EP3673099A1 - Électrode à sélectivité pour l'éthylène comprenant un catalyseur cu4o3 à valence mixte - Google Patents

Électrode à sélectivité pour l'éthylène comprenant un catalyseur cu4o3 à valence mixte

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Publication number
EP3673099A1
EP3673099A1 EP18793627.3A EP18793627A EP3673099A1 EP 3673099 A1 EP3673099 A1 EP 3673099A1 EP 18793627 A EP18793627 A EP 18793627A EP 3673099 A1 EP3673099 A1 EP 3673099A1
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EP
European Patent Office
Prior art keywords
electrode
gas diffusion
cathode
catalyst
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP18793627.3A
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German (de)
English (en)
Inventor
Nemanja Martic
Christian Reller
Günter Schmid
Bernhard Schmid
David Reinisch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP3673099A1 publication Critical patent/EP3673099A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C25B11/032—Gas diffusion electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—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
    • C25B11/093—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 noble metal or noble metal oxide and at least one non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded

Definitions

  • the present invention relates to an electrode comprising CU 4 O 3 , a method for producing such an electrode, ei ne electrolytic cell comprising such an electrode, and a method for the electrochemical reaction of carbon dioxide and / or carbon monoxide using such Elekt rode.
  • the table gives Faraday efficiencies [%] of products resulting from carbon dioxide reduction on various metal electrodes.
  • carbon dioxide is bound to silver, gold,
  • Carbon monoxide C0 2 + 2 e + H 2 0 - ⁇ CO + 2 OH
  • reaction equations show that for the production of ethylene from C0 2, for example, 12 electrons need to be transferred.
  • the product selectivity is thus directly dependent on the crystal surface or its interaction with the surface species.
  • monocrystalline high index surfaces Cu 711, 511) in Journal of Molecular Catalysis A Chemical 199 (1): 39-47, 2003, a heightened ethylene selectivity is shown. Materials that have a high number of crystallographic steps or have surface defects also have increased ethylene selectivities, as described in C. Reller, R. Krause, E. Volkova, B. Schmid, S. Neubauer, A. Rucki, M. Schuster , G. Schmid, Adv. Energy Mater. 2017,
  • the material should retain its product selectivity even at high conversion rates (current densities) or maintain the advantageous structure of the catalyst centers.
  • the defects or nanostructures produced are not always stable over time, so that even after a short time (60 min) a degradation of the electrorocatalyst can be observed.
  • the material loses the property of forming ethylene through the structural change.
  • the potentials vary slightly, so that at certain points in a confined space certain intermediates are preferentially formed, which can then react at some other point. As our own studies show, potential variations well below 50 mV are significant.
  • CU 2 O increases the selectivity of copper over C 2 H 4 and hydrocarbons.
  • copper (II) oxide (CuO) has received little attention because of its poor properties as a catalyst for C0 2 electron reduction.
  • CU 2 O may be selective for various liquid and gaseous CI and C2 products.
  • stability is still one of the major drawbacks to the use of Cu 2 O phases in CCg long-term electroreduction, since they are not stable to reduction under operating conditions, as can be seen in the Pourbaix diagram for copper.
  • GDEs gas diffusion electrodes
  • CU 4 O 3 is excellently suitable as a long-term stable catalyst for the reduction of carbon dioxide to ethylene.
  • CU 4 O 3 has never been used or considered as a catalyst for the electrochemical reduction of CO 2 .
  • CU 4 O 3 is used as a catalyst for the electrochemical reduction of CO 2 .
  • the CU 4 O 3 may also be just one catalyst component.
  • the CU 4 O 3 can be used as a pre-catalyst. Under acidic conditions, a reduction with dendritic formation is also possible.
  • a gas diffusion electrode comprising CU 4 O 3 is disclosed as an electrocatalyst for CCg reduction, which exhibits a high activity (> 400 mA / cm 2 ) and selectivity for ethylene.
