metallic copper in the oxidation state 0.
  • the first layer contains copper oxide, in particular Cu 2 O.
  • the oxide can contribute to stabilizing the oxidation states +1 of the copper and thus to maintain the selectivity for ethylene in the long-term stable. Under electrolysis conditions it can be reduced to copper.
  • the first layer comprises at least 40 at.% (Atomic percent), preferably at least 50 at.%, More preferably at least 60 at.% Copper, based on the layer.
  • Atomic percent preferably at least 50 at.%
  • More preferably at least 60 at.% Copper based on the layer.
  • the copper for producing the gas diffusion electrode according to the invention is provided as particles, which are further defined below.
  • the first layer may also contain other promoters which, in cooperation with the copper, improve the catalytic activity of the GDE.
  • the first layer contains at least one metal oxide selected from ZrO 2 , Al 2 O 3 , CeO 2 , Ce 2 O 3 , ZnO 2 , and MgO; and / or at least one copper-rich intermetallic phase, preferably at least one Cu-rich phase, which is selected from the group of the binary systems Cu-Al, Cu-Zr, Cu-Y, Cu-Hf, CuCe, Cu-Mg and the ternary Systems Cu-Y-Al, Cu-Hf-Al, Cu-Zr-Al, Cu-Al-Mg, Cu-Al-Ce with Cu contents> 60 at%; and / or copper-containing perovskites and / or defect perovskites and / or La 1.85 Sr 0.15 CuO 3.930 cl 0.053 and / or (La, Sr) 2 CuO 4 ,
  • Preferred promoters here are the metal oxides.
  • the metal oxide employed is, according to certain embodiments, water-insoluble so that aqueous electrolytes can be used in electrolysis using the gas diffusion electrode of the invention. It can thereby be ensured that the redox potential of the metal oxide is less than that of the ethylene development, that ethylene can be prepared from CO 2 by means of the GDE according to the invention.
  • the oxides should not be reduced in a carbon dioxide reduction. For example, nickel and iron are unsuitable because hydrogen is formed here.
  • the metal oxides are preferably not inert, but should preferably represent hydrophilic reaction centers that can serve for the provision of protons.
  • the promoters in particular the metal oxide, can in this case promote the function and production of long-term stable electrocatalysts by stabilizing catalytically active Cu nanostructures.
  • the structural promoters can in this case reduce the high surface mobilities of the Cu nanostructures and thus their sintering tendency.
  • the concept originates from heterogeneous catalysis and is successfully used within high-temperature processes.
  • the catalyst has the following inventive features: In contrast to the known and technically used heterogeneous catalysts Cu / Al 2 O 3 , Cu / ZrO 2 , Cu / MgO / Al 2 O 3 are due to the electrochemical reduction of CO 2 the required electrical conductivity according to certain embodiments preferably only very copper-rich catalysts with a mole fraction> 60 At.% Cu used.
  • gas diffusion electrodes according to the invention to metal oxide copper catalyst structures which are produced as follows.
  • the corresponding precursors can be precipitated by co-dosing a metal salt solution and a basic carbonate solution pH controlled.
  • a special feature of these materials is the presence of very fine 4-10 nm sized copper crystallites that are structurally stabilized by the presence of the oxide.
  • the metal oxide can lead to better distribution of the catalyst metal due to its high specific surface; highly dispersed metal centers can be stabilized by the metal oxide; the CO 2 chemisorption can be improved by the metal oxide; Copper oxides can be stabilized.
  • the generated oxide precursors can also be subsequently reduced directly in an H 2 / Ar gas stream, whereby only the Cu 2 O or CuO is reduced to Cu and the oxide promoter is retained.
  • the activation step can also be carried out electrochemically in retrospect.
  • partial oxide precursors and activated precursors may also be mixed.
  • 0-10 wt.% Copper powder can be mixed in similar particle size.
  • the finished calendered electrode is subjected to a subsequent calcining / thermal treatment before the electrochemical activation is carried out.
  • Cu-rich intermetallic phases such as Cu 5 Zr, Cu 10 Zr 7 , Cu 51 Zr 14 , which can be prepared from the melt. Corresponding ingots can be subsequently ground and completely or partially calcined in the O 2 / argon gas stream and converted into the oxide form.
  • Copper-rich phases are for example off E. Kneller, Y. Khan, U. Gorres, The Alloy System Copper-Zirconium, Part I. Phase Diagram and Structural Relations, Zeitschrift für Metallischen 77 (1), pp. 43-48, 1986 for Cu-Zr phases, from Braunovic, M .; Konchits, VV; Myshkin, NK: Electrical contacts, fundamentals, applicationsand technology; CRC Press 2007 for Cu-Al phases, out Petzoldt, F .; Miner, JP; Schürer, R .; Schneider, 2013, 67 Metal, 504-507 (see eg Table 2) for Cu-Al phases, from Landolt-Börnstein - Group IV Physical Chemistry Volume 5d, 1994, pp.
  • the proportion of copper is preferably greater than 40 at.%, More preferably greater than 50 at.%, Particularly preferably greater than 60 at.%.
