EP3418429A1 - Gasdiffusionselektrode zur reduktion von kohlendioxid - Google Patents

Gasdiffusionselektrode zur reduktion von kohlendioxid Download PDF

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Publication number
EP3418429A1
EP3418429A1 EP17177031.6A EP17177031A EP3418429A1 EP 3418429 A1 EP3418429 A1 EP 3418429A1 EP 17177031 A EP17177031 A EP 17177031A EP 3418429 A1 EP3418429 A1 EP 3418429A1
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Prior art keywords
gas diffusion
diffusion electrode
silver
electrode according
electrocatalyst
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EP17177031.6A
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German (de)
English (en)
French (fr)
Inventor
Andre Rittermeier
Michael Venz
Stefanie Eiden
Thomas Burbach
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Covestro Deutschland AG
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Covestro Deutschland AG
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Priority to EP17177031.6A priority Critical patent/EP3418429A1/de
Priority to PCT/EP2018/066293 priority patent/WO2018234322A1/de
Priority to EP18735210.9A priority patent/EP3642391B1/de
Priority to CN201880041586.2A priority patent/CN110770370B/zh
Priority to US16/623,437 priority patent/US20200208283A1/en
Priority to JP2019570373A priority patent/JP7222933B2/ja
Priority to KR1020197037391A priority patent/KR20200020714A/ko
Publication of EP3418429A1 publication Critical patent/EP3418429A1/de
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes 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
    • C25B11/095Electrodes 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
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/23Carbon monoxide or syngas
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031Porous electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031Porous electrodes
    • C25B11/032Gas diffusion electrodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061Metal or alloy
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081Electrodes 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
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes 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
    • C25B11/093Electrodes 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 noble metal or noble metal oxide and at least one non-noble metal oxide
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054Electrodes comprising electrocatalysts supported on a carrier

Definitions

  • the invention relates to a gas diffusion electrode (GDE) for the reduction of carbon dioxide based on porous silver powder as an electrocatalyst and their use as for the electrochemical reduction of carbon dioxide (CO 2 ) to CO.
  • GDE gas diffusion electrode
  • the invention is based on known per se gas diffusion electrodes, which usually comprise an electrically conductive support and a gas diffusion layer and a catalytically active component and are used in the chlor-alkali electrolysis.
  • the known electrodes are used for cathodic oxygen reduction.
  • Gas diffusion electrodes are electrodes in which the three states of matter - solid, liquid and gaseous - are in contact with each other and the solid, electron-conducting catalyst catalyzes an electrochemical reaction between the liquid and the gaseous phase.
  • the carbon dioxide GDE must fulfill a number of basic requirements in order to be usable in technical electrolysers.
  • the catalyst and all other materials used must be chemically stable.
  • a high degree of mechanical stability is required because the electrodes are installed and operated in electrolyzers of a size of usually more than 2 m 2 surface (technical size). Further properties are: a high electrical conductivity, a small layer thickness, a high internal surface and a high electrochemical activity of the electrocatalyst. Suitable hydrophobic and hydrophilic pores and a corresponding pore structure for the conduction of gas and electrolyte are just as necessary as a tightness, so that gas and liquid space remain separated from each other.
  • the long-term stability and low production costs are further special requirements for a technically usable oxygen-consuming electrode.
  • Another important property is a low potential at high current density as large as possible 4kA / m 2 and a high selectivity to carbon monoxide.
  • different silver morphologies and gold and carbon based catalysts are known for the electrochemical reduction of carbon dioxide to carbon monoxide.
  • Hori et al. describes that a polycrystalline gold catalyst with a current strength of 5mA / cm 2 achieves a selectivity of 87% carbon monoxide.
  • nanoporous silver systems are described. All with a similar performance (selectivity of 90% at a current density of 20 mA / cm 2 ).
  • the preparation of these nanoporous systems is very expensive, difficult to transfer to industrial scale and it is difficult to increase the porosity.
  • Porous silver materials can be generated via a colloidal approach, for example, by crystallizing monodisperse polystyrene particles, the interstices between the particles are filled with silver and then the polystyrene particles are dissolved out. This process is very complex and not suitable for industrial use ( Chem. Mater. 2002, 14, 2199-2208 ). In another process, instead of the colloidal particles, a polymer gel is used as a template ( Chem. Mater. 2001, 13, 1114-1123 ), which is similarly expensive. In addition, all of these processes also require high sintering temperatures of up to 800 ° C in order to represent multistage processes.