  • the inventors have found that preferential gas diffusion electrodes or layers, preferably with at least 0.5 mg / cm 2 Cu 4 0 3 catalyst, the following advantages in the electrochemical reduction of CO 2 to hydrocarbons:
  • the present invention relates to an electrode, in particular for an electrochemical implementation in liquid electrolytes, comprising CU 4 O 3 .
  • an electrolytic cell comprising the electrode according to the invention, preferably as a cathode.
  • the present invention also relates to a process for producing an electrode comprising CU 4 O 3 , comprising preparing a powder comprising CU 4 O 3;
  • an electrode according to the invention can be produced using these methods according to the invention.
  • Still further encompassed by the present invention is a process for the electrochemical conversion of carbon dioxide and / or carbon monoxide, wherein carbon dioxide and / or carbon monoxide is introduced and reduced in an electrolytic cell comprising an electrode according to the invention as a cathode at the cathode.
  • the present invention relates to the use of CU 4 O 3 for the reduction of CO 2 , as well as the use of CU 4 O 3 in the electrolysis of CO 2 .
  • FIGS. 2 to 19 represent schematically electrolysis cells in which the electrode according to the invention, in particular in the form of a gas diffusion electrode or a gas diffusion layer, can be used and which are thus possible Embodiments form an electrolysis cell according to the invention.
  • FIGS. 20 and 21 are measurement results of powder X-ray diffractometer (PXRD) data of powder obtained in the Examples comprising CU 4 O 3
  • FIGS. 22 and 23 are photographs of the powder with a scanning electron microscope (FIG. SEM, scanning electron microscope).
  • FIGS. 24 to 31 show measurement results obtained in examples and comparative examples according to the present invention in electrolysis cells in the reduction of CO 2 .
  • An electrode is an electrical conductor that can supply electrical current to a liquid, a gas, a vacuum or a solid body.
  • an electrode is not a powder or a particle, but may comprise particles and / or a powder or be made of a powder.
  • Ei ne cathode is in this case an electrode at which an electrochemical reduction can take place, and an anode, an electrode at which an electrochemical oxidation can take place.
  • the electrochemical conversion takes place according to certain embodiments in the presence of preferably aqueous electrolytes.
  • Quantities in the context of the present invention are based on wt. %, unless otherwise stated or obvious from the context.
  • the weights complement each other.
  • % Shares to 100 wt. %.
  • hydrophobic is 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.
  • the present invention relates, in a first aspect, to an electrode comprising CU 4 O 3 .
  • the inventive electrode is a cathode, so it can be switched as a cathode.
  • CU 4 O 3 is used as a catalyst for the electrochemical see reduction of CO 2 used.
  • the CU 4 O 3 may also be a catalyst component.
  • the CU 4 O 3 may be used as a pre-catalyst according to certain embodiments.
  • the electrode of the present invention may comprise the CU 4 O 3 as dendrites according to specific embodiments, and they are not particularly limited.
  • CU 4 O 3 Paramelaconite (CU 4 O 3) belongs together with copper (I) oxide (CU 2 O) and copper (II) oxide (CuO) to the copper oxide family. Whether CU 2 O and CuO are well studied is less well known about CU 4 O 3 as it is rare and its synthesis is complex. CU 3 O 4 is a metastable phase that is not directly accessible by thermal oxidation of oxygen-free copper.
  • the copper-oxygen system is an example of a simple eutectic system.
  • Oxygen-rich copper contains from 0.01 to 0.05 wt.% Oxygen, but can be up to
  • a phase diagram for copper-oxygen ⁇ 55 at% can be found, for example, in Landolt-Börnstein - Group IV Physical Chemistry Volume 5D: in Springer Materials A Predel, B., E Madelung, Springer-Verlag Berlin Heidelberg 1994, p. 1097, and an oxygen pressure-temperature phase diagram, for example, Landolt-Börnstein - Group IV Physical Chemistry Volume 5D: in Springer Materials A Predel, B., E Madelung, Springer-Verlag Berlin Heidelberg 1994, p. 1097.