  • the intermetallic phases also contain non-metal elements such as oxygen, nitrogen, sulfur, selenium and / or phosphorus, that is, for example, oxides, sulfides, selenides, nirides and / or phosphides are included. According to certain embodiments, the intermetallic phases are partially oxidized.
  • mixtures of these materials can be used for electrode preparation or, if necessary, subsequent calcination or activation steps are carried out.
  • the catalyst particles comprising or consisting of copper, for example copper particles, which are used to produce the GDE according to the invention have a uniform particle size between 5 and 80 .mu.m, preferably 10 to 50 .mu.m, more preferably between 30 and 50 .mu.m. Furthermore, according to certain embodiments, the catalyst particles have a high purity without foreign metal traces. By suitable structuring, if appropriate with the aid of the promoters, high selectivity and long-term stability can be achieved.
  • the promoters for example the metal oxides, may have an appropriate particle size in the production.
  • Cu powder aggregates having a particle diameter of 50 to 600 ⁇ m, preferably 100 to 450 ⁇ m, preferably 100-200 ⁇ m, may be added.
  • the particle diameter of these aggregates, according to certain embodiments, is 1 / 3-1 / 10 of the total layer thickness of the layer.
  • the addition may also be an inert material such as a metal oxide. As a result, an improved formation of pores or channels can be achieved.
  • a gas diffusion electrode according to the invention can be produced in particular by the production process according to the invention, as described below.
  • the first layer comprises less than 5 wt.%, More preferably less than 1 wt.%, And even more preferably no carbon- and / or carbon black-based, for example, conductive, filler with respect to the layer.
  • activated carbons Leitru type (such as volcano XC72), Acetylenblack, or other coals point. According to the invention, however, it has been found that even traces of carbon and / or soot can markedly reduce the selectivity of the catalyst to hydrocarbons and favor the undesired formation of hydrogen.
  • the first layer contains no surfactants.
  • the first and / or second layers do not contain sacrificial material, e.g. a sacrificial material having a release temperature of approximately less than 275 ° C, e.g. of less than 300 ° C or less than 350 ° C, in particular no pore-forming agent, which may usually remain at least partially in the electrode when electrodes are produced using such a material.
  • the content or proportion of binder for example PTFE, is 0-10% by weight, more preferably 0.1-10% by weight, even more preferably 1-10% by weight, particularly preferably 1%. 7 wt.%, Particularly preferably 3-7 wt.%, Based on the first layer.
  • the GDE according to the invention further comprises a second layer comprising copper and at least one binder, wherein the second layer is on the carrier and the first layer is on the second layer, wherein the content of binder in the first layer is smaller than in the second layer, wherein the second layer comprises 3 to 30% by weight of binder, preferably 10 to 30% by weight of binder, more preferably 10 to 20% by weight of binder, based on the second layer.
  • the second layer may comprise coarser Cu or inert material particles, for example with particle diameters of 50 to 700 ⁇ m, preferably 100-450 ⁇ m, in order to provide a suitable channel or pore structure.
  • the second layer comprises 3-30% by weight of binder, preferably 10-30% by weight of binder, more preferably 10-20% by weight of binder, preferably> 10% by weight of binder, more preferably> 10% by weight and up to 20 %
  • binder based on the second layer
  • the first layer comprises 0-10% by weight of binder, for example 0.1-10% by weight of binder, preferably 1-10% by weight of binder, more preferably 1-7% by weight .%, Still more preferably 3-7 wt.% Binder, based on the first layer on.
  • the binder may in this case be the same as in the first layer, for example PTFE.
  • the particles for producing the second layer may be the same as or different from those of the first.
  • the second layer is in this case a metal particle layer (MPL), which lies below the catalyst layer (CL).
  • MPL metal particle layer
  • CL catalyst layer
  • strongly hydrophobic areas in the MPL can be created and a catalyst layer with hydrophilic properties can be generated. Due to the highly hydrophobic nature of the MPL, undesired penetration of the electrolyte into the gas transport channels, ie flooding thereof, can also be prevented.
  • the second layer makes contact with the CO 2 and should therefore also be hydrophobic.
  • the second layer partially penetrates the first layer. This can e.g. can be achieved by the method according to the invention and allows a good transition between the layers with respect to the diffusion.
  • the GDE according to the invention may also have further layers, for example on the first layer and / or on the other side of the support.
  • a mixture for an MPL based on a highly conductive Cu mixture of dendritic Cu with particle sizes between 5 and 100 ⁇ m, preferably less than 50 ⁇ m, may be used and coarser Cu or inert material particles having particle sizes of 100-450 .mu.m, preferably 100-200 .mu.m, with a PTFE content of 3-30 wt.% Preferably 20 wt.%,
  • Corresponding dendritic copper may also be present in the first layer.
  • a further Aufsieben the catalyst / PTFE mixture (CL) for example, with a PTFE content of 0.1-10 wt.%, And a smoothing or stripping, for example, over a 1 mm thick frame done, so that a total layer thickness (Hf) of 1 mm can be obtained.
  • the MPL can provide better mechanical stability, further reduction of electrolyte permeation and better conductivity, especially when using nets as supports.
  • a stepwise production of the GDE by each sifting and rolling of each individual layer can lead to a lower adhesion between the layers and is therefore less preferred.