  • an AlAg or CuAg alloy is first elaborately prepared to dissolve the copper or aluminum, and high temperatures are required to produce the alloy (Nanoenergy 2016).
  • monoliths i. get very large particles that are not suitable for further processing in a GDE.
  • the object was therefore to provide a gas diffusion electrode and a process for their preparation, with which the carbon dioxide reduction at high current density (> 2kA / m 2 ) and high selectivity (> 50%) takes place.
  • the size of the nanoparticles and thus also the porosity can be controlled by the type of addition, the mixing and the concentration of the starting materials.
  • the primary particles have a diameter less than 100 nm.
  • silver nitrate and trisodium citrate are dissolved in water.
  • a solution consisting of a reducing agent such as NaBH4, KBH4 or formaldehyde dissolved in water is added with stirring.
  • the porous particles are formed in a particle size greater than 1 micron, are then filtered off, washed and dried.
  • porous particles By means of these porous particles to obtain selective GDEn, when these porous particles are mixed with a fluoropolymer according to the present inventive method and then pressed the powder mixture obtained with a support member.
  • the invention relates to a gas diffusion electrode for the reduction of carbon dioxide, wherein the gas diffusion electrode comprises at least one planar, electrically conductive support and an applied on the support gas diffusion layer and applied electrocatalyst, wherein the gas diffusion layer consists of at least a mixture of electrocatalyst and a hydrophobic polymer, and wherein the silver acts as an electrocatalyst, characterized in that the electrocatalyst contains silver in the form of highly porous agglomerated nanoparticles and the nanoparticles have a BET surface area of at least 2 m 2 /.
  • the thickness of the catalytically active coating consisting of PTFE and silver of the gas diffusion electrode is preferably from 20 to 1000 ⁇ m, particularly preferably from 100 to 800 ⁇ m, very particularly preferably from 200 to 600 ⁇ m.
  • the proportion of electrocatalyst is preferably from 80 to 97 wt .-%, particularly preferably from 90 to 95 wt .-% based on the total weight of electrocatalyst and hydrophobic polymer.
  • the proportion of hydrophobic polymer is preferably from 20 to 3 wt .-%, particularly preferably from 10 to 5 wt .-% based on the total weight of electrocatalyst and hydrophobic polymer.
  • the hydrophobic polymer is a fluorine-substituted polymer, more preferably polytetrafluoroethylene (PTFE).
  • a further preferred embodiment of the gas diffusion electrode is characterized in that the electrode has a total loading of catalytically active component in a range from 5 mg / cm 2 to 300 mg / cm 2 , preferably from 10 mg / cm 2 to 250 mg / cm 2 .
  • the gas diffusion electrode which is characterized in that the silver particles are present as an agglomerate of silver nanoparticles with a mean agglomerate diameter (d 50 measured by laser diffraction) in the range of 1 to 100 .mu.m, preferably in the range of 2 to 90 .mu.m.
  • a gas diffusion electrode in which the silver nanoparticles have an average diameter in the range from 50 to 150 nm was also determined by means of scanning electron microscopy with image evaluation.
  • the new gas diffusion electrode preferably comprises a support consisting of a material selected from the group consisting of silver, nickel, coated nickel, e.g. with silver, plastic, nickel-copper alloys or coated nickel-copper alloys, e.g. Silver-plated nickel-copper alloys on which flat textile structures were produced.
  • the electrically conductive carrier may in principle be a net, fleece, foam, woven fabric, braid, expanded metal.
  • the support is preferably made of metal, more preferably nickel, silver or silver-plated nickel.
  • the carrier may be single-layered or multi-layered.
  • a multilayer carrier may be constructed of two or more superposed nets, nonwovens, foams, woven fabrics, braids, expanded metals.
  • the nets, nonwovens, foams, fabrics, braids, expanded metals can be different. They may, for example, be different thicknesses or different porosity or have a different mesh size.