  • CU 4 O 3 is a mixed-valent oxide with equal proportions of mono- and divalent Cu ions and is therefore sometimes formally expressed as Cu + 2 Cu 2+ 2 0 3 .
  • the crystal structure (space group I i / amd) of paramelaconite was identified as tetragonal, consisting of interpenetrating chains of Cu + -0 and Cu 2+ -0.
  • the Cu 2+ ions are coordinated with two 0 2 ions, while the Cu + ions are planarly coordinated with four 0 2 ions.
  • Paramelaconite is thermodynamically stable below half of 300 ° C, at temperatures above 300 ° C it decomposes into CuO and CU 2 O.
  • the electrochemical stability of paramelaconite is shown in the Pourbaix diagram in FIG.
  • the graph shows the higher electrochemical stability of CU 4 O 3 over the reduction compared to CU 2 O. As can be seen from the graph, it is a preferred operating range of
  • the Cu 4 0 3 microspheres were obtained by reacting the precursor Kup fer (II) nitrate trihydrate (Cu (NO 3) 2 ' 3H 2 O) in a mixed solvent of ethanol and N, N-dimethylformamide (DMF). The reaction was carried out in a 50 mL Teflon-lined stainless steel autoclave at 130 ° C for several hours. As shown in the examples, the inventors could synthesize along the route of Zhao et al. increase the reaction volume to 1.1 1 and increase the yield to more than 10 g.
  • the amount of CU 4 O 3 is not particularly limited.
  • the CU 4O3 is in an amount of 0.1-100 wt. %, preferably 40-100 wt. %, more preferably 70-100 wt. %, based on the electrode.
  • the CU is 4O3 in an amount of 0.1-100 wt. %, preferably 40-100 wt.%, more preferably 70-100 wt.
  • % based on the catalytically active part of the electrode, for example, in a layer of the electrode according to the invention, for example when the electrode according to the invention Herschich tig, eg with a gas diffusion layer, and / or gas diffusion electrode is executed.
  • the CU 4 O 3 is applied to a carrier, which is not particularly limited, both in terms of the material as well as the embodiment.
  • a carrier may in this case be, for example, a compact Festkör by, for example in the form of a pin or strip, for example a metal strip, for example comprising a metal such as Cu or an alloy thereof or consisting of a metal such as Cu or an alloy thereof, or a porous structure, For example, a fabric such as a net, a knit, etc., or a coated body.
  • the carrier may also be formed, for example, as a gas diffusion electrode, possibly also with meh reren, for example 2, 3, 4, 5, 6 or more layers of a geeigne th material or as a gas diffusion layer on a suitable substrate, which also not limited FITS is and also several layers, eg 2, 3, 4,
  • an electrode according to the invention is a gas diffusion electrode or an electrode comprising a gas diffusion layer, wherein the gas diffusion electrode or the gas diffusion layer contains CU 4 O 3 or even be it. If a gas diffusion layer comprising CU 4 O 3 is present, it can be applied to a porous or non-porous substrate.
  • the CU 4 O 3 is applied to a carrier, it is applied according to certain embodiments with a mass density of at least 0.5 mg / cm 2 .
  • the application is preferably non-planar in order to be able to provide a larger active surface area.
  • pores or pores of the carrier are preferably not substantially sealed with the application, so that a gas such as carbon dioxide can easily reach the CU 4 O 3 .
  • gas diffusion electrodes or layers preferably with at least 1 mg / cm 2 of Cu 4 O 3 catalyst, have the following advantages in the electrochemical reduction of CO 2 to hydrocarbons:
  • the electrode according to the invention is a gas diffusion electrode, which is not particularly limited and single or multi-layered, e.g. with 2, 3, 4, 5,
  • the CU 4 O 3 can then only in one layer or not in all
  • Layers be present, so for example, form one or meh er gas diffusion layers.