  • the preparation of the first and second mixtures or of the first mixture here is not particularly limited and can be carried out in a suitable manner, for example by stirring, dispersing, etc.
  • the first mixture can also comprise 0% by weight of binder, ie no binder, since, during rolling, binder from the second mixture can diffuse into the first layer forming from the first mixture and thus also the first layer Binder content of, for example, at least 0.1% by weight, for example 0.5% by weight, as prepared in preliminary experiments.
  • the first blend when applying 2 or more blends, contains binders.
  • the binder comprises a polymer, for example a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE.
  • a polymer for example a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE.
  • PTFE particles with a particle diameter of between 5 and 95 ⁇ m, preferably between 8 and 70 ⁇ m, are used to produce the first layer.
  • Suitable PTFE powders include, for example, Dyneon® TF 9205 and Dyneon TF 1750.
  • the copper for the preparation of the mixture in the form of particles or catalyst particles for example, dendritic copper, which have a uniform particle size between 5 and 80 .mu.m, preferably 10 to 50 .mu.m, more preferably between 30 and 50 microns ,
  • the catalyst particles have a high purity without foreign metal traces.
  • the pores and / or channels, ie the hydrophobic and hydrophilic pores and / or channels, of the GDE can be adjusted in a targeted manner the passage of gas and / or electrolyte and thus for the catalytic reaction.
  • the first and / or second mixture contains no sacrificial material, e.g. a sacrificial material having a release temperature of approximately less than 275 ° C, e.g. of less than 300 ° C or less than 350 ° C, in particular no pore-forming agent, which may usually remain at least partially in the electrode when electrodes are produced using such a material.
  • a sacrificial material e.g. a sacrificial material having a release temperature of approximately less than 275 ° C, e.g. of less than 300 ° C or less than 350 ° C, in particular no pore-forming agent, which may usually remain at least partially in the electrode when electrodes are produced using such a material.
  • the first and / or second mixtures are not pasty, e.g. in the form of inks or pastes, but in the form of powder mixtures.
  • first, second and further mixture (s) is not particularly limited and can be done, for example, by sprinkling, sifting, knife coating, etc.
  • the rolling is not particularly limited and can be done appropriately. Rolling of the mixture or mass (particles) into the structure of the carrier, for example a network structure, is expressly desired according to certain embodiments in order to ensure a high mechanical stability of the electrode.
  • the mixtures for the layers be applied one at a time to the backing and then rolled all together to achieve better adhesion between the layers. This can cause the layers penetrate at least partially, for example in a thickness of 1 - 20 microns.
  • a binder content in the second mixture is from 10-30% by weight, preferably 10-20% by weight, based on the second mixture, and a proportion of binder in the first mixture from 0-10% by weight, preferably 0.1-10% by weight, more preferably 1-10% by weight, even more preferably 1-7% by weight, even more preferably 3-7% by weight proved to be suitable.
  • a binder for example PTFE, content of 3-30% by weight, preferably 3-20% by weight, more preferably 3-10% by weight, even more preferably 3-7, has proven particularly suitable % By weight of the binder, based on the first mixture.
  • the degree of fibrillation of the binder for example PTFE, (structural parameter ⁇ ) correlates directly with the applied shear rate, since the binder, for example a polymer, behaves as a shear-thinning (pseudoplastic) fluid during rolling. After extrusion, the resulting layer has an elastic character due to the fibrillation. This structural change is irreversible, so that this effect can not be subsequently enhanced by further rolling, but the layer is damaged by the elastic behavior upon further action of shear forces. A particularly strong fibrillation can disadvantageously lead to a layer-side coiling of the electrode, so that too high contents of binder should be avoided.
  • the water content during rolling for example, corresponds at most to the room humidity.
  • the content of water and solvents during rolling is less than 5% by weight, preferably less than 1% by weight, and for example also 0% by weight.
  • the copper-containing carrier is a copper mesh having a mesh width w of 0.3 mm ⁇ w ⁇ 2.0 mm, preferably 0.5 mm ⁇ w ⁇ 1.4 mm and a wire diameter x of 0.05 mm ⁇ x ⁇ 0.5 mm, preferably 0.1 mm ⁇ x ⁇ 0.25 mm.
  • the preparation of the gas diffusion electrode according to the invention is based on the exclusion of carbon and / or soot-based, for example conductive, fillers.
  • the catalyst itself or dendritic copper (for example, formed by activation of the catalyst) or mixtures of both.
  • the method according to the invention does not contain surface-active substances or thickeners and additives (such as flow improvers) which have been identified as catalyst poisons.
  • the bulk level y of the first mixture on the carrier when applied is in the range of 0.3 mm ⁇ y ⁇ 2.0 mm, preferably 0.5 mm ⁇ y ⁇ 1.0 mm.
  • each layer may have a corresponding bed height y, but the bed heights of all the layers preferably add up to not more than 2.0 mm, preferably not more than 1.5 mm, more preferably not more than 1 mm.
  • the nip roll width H 0 is the height of the support + 40% to 50% of the total height Hf of the mixtures of the different layers, for example the bulk height y of the first mixture, if only it is used.