  • Two or more nets, nonwovens, foams, woven fabrics, braids, expanded metals can be connected to one another, for example, by sintering or welding.
  • a net of nickel with a wire diameter of 0.04 to 0.4 mm and a mesh size of 0.2 to 1.2 mm is used.
  • the carrier of the gas diffusion electrode is based on nickel, silver or a combination of nickel and silver.
  • the carrier is in the form of a net, woven fabric, knitted fabric, knitted fabric, fleece, expanded metal or foam, preferably a woven fabric.
  • the different forms of carbon dioxide electrolysis can be distinguished by how the GDE is incorporated and how this establishes the distance between the ion exchange membrane and the GDE.
  • Many cell designs allow a gap between the ion exchange membrane and the GDE, the so-called finite-gap arrangement.
  • the gap can be 1 to 3mm, the gap is traversed by eg KHCO3.
  • the flow can be carried out in an upright arrangement of the electrode from top to bottom (principle of the falling film cell see eg WO 2001 / 057290A2 ) or from bottom to top (gas pocket principle, see eg DE 4,444,114A2 )
  • a particular embodiment of the invention represent plastic-bonded electrodes, wherein the gas diffusion electrode are provided with both hydrophilic and hydrophobic areas. These gas diffusion electrodes are chemically very resistant, especially when PTFE (polytetrafluoroethylene) is used.
  • PTFE polytetrafluoroethylene
  • PTFE catalyst mixtures take place in principle, for example, by using dispersions of water, PTFE and catalyst.
  • emulsifiers are added in particular, and thickeners are preferably used to process the dispersion.
  • thickeners are preferably used to process the dispersion.
  • Alternative to this wet production process is the production by dry mixing of PTFE powder and catalyst powder.
  • the gas diffusion electrodes according to the invention can be prepared as described above, by wet or dispersion and drying process. Particularly preferred is the dry production process.
  • Dispersion methods are chosen mainly for electrodes with polymeric electrolyte - such.
  • the dry process When using the GDE in liquid electrolytes, the dry process provides more suitable GDEn.
  • Dispersion process can be dispensed by strong evaporation of the water and sintering of the PTFE at 340 ° C on a strong mechanical pressing.
  • These electrodes are usually very porous. But on the other hand, if the drying conditions are wrong, cracks can quickly form in the electrode that can penetrate liquid electrolyte. Therefore, for dry electrolyte applications such as the zinc-air battery or the alkaline fuel cell, the dry method has become established.
  • the catalyst is intensively mixed with a polymer component (preferably PTFE).
  • a polymer component preferably PTFE
  • the powder mixture can be formed by pressing, preferably by pressing by means of rolling process, to form a sheet-like structure, which is then applied to the carrier (see, for example, US Pat DE 3,710,168 A2 ; EP 144.002 A2 ).
  • a likewise applicable preferred alternative describes the DE 102005023615 A2 ; In this case, the powder mixture is sprinkled on a support and pressed together with this.
  • the electrode is made of a powder mixture consisting of silver and / or its oxides and PTFE. It is likewise possible to use doped silver and / or its oxides or mixtures of silver and / or its oxides with silver and PTFE.
  • the catalysts and PTFE for example, as in US 6,838,408 described in a dry mixing process and the powder compacted into a coat.
  • the coat is then pressed together with a mechanical support.
  • Both the fur-forming process as well as the compression of fur and carrier can be done for example by a rolling process.
  • the pressing force has an influence on the pore diameter and the porosity of the GDE. Pore diameter and porosity influence the performance of the GDE.
  • the preparation of the GDE invention analogous to the DE 10.148.599A1 be carried out by applying the catalyst-powder mixture directly on a support.
  • the powder mixture is produced in a particularly preferred embodiment by mixing the catalyst powder and the binder and optionally other components.
  • the mixing is preferably done in a mixing device which has fast rotating mixing elements, such as beater knives.
  • the mixing elements rotate preferably at a speed of 10 to 30 m / s or at a speed of 4000 to 8000 U / min.
  • the powder mixture is preferably sieved.
  • the sieving is preferably carried out with a sieve device or the like with nets. equipped, whose mesh size 0.04 to 2 mm.
  • the temperature during the mixing process is preferably 35 to 80 ° C.