  • a gas diffusion electrode good contact with a gas comprising CO 2 or consisting essentially of CO 2 is very well possible, so that an efficient electrochemical production of C 2 H 4 is possible here.
  • this is of course also with an electrode comprising a gas diffusion layer containing or consisting of CU 4 O 3 well possible, since here also a large reaction surface can be offered for such a sol cal gas.
  • the ratio between hydrophilic and hydrophobic Po renvolumen should preferably in the range of about (0.01-1): 3, more preferably in the range of (0, l-0.5): 3 and preferably at about 0 , 2: 3 lie.
  • a gas diffusion electrode or a gas diffusion layer medium pore sizes in the range of 0.2 to 7 ym, preferably in the range of 0.4 to 5ym and preferably in the range of 0.5 to 2ym Issuer has Issue.
  • catalyst particles comprising or consisting of CU 4 O 3 , for example CU 4 O 3 particles, which are used for producing the electrodes according to the invention, in particular a gas diffusion electrode or a gas diffusion layer, have a uniform particle size, for example between 0 , 01 and 100 ym, for example between 0.05 and 80 ym, preferably 0.08 to 10 ym, more preferably between 0.1 and 5 ym, for example between 0.5 and 1 ym.
  • the catalyst particles furthermore have a suitable electrical conductivity, in particular a high electrical conductivity s of> 10 3 S / m, preferably 10 4 S / m or more, more preferably 10 5 S / m or more, in particular 10 6 S / m or more, where appropriate suitable additives for the parametric conit can be added to increase the conductivity of the particles, eg metal particles.
  • the catalyst particles have a low overpotential for the electroreduction of CCg.
  • the catalyst particles according to certain embodiments have a high purity without foreign metal traces.
  • a gas diffusion electrode or an electrode with gas diffusion layer should have hydrophilic and hydrophobic areas, the chen ei ne good three-phase relationship, solid, gaseous ermögli.
  • Particularly active catalyst centers are in the three-phase liquid, solid, gaseous.
  • An ideal Gasdiffusi onselektrode thus has a penetration of the bulk material than with hydrophilic and hydrophobic channels in order to keep as many three-phase areas for active catalyst centers to it.
  • a gas diffusion layer should accordingly have hydrophilic and hydrophobic channels.
  • the inven tion proper electrode in addition to CU 4 O 3 other ingredients such as promoters, conductivity additives, co-catalysts and / or binder / binder (the terms binders and binders are in the context of the present invention as synonymous synonymous words with treated with the same meaning).
  • additives for increasing conductivity are added in order to chen ermögli a good elec- and / or ionic contacting of the CU 4 O 3 .
  • cocatalysts may optionally catalyze the formation of further products from ethylene and / or the formation of intermediates in the electrochemical reduction of CO 2 to ethylene, but may also catalyze completely different reactions, for example if another reactant is used as CCg in an electrochemical reaction, eg an electrolysis.
  • At least one binder be wel Ches is not particularly limited. and two or more different binders, even in different layers of the electrode, can be used.
  • the binder for the gas diffusion electrode of the present invention if present, is not particularly limited, and includes, for example, a hydrophilic and / or hydrophobic polymer, for example, a hydrophobic polymer. In this way, a suitable adjustment of the predominantly hydrophobic pores or channels can be achieved.
  • the at least one binder is an organic binder, e.g.
  • hydrophilic materials such as polysulfones, i. Polyphenylsulfones, polyimides, polybenzoxazoles or polyether ketones or polymers which are generally electrochemically stable in the electrolyte, as is the case, for example. polymerized "ionic liquids", or organic conductors such as
  • PEDOT PSS or PANI (champansulfonic acid sorted polyaniline).
  • PTFE particles having a particle diameter between 0.01 and 95 ⁇ m, preferably between 0.05 and 70 ⁇ m, more preferably between 0.1 and 40 ⁇ m, for example 0.3 to 20 ⁇ m, for example 0, can be used to produce the gas diffusion electrodes , 5 to 20 ym, for example about 0.5 ym.