  • the rolling is performed by a calender.
  • the copper content in the mixture is at least 40 at.%, Preferably at least 50 at.%, More preferably at least 60 at.% Of copper, based on the mixture.
  • the mixture further contains at least one metal oxide which has a lower reduction potential than ethylene evolution, preferably ZrO 2 , Al 2 O 3 , CeO 2 , Ce 2 O 3 , ZnO 2 , MgO; and / or the mixture further at least one copper-rich intermetallic phase, preferably at least one Cu-rich phase selected from the binary systems Cu-Al, Cu-Zr, Cu-Y, Cu-Hf, CuCe, Cu-Mg and / or the ternary Systems Cu-Y-Al, Cu-Hf-Al, Cu-Zr-Al, Cu-Al-Mg, Cu-Al-Ce with Cu contents> 60 At .-%; and / or the mixture at least one metal to form a copper-rich metallic phase, preferably Al, Zr, Y, Hf, Ce, Mg, or at least two metals to form ternary phases, preferably Y-Al, Hf-Al, Zr-Al, Al-Mg,
  • a copper-rich metallic phase preferably Al, Zr, Y, Hf, Ce, Mg, or at least two metals to form ternary phases
  • Y-Al, Hf-Al, Zr-Al, Al-Mg, Al-Ce so that the Cu content is> 60 at.%
  • Y-Al, Hf-Al, Zr-Al, Al-Mg, Al-Ce so that the Cu content is> 60 at.%
  • Y-Al, Hf-Al, Zr-Al, Al-Mg, Al-Ce so that the Cu content is> 60 at.%
  • Such a melt in the mixture takes place before the binder is added. It follows in such a case, therefore, a sequence that first the metal is added and fused with copper, before the mixture of the binder and possibly other substances are added.
  • the method according to the invention can thus be carried out by a calendering process, as shown schematically in FIG. 2 is shown.
  • the catalyst particles 6 and the binder particles 7, for example PTFE particles with the aid of the calender 11 on the support 8, here in the form of a copper network, rolled.
  • the rolling or calendering is carried out at a rolling speed between 0.3 to 3 U / min, preferably 0.5-2 U / min.
  • the flow rate (the GDE in length per time, for example, calendering) Q is in the range of 0.04 to 0.4 m / min, preferably 0.07 to 0.3 m / min.
  • Cu powder aggregates having a particle diameter of 50 to 600 microns, preferably 100 to 450 microns, more preferably 100 to 200 microns, especially in the second mixture when applying multiple layers, can be added.
  • the particle diameter of these aggregates is 1 / 3-1 / 10 of the total layer thickness of the layer.
  • the addition may also be an inert material such as a metal oxide. As a result, an improved formation of pores or channels can be achieved.
  • a method for producing a gas diffusion electrode can thus be carried out, for example, as follows:
  • a dry calendering process can be used in which a mixture of a cold-flowing polymer (preferably PTFE) and the respective precalcined catalyst powder, comprising Cu and optionally a promoter, prepared in an intensive mixing device or on a laboratory scale with a knife mill (IKA) becomes.
  • the mixing procedure may be followed by, but not limited to, 30 seconds of grinding / mixing and 15 seconds of pause for a total of 6 minutes, this indication referring, for example, to the knife mill with 50 grams of total loading.
  • the mixed powder reaches a slightly sticky consistency after the mixing process, in which case, for example, a fibrillation of the binder, for example PTFE, takes place.
  • a fibrillation of the binder for example PTFE
  • the mixing time may also vary until this state is reached.
  • the resulting powder mixture is then spread or screened onto a copper mesh with a mesh size of> 0.5 mm and ⁇ 1.0 mm and a wire diameter of 0.1-0.25 mm in a bulk thickness of 1 mm.
  • the applied powder mixture is then removed, for example with a doctor blade. This process can be repeated several times until a uniform layer is obtained.
  • the powder mixture can be granulated during or after the mixing operation to obtain a pourable material, for example with an agglomerate diameter of 0.05 to 0.2 mm.
  • the back of the Cu mesh can be sealed with a film that is not further limited.
  • the prepared layer is compacted by means of a two-roller rolling device (calender).
  • the rolling process itself is characterized in that a reservoir of material forms in front of the roll.
  • the speed of rotation of the roller is between 0.5-2 rpm and the gap width has been adjusted to the height of the carrier + 40% to 50% of the height Hf of the powder, or corresponds to almost the thickness of the net + 0.1-0, 2mm delivery.
  • the calender can also be heated. Preference is given to temperatures in the range from 20 to 200 ° C., preferably from 20 to 50 ° C.
  • the catalyst itself can be processed before application in the calcined state, for example as a metal oxide precursor, or even in the reduced state. Mixtures of both forms are possible. This also applies to the case of the described intermetallic phases or alloys, so that they can also be used in the oxide form or in the metallic state. Furthermore, it is not excluded to subsequently calcine the calendered electrode, for example for 5 to 15 minutes at 300-360 ° C.
  • the gas diffusion electrode according to the invention it is advantageous, in particular in the case of hydrocarbon-selective copper catalyst electrodes, for better contacting of nanoscale materials, while maintaining a high porosity, to apply a copper-PTFE base layer as a second layer.