  • a coolant e.g. liquid nitrogen or other inert heat-absorbing substances.
  • Another way of controlling the temperature may be that the mixing is interrupted to allow the powder mixture to cool or by selecting suitable mixing units or changing the fill in the mixer.
  • the application of the powder mixture to the electrically conductive carrier takes place, for example, by scattering.
  • the spreading of the powder mixture onto the carrier can e.g. done by a sieve.
  • a frame-shaped template is placed on the carrier, wherein the template is preferably selected so that it just covers the carrier.
  • the template can also be chosen smaller than the surface of the carrier. In this case remains after sprinkling the powder mixture and the pressing with the carrier an uncoated edge of the carrier free of electrochemically active coating.
  • the thickness of the template can be selected according to the amount of powder mixture to be applied to the carrier.
  • the template is filled with the powder mixture. Excess powder can be removed by means of a scraper. Then the template is removed.
  • the powder mixture is pressed in a particularly preferred embodiment with the carrier.
  • the pressing can be done in particular by means of rollers.
  • a pair of rollers is used.
  • the pressing can be done by a ram.
  • the forces during pressing are in particular 0.01 to 7 kN / cm.
  • a GDE according to the invention can basically be constructed as a single layer or as a multilayer.
  • powder mixtures having different compositions and different properties are applied to the carrier in layers.
  • the layers of different powder mixtures are preferably not pressed individually with the carrier, but first applied successively and then pressed together in one step together with the carrier.
  • a layer of a powder mixture can be applied, which has a higher content of the binder, in particular a higher content of PTFE, than the electrochemically active layer.
  • a layer with a high PTFE content of 6 to 100%. can act as a gas diffusion layer.
  • a gas diffusion layer made of PTFE can also be applied.
  • a layer with a high content of PTFE can be applied directly to the support as the lowest layer.
  • Other layers of different composition can be applied for the preparation of the gas diffusion electrode.
  • the desired physical and / or chemical properties can be specifically adjusted. These include u.a. the hydrophobicity or hydrophilicity of the layer, the electrical conductivity, the gas permeability.
  • a gradient of a property can be built up by increasing or decreasing the measure of the property from layer to layer.
  • the thickness of the individual layers of the GDE can be adjusted by the amount of powder mixture applied to the carrier and by the pressing forces during pressing.
  • the amount of the applied powder mixture can be adjusted, for example, by the thickness of the template which is placed on the carrier to spread the powder mixture on the carrier.
  • a coat is produced from the powder mixture.
  • the thickness or density of the coat can not be set independently of one another, since the parameters of the rolls, such as roll diameter, roll spacing, roll material, tensile holding force and peripheral speed, have a decisive influence on these sizes.
  • the pressing force when pressing the powder mixture or layers of different powder mixtures with the carrier takes place e.g. by roll pressing with a line pressing force in the range of 0.01 to 7 kN / cm.
  • the carbon dioxide GDE is preferably connected as a cathode, in particular in an electrolytic cell for the electrolysis of alkali metal chlorides, preferably of sodium chloride or potassium chloride, more preferably of sodium chloride, or of hydrochloric acid.
  • alkali metal chlorides preferably of sodium chloride or potassium chloride, more preferably of sodium chloride, or of hydrochloric acid.
  • the carbon dioxide GDE is particularly preferably used as a cathode in the chlorine electrolysis or 02 electrolysis.
  • Another object of the invention is therefore the use of the new gas diffusion electrode for the electrolysis of carbon dioxide to carbon monoxide, especially in the chloralkali electrolysis,
  • the invention also provides a process for the electrochemical conversion of carbon dioxide to carbon monoxide, characterized in that the carbon dioxide is converted cathodically to carbon monoxide at a new gas diffusion electrode as described above and chlorine or oxygen is simultaneously produced at the anode side.
  • the current density in the reaction is at least 2 kA / m 2, preferably at least 4 kA / m 2 .
  • the invention is also an electrolysis device having a new gas diffusion electrode as a carbon dioxide consuming cathode.