  • 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. According to certain embodiments, 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 8ym according to ISO 13321, TF 1750: mean particle size 25ym according to ASTM D4894-98a).
  • the binder may, for example, in a proportion of 0.1 to 50 wt. %, for example when using a hydrophilic ion transport material, e.g. 0.1 to 30 wt. %, preferably from 0.1 to 25 wt. %, e.g. 0.1 to 20% by weight, more preferably from 3 to 20% by weight, more preferably 3 to 10% by weight, even more preferably 5 to 10% by weight, based on the gas diffusion selective element.
  • the binder has a pronounced shear thinning of the behavior such that fiber formation occurs during the course of the fiber
  • ion transport materials can be mixed in at higher levels if they contain hydrophobic or hydrophobicizing structural units, in particular containing F, or fluorinated alkyl or acryl moieties.
  • fibers formed during manufacture should wrap around the particles without completely surrounding the surface.
  • the optimal Mixing time can be determined for example by direct visualization of fiber formation in the scanning electron microscope who the.
  • an ion transport material can be used in the electrode according to the invention, which is not particularly limited be.
  • the ion transport material for example, a Ionenaus- dauchermaterial, according to the invention is not particularly limited and may, for example, an ion transport resin, for example, an ion exchange resin, but also on those ion transport material, such as a Ionenaustau shear material such as a zeolite, etc.
  • the ion transport material is an ion exchange resin. This is not particularly limited.
  • the ion transport material is an anion transport material, for example an anion exchange resin.
  • the anion transport material or the anion transporter is an anion exchange material, for example an anion exchange resin.
  • the ion transport material also has a cation blocker function, ie it can prevent or at least reduce penetration of cations into the electrode, in particular a gas diffusion electrode or an electrode with a gas diffusion layer.
  • a cation blocker function ie it can prevent or at least reduce penetration of cations into the electrode, in particular a gas diffusion electrode or an electrode with a gas diffusion layer.
  • an integrated anion transporter or a Anio nentransportmaterial with tightly bound cations can represent here at a blockade for mobile cations by Coulombabsto tion, which ons Mrs a salt precipitation, in particular within a gas diffusion electrode or a Gasdiffusi, additionally counteract. It is un significant whether the gas diffusion electrode is completely interspersed with the anion transporter.
  • Anion-conducting additives which are not particularly limited, can additionally improve the performance of the electrode, in particular during a reduction. heights.
  • an ionomer such as, for example, 20% by weight alcoholic suspension or a 5% by weight suspension of an anion exchanger ionomer (eg AS 4 Tokuyama) can be used.
  • an anion exchanger ionomer eg AS 4 Tokuyama
  • Type 1 typically trialkyl ammonium functionalized resins
  • Type 2 typically alkylhydroxyalkyl functionalized resins
  • the present invention relates to an electrolytic cell comprising the invention Elekt rode.
  • the electrode may in this case be formed as a compact solid, as a porous electrode, for example a gas diffusion electrode, or as a coated body, for example with a gas diffusion layer, embodiments as gas diffusion electrode or electrode with gas diffusion layer comprising or consisting of CU 4 O 3 being preferred.
  • the electrode according to the invention is preferably the cathode in order to allow a reduction, for example of a gas comprising or consisting of CO 2 and / or CO.
  • the other components of the electrolysis cell are not particularly limited, and it includes those which are commonly used in electrolysis cells, e.g. a counter electrode.
  • the electrode according to the invention in the electrolytic cell is a cathode, that is connected as Ka method.
  • the electrolysis cell according to the invention further comprises an anode and at least one membrane and / or at least one diaphragm between the cathode and anode, for example at least one anion exchange membrane.