  • the base layer can be characterized by a very high conductivity, for example 7 mOhm / cm or more, and preferably has a high porosity, for example of 50-70%, and a hydrophobic character.
  • the binder content, for example PTFE can be selected between 3-30% by weight, for example 10-30% by weight.
  • the copper intermediate layer as a second layer can be catalytically active in the region of the overlap zone to the catalyst layer as the first layer itself, and serves in particular for better planar electrical connection of the electrocatalyst and can improve the CO 2 availability due to the high porosity.
  • the corresponding electrocatalyst / binder (eg PTFE) mixture can be screened out in a first step on the back of the power distribution and calendered.
  • the binder used, especially PTFE should be pretreated beforehand in a knife mill to achieve fiber formation, according to certain embodiments.
  • Suitable PTFE powders for example, Dyneon® TF 9205 and Dyneon® TF 1750 have proven particularly useful.
  • abrasive hard materials in the range between 0-50 wt.% Can be mixed.
  • the following materials are suitable, for example: SiC, B 4 C, Al 2 O 3 (high-grade corundum), SiO 2 (glass breakage), preferably in a grain size of 50-150 ⁇ m.
  • the preparation of the gas diffusion electrode with binder (eg PTFE) based diffusion barrier based on several layers that are not to be considered isolated from each other, but preferably in the border areas as wide as possible overlap zone, for example 1-20 microns.
  • the method of the two-layer structure offers the possibility of dispensing with binder materials as the first layer within the catalyst layer, as a result of which better electrical conductivity can be achieved. It can also be processed very ductile or brittle powder particles. This is not possible in a single-layered structure.
  • mechanically sensitive catalysts can be dispensed with the process step of the knife mill, whereby the catalyst remains unchanged, since a mechanical stress can be avoided by the mixing process.
  • Electrode activation of the obtained electrode may optionally be performed according to certain embodiments, for example by chemical or electrochemical activation, and is not particularly limited.
  • An electrochemical activation procedure can lead to cations of the conductive salt of the electrolyte (eg KHCO 3 , K 2 SO 4 NaHCO 3 , KBr, NaBr) penetrate the hydrophobic GDE channels, creating hydrophilic areas. This effect is particularly advantageous and has not previously been described in the literature.
  • the present invention relates to an electrolytic cell comprising a gas diffusion electrode according to the invention, which is preferably used as a cathode.
  • the gas diffusion electrodes of the invention may be operated especially in plate electrolyzers.
  • the other components of the electrolysis cell such as the anode, optionally one or more membranes, supply line (s) and discharge (s), the voltage source, etc., and other optional devices such as cooling or heating devices are not particularly limited according to the invention, as well not anolyte and / or catholyte used in such an electrolytic cell, the electrolytic cell according to certain embodiments being used on the cathode side to reduce carbon dioxide.
  • the configuration of the anode compartment and the cathode compartment is also not particularly limited.
  • An electrochemical reduction of, for example, CO 2 takes place in an electrolysis cell, which usually consists of an anode and a cathode compartment.
  • an electrolysis cell which usually consists of an anode and a cathode compartment.
  • FIGS. 4 to 6 Examples of a possible cell arrangement are shown.
  • a gas diffusion electrode according to the invention can be used, for example as a cathode.
  • Exemplary is the cathode compartment II in FIG. 4 designed such that a catholyte is supplied from below and then leaves the cathode space II upwards.
  • the catholyte can also be supplied from above, as for example with falling film electrodes.
  • the anode A which is electrically connected to the cathode K by means of a current source for providing the voltage for the electrolysis, takes place in the anode compartment I, the oxidation of a substance, which is supplied from below, for example with an anolyte, and the anolyte with the product the oxidation then leaves the anode compartment.
  • a reaction gas such as carbon dioxide can be conveyed through the gas diffusion electrode into the cathode compartment II for reduction.
  • a reaction gas such as carbon dioxide
  • FIG. 4 the spaces I and II are separated by a membrane M.
  • the PEM (proton or ion exchange membrane) structure of the FIG. 5 the gas diffusion electrode K and a porous anode A directly on the membrane M, whereby the anode compartment I is separated from the cathode compartment II.
  • the construction in FIG. 6 corresponds to a mixed form of the structure FIG. 4 and the structure FIG.
  • FIGS. 4 to 6 are schematic representations.
  • the electrolysis cells off FIGS. 4 to 6 can also be combined to mixed variants.
  • the anode compartment may be in the form of a PEM half cell, as in FIG FIG. 5
  • the cathode compartment consists of a half-cell containing a certain volume of electrolyte between the membrane and the electrode, as shown in FIG FIG. 4 shown.
  • the distance between the electrode and the membrane is very small or 0, if the membrane is made porous and includes a supply of the electrolyte.
  • the membrane can also be configured as a multilayer, so that separate supply of anolyte or catholyte is made possible.
  • the membrane may be an ion-conducting membrane, or a separator, which causes only a mechanical separation and is permeable to cations and anions.
  • the gas diffusion electrode By using the gas diffusion electrode according to the invention, it is possible to construct a three-phase electrode.