  • the invention furthermore relates to a gas diffusion electrode, characterized in that the gas diffusion electrode has at least one planar electrically conductive carrier element and a gas diffusion layer applied to the carrier element and an electrocatalyst, characterized in that the gas diffusion layer consists of a mixture of silver particles and PTFE, wherein the silver particles and the fluoropolymer is applied and compacted in powder form on the carrier element, wherein the silver particles form the electrocatalyst.
  • Preferred is a gas diffusion electrode obtained from a manufacturing method of the invention described above.
  • the GDEn prepared according to the following examples were used in the oxygen electrolysis.
  • a laboratory cell was used, which consisted of an anode compartment and separated by an ion exchange membrane, a cathode compartment.
  • a KHCO 3 solution with a concentration of 300 g / l was used, in which oxygen was produced on a commercially available DSA with iridium-coated titanium electrode.
  • the cathode compartment was separated from the anode compartment by a commercially available Asahi Glass type F133 cation exchange membrane. Between GDE and the cation exchange membrane there was an electrolyte gap in which a NaHCO 3 solution of the concentration of 300 g / l was circulated.
  • the GDE was supplied via a gas space with carbon dioxide whose concentration was greater than 99.5 vol%. Anodes, membrane and gas diffusion electrode area were 3 cm 2 each. The temperature of the electrolytes was 25 ° C. The current density of the electrolysis was 4 kA / m 2 in all experiments.
  • the GDEn were prepared as follows: 3.5 kg of a powder mixture consisting of 7% by weight of PTFE powder, 93% by weight of silver powder (eg type 331 from Ferro) were mixed in an Ika mill A11 basic such that the temperature of the powder mixture did not exceed 55 ° C. This was achieved by stopping the mixing and cooling the powder mixture. Overall, mixing was performed three times with a mixing time of 10 seconds. After mixing, the powder mixture was screened with a 1.0 mm mesh screen. The sieved powder mixture was subsequently applied to an electrically conductive carrier element.
  • the support element was a nickel mesh with a wire thickness of 0.14 mm and a mesh size of 0.5 mm.
  • the application was carried out using a 1 mm thick template, wherein the powder was applied with a sieve with a mesh size of 1.0 mm. Excess powder extending beyond the thickness of the stencil was removed by means of a wiper. After removing the template, the carrier with the applied powder mixture is pressed by means of a roller press with a pressing force of 0.4 to 1.7 kN / cm. The roller press was removed from the gas diffusion electrode.
  • the powder was characterized by BET, laser diffraction and scanning electron microscopy.
  • Particle size is about 145 nm in diameter and the BET 2.23 m2 / g (N 2 adsorption).
  • Particle size is about 290 nm in diameter and the BET 0.99 m2 / g (N 2 adsorption).
  • the GDE was prepared by the dry process, wherein 93 wt .-% silver powder according to Example 1 and 2 and silver LCP-1 Ames Goldsmith, 7 wt .-% PTFE from DYNEON TF2053 mixed in an IKA mill A11 basic and then was pressed with roller press at a force of 0.5 kN / cm.
  • the electrode was used in the above electrolytic cell and operated at 2 and 4 kA / m 2 .
  • the Faraday efficiency for CO is shown in the table below. example BET m2 / g Current density 2 kA / m2 Current density 4kA / m2 1 2.23 66 43 2 0.99 19 7 LCP-1 0.5-0.9 0 0
  • the BET measurements were carried out under the following conditions.
  • the physisorption of gases at cryogenic temperature conditions is used to determine the specific surface area (SSA) of compact finely dispersed or porous solids.
  • the amount of nitrogen that physiorizes on the accessible surface of the sample is measured in a static volumetric analyzer by adding a well-defined amount of nitrogen gas to the sample cell. At the same time, the pressure increase due to the added gas is recorded after the equilibrium state is reached.
  • the total area in the measuring cell the smaller the increase in pressure (in equilibrium), since the nitrogen content adsorbed on the surface can not contribute to the increase in pressure.
  • Form the adsorbed molar amount of nitrogen on a sample the total area of the sample can be calculated by multiplying the molar amount with the known adsorbent gas adsorption area.
  • all desorbable molecules must be evaporated from the sample surface.