  • the other components of the electrolysis cell such as the counter electrode, for example the anode, possibly a membrane and / or a diaphragm, supply line (s) and discharge (s), the voltage source voltage, etc., and other optional devices such as cooling or heating are Not particularly limited according to the invention, as well as not anolyte and / or catholyte, which are used in such an electrolytic cell, wherein the electrolysis cell according to certain embodiments on the cathode side for the reduction of carbon dioxide and / or CO is used.
  • the configuration of the anode compartment and the cathode compartment is also not particularly limited.
  • an electrolysis cell according to the invention can be used in an electrolysis plant.
  • an electrolysis cell according to the invention can be used in an electrolysis plant.
  • Electrolysis system disclosed comprising the electrode according to the invention or the electrolysis cell according to the invention.
  • a suitable electrolytic cell for the use of the inventions to the invention electrode, eg gas diffusion electrode comprises, for example, the electrode according to the invention as a cathode with a not further limited anode.
  • the electrochemical reaction at the anode / counter electrode is also not limited FITS.
  • the cell is preferably divided from the electrode according to the invention as a gas diffusion electrode or as an electrode with a gas diffusion layer into at least two chambers, of which the chamber facing away from the counterelectrode (behind the GDE) acts as a gas chamber.
  • the rest of the cell may be flowed through by one or more electrolytes.
  • the cell may further comprise one or more separators, such that the cell may also include, for example, 3 or 4 chambers.
  • separators may be non-intrinsic ion-conducting gas separators (diaphragms) as well as ion-selective membranes (anion exchangers Membrane, cation exchange membrane, proton exchange membrane) or bipolar membranes, which are not particularly limited. These separators can be flowed around by one or more electrolytes from both sides as well as, if you own one for this operation, directly against one of the electrodes.
  • both the cathode and the anode be designed as a half-membrane electrode composite, wherein in the case of the cathode, the electrode according to the invention, in particular onselektrode Gasdiffusi or as an electrode with gas diffusion layer, preferably be part of this composite.
  • the counter electrode may also be performed, for example, as a catalyst-coated membrane. In a two-chamber cell, both electrodes can also abut directly on a common membrane.
  • the electrode according to the invention is not applied directly to a separator membrane as a gas diffusion selective element, a flow-through mode in which the electrode is flowed through by the feed gas and also a flow-by mode is possible. wherein the feed gas is passed past the side facing the electrolyte ask. If the gas diffusion electrode is directly connected to the separator or one of the separators, only “flow-by" operation is possible, especially when more than 95% by volume, preferably more than 98% by volume, of the product gases is used over the gas side of the
  • Electrode be discharged.
  • Exemplary embodiments for an exemplary construction of general electrolysis cells - also in accordance with the above statements - as well as possible anode and Katho den office are shown schematically in Figures 2 to 19, wherein in Figures 17 to 19 further components in the sense of an electrolysis system shown schematically are.
  • the following part shows in particular an illustration of electrolyte-cell concepts that are obtained by the method according to the invention for the electrochemical conversion of carbon dioxide and / or carbon monoxide are compatible.
  • I-IV spaces in the electrolysis cell, as described below in each case
  • AEM anion exchange membrane
  • exemplary structures are shown with different membranes, which, however, should not limit the cells shown. So may be provided instead of a membrane in example a diaphragm.
  • the figures also show on the cathode side a reduction of a gas, for example comprising or consisting essentially of CO 2 , wherein the electrolytic cells are not limited thereto and accordingly reactions on the cathode side in the liquid phase or solution, etc., are possible. Also in this regard, the figures do not restrict the electrolytic cell according to the invention.
  • anolyte, catholyte and, if appropriate, electrolyte can be used in an intermediate the same or different and are not particularly limited.
  • FIG. 2 shows an arrangement in which both the cathode K and the anode A abut a membrane M and behind the cathode K a reaction gas flows past in the cathode space I.
  • FIG. 3 On the anode side, there is the anode compartment II.