  • a gas can be fed from the rear to the electrically active front side of the electrode in order to carry out an electrochemical reaction there.
  • the gas diffusion electrode may only be trailing behind, ie, a gas such as CO 2 is conducted past the rear of the gas diffusion electrode relative to the electrolyte, which gas may then pass through the pores of the gas diffusion electrode and the product may be removed at the rear.
  • the gas flow during the backflow is reversed to the flow of the electrolyte, so that any squeezed through liquid can be removed.
  • a gap between the gas diffusion electrode and the membrane as an electrolyte reservoir is advantageous.
  • a cell variant (a) allows a direct active flow through the GDE with a gas such as CO 2 .
  • the resulting products are removed from the electrolysis cell through the catholyte outlet and separated from the liquid electrolyte in a subsequent phase separator.
  • Disadvantage of this method is the increased mechanical load of the GDE and a partial or complete squeezing out of the electrolyte from the pores.
  • As also disadvantageous proved the increased gas volume in the electrolyte space and a displacement of the electrolyte.
  • a high excess of CO 2 is required for the mode of operation.
  • only gas diffusion electrodes with a porosity> 70% and an increased mechanical stability are suitable for this mode of operation.
  • the second cell variant describes a mode of operation in which the CO 2 flows in the rear region of the GDE through a matched gas pressure.
  • the gas pressure should be chosen so that it is equal to the hydrostatic pressure of the electrolyte in the cell, so that no electrolyte is pushed through.
  • An essential advantage of the cell variant is a higher conversion of the reaction gas used, for example CO 2 , in contrast to the flow-through variant.
  • a film may be applied to prevent the electrolyte from passing to the gas.
  • the film may in this case be suitably provided and is, for example, hydrophobic.
  • the electrolytic cell has a membrane which separates the cathode space and the anode space of the electrolytic cell to prevent mixing of the electrolytes.
  • the membrane is not particularly limited here, as long as it separates the cathode space and the anode space. In particular, it essentially prevents a transfer of the gases produced at the cathode and / or anode to the anode or cathode space.
  • a preferred membrane is one Ion exchange membrane, for example based on polymers.
  • a preferred material of an ion exchange membrane is a sulfonated tetrafluoroethylene polymer such as Nafion®, for example Nafion® 115.
  • ceramic membranes can also be used, for example those described in US Pat EP 1685892 A1 mentioned and / or loaded with zirconium oxide polymers, for example polysulfones.
  • the material of the anode is not particularly limited and depends primarily on the desired reaction.
  • exemplary anode materials include platinum or platinum alloys, palladium or palladium alloys, and glassy carbon.
  • Further anode materials are also conductive oxides such as doped or undoped TiO 2 , indium-tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), iridium oxide, etc.
  • these catalytically active compounds can also be superficially applied only in thin-film technology, for example on a titanium support.
  • the anode compartment can be designed as a proton exchange membrane (PEM) half cell, while the cathode compartment consists of a half cell, which contains a certain volume of electrolyte between the membrane and the electrode.
  • PEM proton exchange membrane
  • the cathode compartment consists of a half cell, which contains a certain volume of electrolyte between the membrane and the electrode.
  • the distance between the electrode and the membrane is very small or 0, if the membrane is porous and contains a supply of the electrolyte.
  • the membrane can also be configured as a multilayer, so that separate supply of anolyte or catholyte is made possible. Separation effects are achieved in aqueous electrolytes, for example by the hydrophobicity of intermediate layers. Nevertheless, conductivity can be ensured if conductive groups are integrated in such separation layers.
  • the membrane may be an ion-conducting membrane, or a separator which causes only a mechanical separation.
  • a reaction gas for example CO 2
  • different gas distribution chambers may be provided, of which two exemplary in FIGS. 7 and 8 are shown. These can be provided in order to further increase the residence time of a reaction gas such as CO 2 and the associated conversion.
  • the gas distributors in particular in the case of a gas diffusion electrode which flows behind, can contribute to an increased mass transfer over the entire electrode surface.
  • an electrolysis plant comprising an electrode according to the invention or an electrolysis cell according to the invention, and the use of the gas diffusion electrode according to the invention in an electrolysis cell or an electrolysis plant.
  • the other components of the electrolysis system are not limited and can be suitably provided.
  • Comparative Example 1 a multilayer gas diffusion electrode according to the specifications of R. Cook (J.Electrochem.Soc., 1990, 137, 2 ) manufactured.
  • the production of the hydrophobic gas transport layer was carried out as published: 2.5 g of Volcano XC 72 and 2.8 g of Teflon 30B (Dupont) were dispersed in 25 ml of water and applied to a tight mesh (100 mesh). The coated layer was dried in air and pressed at 344 bar for 2 min. A total of three layers were produced using this procedure. This was followed by the pressing on of three further catalyst-containing layers with the following mixing ratio: 2.5 g of volcano XC 72, 2.61 g of Cu (OAc) 2 .H 2 O, 0.83 g of Teflon 30B dispersed in 25 ml of H 2 O. After each applied layer was dried in air and then pressed with 69 bar. The finished GDE was activated at 324 ° C in a 10 vol .-% H 2 / Ar gas mixture for 3-4h and last pressed again with 69 bar for 30 sec.