  • the sample was kept under vacuum conditions at 200 ° C for several hours. The measurement is then carried out analogously to DIN ISO standard 9277 with nitrogen of purity class 5.0

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EP17177031.6A 2017-06-21 2017-06-21 Gasdiffusionselektrode zur reduktion von kohlendioxid Withdrawn EP3418429A1 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP17177031.6A EP3418429A1 (de) 2017-06-21 2017-06-21 Gasdiffusionselektrode zur reduktion von kohlendioxid
PCT/EP2018/066293 WO2018234322A1 (de) 2017-06-21 2018-06-19 Gasdiffusionselektrode zur reduktion von kohlendioxid
EP18735210.9A EP3642391B1 (de) 2017-06-21 2018-06-19 Verfahren, verwendung und elektrolysezelle mit gasdiffusionselektrode zur reduktion von kohlendioxid
CN201880041586.2A CN110770370B (zh) 2017-06-21 2018-06-19 用于还原二氧化碳的气体扩散电极
US16/623,437 US20200208283A1 (en) 2017-06-21 2018-06-19 Gas diffusion electrode for reducing carbon dioxide
JP2019570373A JP7222933B2 (ja) 2017-06-21 2018-06-19 二酸化炭素を還元するガス拡散電極
KR1020197037391A KR20200020714A (ko) 2017-06-21 2018-06-19 이산화탄소의 환원을 위한 기체 확산 전극

Applications Claiming Priority (1)

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DE102018210457A1 (de) * 2018-06-27 2020-01-02 Siemens Aktiengesellschaft Gasdiffusionselektrode zur Kohlendioxid-Verwertung, Verfahren zu deren Herstellung sowie Elektrolysezelle mit Gasdiffusionselektrode
CN114373940A (zh) * 2021-12-16 2022-04-19 清华大学 气体扩散电极及其制备方法和应用
KR20240010402A (ko) 2022-07-15 2024-01-23 주식회사 엘지화학 전기화학적 이산화탄소 전환 시스템
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WO2024185870A1 (ja) * 2023-03-09 2024-09-12 三井金属鉱業株式会社 電極触媒、電気化学反応装置及び電極触媒の製造方法
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CN116876005B (zh) * 2023-07-21 2024-07-16 深圳先进技术研究院 用于电催化co2还原制co的气相扩散电极、制备方法及应用

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0144002A2 (de) 1983-11-28 1985-06-12 VARTA Batterie Aktiengesellschaft Poröse Gaselektrode
DE3710168A1 (de) 1987-03-27 1988-10-13 Varta Batterie Verfahren zur herstellung einer kunststoffgebundenen gasdiffusionselektrode mit metallischen elektrokatalysatoren
DE4444114A1 (de) 1994-12-12 1996-09-19 Bayer Ag Druckkompensierte elektrochemische Zelle
WO2001057290A1 (en) 2000-02-02 2001-08-09 Uhdenora Technologies S.R.L. Electrolysis cell provided with gas diffusion electrodes
WO2002018675A2 (en) 2000-09-01 2002-03-07 De Nora Elettrodi S.P.A. Process for the electrolysis of technical-grade hydrochloric acid contaminated with organic substances using oxygen-consuming cathodes
DE10148599A1 (de) 2001-10-02 2003-04-10 Bayer Ag Verfahren zur Herstellung von Gasdiffusionselektroden aus trockenen Pulvermischungen mittels Walzen
US20060175195A1 (en) * 2005-02-08 2006-08-10 Permelec Electrode Ltd. Gas diffusion electrode
DE102005023615A1 (de) 2005-05-21 2006-11-23 Bayer Materialscience Ag Verfahren zur Herstellung von Gasdiffusionselektroden
US20080116063A1 (en) * 2006-11-21 2008-05-22 Permelec Electrode Ltd Oxygen gas diffusion cathode for sodium chloride electrolysis
US20120208094A1 (en) * 2006-09-22 2012-08-16 Ernst Khasin Porous clusters of silver powder promoted by zirconium oxide for use as a catalyst in gas diffusion electrodes, and method for the production thereof
US20130078536A1 (en) * 2011-09-23 2013-03-28 Bayer Intellectual Property Gmbh Gas diffusion electrodes and process for production thereof
DE102015212504A1 (de) * 2015-07-03 2017-01-05 Siemens Aktiengesellschaft Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung
US20170037522A1 (en) * 2010-07-04 2017-02-09 Dioxide Materials, Inc. Method And System For Electrochemical Production Of Formic Acid From Carbon Dioxide

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2587678T3 (es) 2006-09-22 2016-10-26 Bar Ilan University Aglomeraciones porosas de polvo de plata promovidas por óxido de zirconio para usar como un catalizador en electrodos de difusión de gas, y usos de estos
EP2055807B1 (en) * 2007-10-31 2010-07-14 Daiki Ataka Engineering Co., Ltd. Oxygen Evolution Electrode
JP6021074B2 (ja) 2011-02-28 2016-11-02 国立大学法人長岡技術科学大学 二酸化炭素の還元固定化システム、二酸化炭素の還元固定化方法、及び有用炭素資源の製造方法
US10329676B2 (en) 2012-07-26 2019-06-25 Avantium Knowledge Centre B.V. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
WO2015184388A1 (en) * 2014-05-29 2015-12-03 Liquid Light, Inc. Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode
CN106715760B (zh) * 2014-09-08 2018-08-10 3M创新有限公司 用于二氧化碳电解槽的离子聚合物膜
DE102017204096A1 (de) * 2017-03-13 2018-09-13 Siemens Aktiengesellschaft Herstellung von Gasdiffusionselektroden mit Ionentransport-Harzen zur elektrochemischen Reduktion von CO2 zu chemischen Wertstoffen

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0144002A2 (de) 1983-11-28 1985-06-12 VARTA Batterie Aktiengesellschaft Poröse Gaselektrode
DE3710168A1 (de) 1987-03-27 1988-10-13 Varta Batterie Verfahren zur herstellung einer kunststoffgebundenen gasdiffusionselektrode mit metallischen elektrokatalysatoren
DE4444114A1 (de) 1994-12-12 1996-09-19 Bayer Ag Druckkompensierte elektrochemische Zelle
WO2001057290A1 (en) 2000-02-02 2001-08-09 Uhdenora Technologies S.R.L. Electrolysis cell provided with gas diffusion electrodes
WO2002018675A2 (en) 2000-09-01 2002-03-07 De Nora Elettrodi S.P.A. Process for the electrolysis of technical-grade hydrochloric acid contaminated with organic substances using oxygen-consuming cathodes
US6838408B2 (en) 2001-10-02 2005-01-04 Bayer Materialscience Ag Method for producing gas diffusion electrodes
DE10148599A1 (de) 2001-10-02 2003-04-10 Bayer Ag Verfahren zur Herstellung von Gasdiffusionselektroden aus trockenen Pulvermischungen mittels Walzen
US20060175195A1 (en) * 2005-02-08 2006-08-10 Permelec Electrode Ltd. Gas diffusion electrode
DE102005023615A1 (de) 2005-05-21 2006-11-23 Bayer Materialscience Ag Verfahren zur Herstellung von Gasdiffusionselektroden
US20120208094A1 (en) * 2006-09-22 2012-08-16 Ernst Khasin Porous clusters of silver powder promoted by zirconium oxide for use as a catalyst in gas diffusion electrodes, and method for the production thereof
US20080116063A1 (en) * 2006-11-21 2008-05-22 Permelec Electrode Ltd Oxygen gas diffusion cathode for sodium chloride electrolysis
US20170037522A1 (en) * 2010-07-04 2017-02-09 Dioxide Materials, Inc. Method And System For Electrochemical Production Of Formic Acid From Carbon Dioxide
US20130078536A1 (en) * 2011-09-23 2013-03-28 Bayer Intellectual Property Gmbh Gas diffusion electrodes and process for production thereof
DE102015212504A1 (de) * 2015-07-03 2017-01-05 Siemens Aktiengesellschaft Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEM. COMMUN., 2009, pages 301 - 303
CHEM. MATER, vol. 14, 2002, pages 2199 - 2208
CHEM. MATER., vol. 13, 2001, pages 1114 - 1123
LU; JIAO, NANOENERGY, 2016
NANOENERGY, 2016
NAT. COM, vol. 5, 2014
Y. CHEN ET AL., JACS, 2012, pages 19969

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CN110770370B (zh) 2022-11-25
EP3642391B1 (de) 2023-08-02
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