  • FIG. 3 in comparison to FIG. 2, there is no membrane, and cathode K and anode A are separated by the space II.
  • the structure in Figure 4 corresponds in construction substantially to that of Figure 3, in which case the cathode K is flowed through.
  • FIG. 5 shows a two-membrane arrangement, wherein between two membranes M a bridge space II is provided which electrolytically couples the cathode K and the anode A.
  • the Katho denraum I corresponds to that of Figure 1, and the anode compartment III to the anode compartment II of Figure 1.
  • the arrangement in Figure 6 un differs from that of Figure 5 in that the
  • Anode A does not abut the second membrane M on the right.
  • FIGS. 7 to 11 in turn, arrangements with only one membrane can be seen.
  • the cathode K flows behind in space I, wherein on the other side a Katho denraum II adjacent to the membrane M.
  • the membrane M is in turn separated from the anode A by the anode compartment III.
  • the structure in Figure 8 corresponds to that in Figure 7, wherein the Katho de K flows through here.
  • the membrane M is directly adjacent to the anode A, so that the anode room III is located on the side facing away from the membrane M of the anode A, otherwise they each show the back-flowed and flow-through variant of Figures 7 and 8.
  • FIG 11 shows a flow-behind variant in which the membrane M abuts the cathode, the space II the electrolytic contact with the Anode A produces and space III is located on the opposite side of the anode A.
  • Figures 12 to 16 show further variants of two-membrane arrangements, with backflowed Varian th at the cathode in Figures 12, 14 and 16, and flows through th variants in Figures 13 and 15.
  • Figures 12 and 13 is a membrane (Right) at the anode, so that the Ano denraum IV joins the right to the anode and a Kopp ment to the cathode compartment II on the bridge space III saufin det.
  • FIGS. 14 and 15 in which case the anode space IV lies between membrane M and anode A.
  • a membrane M (left) adjoins the cathode K, so that a coupling to the anode space III is provided via the bridge space II, to the right of the anode A a further space IV being provided, in which e.g. a further reactant gas for the oxidation at the anode A can be supplied.
  • FIGS. 17 to 19 show cell variants in which a reduction of CO 2 at the cathode K after supply to the space I and an oxidation of water at the anode A - which is supplied with the anolyte a to the anode space III - are shown to oxygen is, these reactions do not restrict the ge showed electrolysis cells and electrolysis systems be. It is also shown in FIGS. 17 and 18 that the CO 2 is moistened in a gas moistening GH in order to facilitate ionic contacting with the cathode K. In addition, in FIGS. 17 to 19, moreover, the product gas of the reduction is analyzed with a gas chromatograph GC, and in FIGS. 17 and 18 after separation of a permeate p the educt gas.
  • a catholyte K is supplied to the bridge space II, which allows an electrolytic coupling between the cathode K and the anode A, the cathode K being connected to an anion exchanger.
  • Figure 18 only one Kationenaus exchange membrane CEM is present, otherwise corresponds to the structure of the figure 17, wherein the space II here directly the Ka method contacted K, so represents no bridge space.
  • the cation exchange membrane CEM does not attach to the anode.
  • cell variants are also possible, as they are already described in DE 10 2015 209 509 Al, DE 10 2015 212 504 Al, DE 10 2015 201 201 Al, DE 102017208610.6, DE 102017211930.6, US 2017037522 Al or US 9481939 B2 and in which a he inventive electrode can also find application.
  • the following aspects relate to various methods of manufacturing an electrode.
  • the method according to the invention in particular, it is possible to produce a fiction, contemporary electrode, so that explanations of certain components of the electrode can also be applied to the process.
  • Another aspect of the present invention relates to a process for producing an electrode comprising CU 4 O 3 on a support comprising
  • a mixture for example a powder mixture, or a powder
  • an electrode for example a gas diffusion electrode or an electrode with gas diffusion layer, for example, in DE
  • the preparation of the mixture comprising CU 4 O 3 and optionally at least one binder is not particularly limited be and can be carried out in a suitable manner.