  • test setup was used which was essentially that of the above-described electrolysis plant of FIG. 6 corresponds to flow cells for electrolysis.
  • the respective gas diffusion electrode (GDE) having an active area of 3.3 cm 2 was used as the cathode, the gas feed rate of carbon dioxide on the cathode side was 50 ml / min, and the flow of the electrolyte was 130 ml / min on both sides.
  • the anode was iridium oxide on a titanium support with an active area of 10 cm 2 .
  • the catholyte was a 1M KHCO 3 solution with KHCO 3 in a 1M concentration, and the anolyte was 1M KHCO 3 , each in deionized water (18 M ⁇ ), each in an amount of 100 mL, and the temperature was 25 ° C.
  • 0.5MK 2 SO 4 was also tried as catholyte and 2.5M KOH as anolyte.
  • Comparative Example 2 is otherwise Comparative Example 1, unless otherwise stated.
  • the use of the higher-boiling dispersant prevented cracking, but again no ethylene selectivity was observed.
  • the solvent was removed in a drying oven at 270 ° C with a ramp of 10K / min and 1h isotherm.
  • a layer corresponding to the first layer was applied (thickness 100 .mu.m) and again the solvent was removed as above and allowed to air dry for 24 h.
  • the electrode was then calcined in the oven at 350 ° C with a ramp of 10K / min and an isotherm for 2h and pressed at 5 bar and 160 ° C for 2 min.
  • the substrate used in Comparative Example 3.1 was a commercially available carbon cloth for gas diffusion electrodes (Elat® LT1400W, NuVant) in the form of a microporous layer.
  • a Nafion® D521 dispersion was applied as an electrocatalyst, which was prepared as follows.
  • the mixture was then calcined in the oven at 250 ° C with a slope of 10K / min in an atmosphere of 10 vol .-% H 2 in argon, the calcination was continued for a total of 240 min at the isotherm.
  • the electrode obtained in this way was subsequently characterized in terms of its electrochemical properties with a test setup which, with the exception of the GDE, corresponded to that of Comparative Example 1.
  • the copper catalyst was provided by reduction of Cu (OAc) 2 .H 2 O.
  • Comparative Example 3.1 the results shown in Table 3 were achieved by varying the support (Cu mesh with a mesh size of 0.25 and a wire diameter of 0.14 mm) and the applied mixture.
  • Comparative Example 3.2 PTFE was also used instead of Nafion®.
  • Table 3 Quantities and results in Comparative Examples 3.2 - 3.5 carrier Binder carbon [wt.%] Nafion® [wt.%] Precursor of the catalyst Amount of catalyst [mg / cm 2 ] Catalyst [wt.%] Max.
  • a multilayer gas diffusion electrode was prepared as in Comparative Example 3.1, using as catalyst a Cu / ZrO 2 catalyst obtained from Cu 8 Zr 3 .
  • the GDE was also reduced prior to measurement
  • 4.3 refers to an electrochemically activated electrode
  • 4.4 refers to a hydrogen activated electrode.
  • Table 4 The amounts and results obtained in Comparative Examples 4.1-4.4 are shown in Table 4, and for Comparative Example 4.3 the results are also given in Figures 10 and 11 are shown. In Fig. 10 Here, a series of currents is shown, and in Fig. 11 a measurement at constant current.
  • coal-based GDE in Comparative Examples 1 to 4 showed increased Faraday efficiencies for hydrogen. It was concluded that carbon in the form of carbon blacks or activated carbon is less suitable for the production of ethylene-selective gas diffusion electrodes.
  • GDE based on 0.5 wt% PTFE was prepared according to the same procedure.
  • the gas diffusion electrodes produced had very poor wettability and, in the case of the 0.5% PTFE content, poor porosities, as determined optically and microscopically.
  • the GDEs contain significant amounts of the surfactant used, which was identified as a catalyst poison in a control experiment.
  • the corresponding catalyst poison Triton X 100 ((p-tert-octylphenoxy) polyethoxyethanol) likewise could not be expelled without leaving a residue at temperatures> 340 ° C., as confirmed by scanning electron microscopy.
  • a corresponding hydrotalcite precursor having the composition Cu 0.6 Al 0.4 (OH) 2 ] (CO 3 ) 0.4 .mH 2 O (unknown water content for the freshly precipitated hydrotalcite) is prepared by co-precipitation.
  • a catalyst powder is prepared by co-precipitating Cu (NO 3 ) 2 .3H 2 O and ZrO (NO 3 ) 2 .xH 2 O according to Reference Example 1 with the respective molar amounts (mol).
  • the mixing procedure follows the procedure: 30 sec. Milling / mixing and 15sec rest for a total of 6 min. This information refers to the knife mill with 50g total load.
  • the mixed powder reaches a slightly sticky consistency after mixing. Depending on the amount of powder or selected polymer or chain length, the mixing time may also vary until this state is reached.
  • the resulting powder mixture is then spread or screened onto a copper mesh with a mesh size of> 0.5 mm and ⁇ 1.0 mm and a wire diameter of 0.1-0.25 mm in a bulk thickness of 1 mm.
  • the back of the Cu mesh can be sealed with a film that is not further limited.
  • the prepared layer is compacted by means of a two-roller rolling device (calender).
  • the rolling process itself is characterized in that a reservoir of material forms in front of the roll.
  • the speed of rotation of the roller is between 0.5 and 2 rpm, and the gap width has been adjusted to the height of the carrier + 40% to 50% of the height Hf of the powder, or nearly equal to the thickness of the net + 0.1-0 , 2mm delivery.
  • the resulting gas diffusion electrode is activated in an electrolytic bath in a 1M KHCO 3 solution for 6 hours at a current density of 15 mA / cm 2 .
  • Dendritic Cu powder (45 g, particle size ⁇ 45 ⁇ m, determined by sieving with a corresponding mesh size (45 ⁇ m)) is mixed with 5 g PTFE in an IKA knife mill according to the procedure described in Comparative Example 6 and processed under the same conditions into a GDE.
  • the described GDE provided a Faraday efficiency of 16% at 170mA / cm 2 after activation, which remained constant over the measurement time of about 90 min.
  • the prepared oxide precursor is ground for 3 minutes in a planetary ball mill (pulverisette) before being used and subsequently sieved (particle size ⁇ 75 ⁇ m).
  • 45 g of the resulting catalyst are mixed with 5 g of PTFE in an IKA knife mill according to the procedure described in Comparative Example 6 and processed under the same conditions to form a GDE.
  • the GDEs of Comparative Examples 6 to 8 can be used in an electrolytic cell as described above or below, for example, as a cathode with which CO 2 can be reduced.
  • Copper powder with a particle diameter of 100-200 ⁇ m and PTFE TF 1750 Dyneon were mixed for 6 minutes in an IKA A10 knife mill (15 seconds grinding, 30 seconds rest).
  • the powder layer was then screened over a 0.5 mm thick template and straightened to form a basecoat. This was followed by extrusion with a 2-roll calender with a roll spacing of 0.5 mm.
  • the result was a highly porous base layer with a porosity> 70%, good mechanical stability and very good conductivity with 5 mOhm / cm. It could be used catalysts with 40 wt.% Cu content.
  • the catalysts have a purity which is above the commercially available materials or quality standards, as in the example. This could be detected by (surface-sensitive) XPS. Also, REM / EDX mapping analyzes also indicated no contamination of the hydrophobic base layer.
  • the anode compartment can be designed as a proton exchange membrane (PEM) half cell, while the cathode compartment consists of a half cell, which contains a certain volume of electrolyte between the membrane and the electrode.
  • PEM proton exchange membrane
  • the cathode compartment consists of a half cell, which contains a certain volume of electrolyte between the membrane and the electrode.
  • the distance between the electrode and the membrane is very small or 0, if the membrane is porous and contains a supply of the electrolyte.
  • the membrane can also be configured as a multilayer, so that separate supply of anolyte or catholyte is made possible. Separation effects are achieved in aqueous electrolytes, for example by the hydrophobicity of intermediate layers. Nevertheless, conductivity can be ensured if conductive groups are integrated in such separation layers.
  • the membrane can be an ion-conducting membrane, or a separator which causes only a mechanical separation.
  • the present invention provides the ability to produce ethylene-selective, dimensionally stable, catalyst powder-based gas diffusion electrodes.
  • This technique provides the basis for the production of electrodes on a larger scale, which can achieve current densities> 170mA / cm 2 depending on the mode of operation. All previously known methods for producing ethylene-selective Cu electrodes are not suitable for scale-up or are not dimensionally stable.
  • gas diffusion electrodes according to the invention can be obtained by suitably adapting a rolling process, in particular a calendering process.
  • the preparation of the gas diffusion electrode according to the invention is based on the exclusion of conductive fillers based on carbon blacks or carbon blacks.
  • a coal substitute here serves the catalyst itself or dendritic copper or mixtures of both.
  • the method according to the invention does not contain surface-active substances or thickeners and additives (such as flow improvers) which have been identified as catalyst poisons.

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EP16741915.9A 2015-08-11 2016-07-19 Präparationstechnik von kohlenwasserstoffselektiven gasdiffusionselektroden basierend auf cu-haltigen-katalysatoren Active EP3307924B1 (de)

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PL16741915T PL3307924T3 (pl) 2015-08-11 2016-07-19 Sposób wytwarzania dyfuzyjnych elektrod gazowych selektywnych wobec węglowodorów bazujących na zawierających Cu katalizatorach

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CN111074294B (zh) * 2019-12-12 2021-12-14 中国科学技术大学 一种铜合金材料电催化二氧化碳制备含碳化合物的方法
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AU2016305184B2 (en) 2019-02-28
AU2016305184A1 (en) 2018-02-01
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PL3307924T3 (pl) 2020-01-31
EP3307924A1 (de) 2018-04-18
DK3307924T3 (da) 2019-09-02
ES2746118T3 (es) 2020-03-04
CN107923052B (zh) 2020-06-19
SA518390888B1 (ar) 2021-10-10
CN107923052A (zh) 2018-04-17
US20180230612A1 (en) 2018-08-16

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