  • mixing may be done with a knife mill, but is not limited thereto.
  • a preferred mixing time is in the range of 60-200 s, preferably between 90-150 s.
  • the preparation of the mixture comprises mixing for 60-200 seconds, preferably 90-150 seconds.
  • the orders of the mixture or the powder on a, for example, copper-containing carrier, preferably in the form of a sheet is also not particularly limited, and may, for example, by application in powder form, etc. he follow.
  • the carrier is not particularly limited in this case and may speak the same as described above with respect to the electrode, where it can be embodied here, for example, as a net, grid, etc.
  • the dry rolling of the mixture or the powder on the carrier is not particularly limited, and can be done, for example, with a roller. In certain embodiments, rolling is carried out at a temperature of 25-100 ° C, preferably 60-80 ° C.
  • the catalyst is screened onto an already existing electrode without an additional binder.
  • the base layer can then, for example, from powder mixtures of a Cu powder, for example with a grain size of 100-160 ym, with a binder, eg 10-15 wt.% PTFE Dyne on TF 1750 or 7-10 wt.% Dyneon TF 2021, who made the.
  • Another aspect of the present invention relates to a process for producing an electrode comprising CU 4 O 3 on a support comprising
  • CU 4 O 3 or a mixture comprising CU 4 O 3 from the gas phase it is also possible to produce an electrode according to the invention with this method, as well as the other methods according to the invention.
  • the provision of the support is not particularly limited, and it can be used, for example, the discussed in the context of the electrode carrier, for example, a gas diffusion electrode or a gas diffusion layer, for example on a suitable substrate.
  • the application of the suspension is not particularly limited, and may be done by, for example, dripping, dipping, etc.
  • the material can be applied as a suspension to a commercially available GDL (eg Freudenberg C2, Sigracet 35 BC).
  • an ionomer such as, for example, 20% by weight alcoholic suspension or a 5% by weight suspension of an anion exchanger ionomer (for example AS 4 Tokuyama), is used, and / or other additives, binders , etc., which were discussed in the context of the erfindungsge MAESSEN electrode.
  • an ionomer such as, for example, 20% by weight alcoholic suspension or a 5% by weight suspension of an anion exchanger ionomer (for example AS 4 Tokuyama)
  • an anion exchanger ionomer for example AS 4 Tokuyama
  • the use of Type 1 (typically trialkyl ammonium functionalized resins) and Type 2 (typically alkyl hydroxyalkyl functionalized resins) anion exchange resins is also possible.
  • the drying of the suspension is likewise not restricted and can be carried out, for example, by solidification by evaporation or precipitation with removal of the solvent or solvent mixture of the suspension, which are not particularly limited.
  • CU 4 O 3 or a mixture comprising CU 4 O 3 from the gaseous phase is also the provision of a support, not particularly limited, and can be done as above.
  • the application of CU 4 O 3 or a gas phase mixture comprising CU 4 O 3 is also not particularly limited, and may be based on, for example, physical vapor deposition methods such as Laser ablation or chemical vapor deposition (CVD, Che mical vapor deposition) take place. As a result, thin films comprising paramelaconite can be obtained.
  • the carrier is a gas diffusion electrode or a gas diffusion layer.
  • the at least one binder is contained in the mixture or suspension, the at least one binder preferably being an ionomer includes. According to certain embodiments, the at least one binder in an amount of> 0 to 30 wt.%, Based on the total weight of CU 4 O 3 and at least one binder, in the mixture or the suspension.
  • Another aspect relates to a process for producing an electrode comprising CU 4 O 3 , comprising preparing a powder comprising CU 4 O 3; and rolling out the powder to an electrode.
  • the preparation of the powder comprising CU 4 O 3 is not particularly limited here, nor is rolling out to a powder, for example with a roller.
  • the off rolling can for example at a temperature of 15 to 300 ° C, for example 20 to 250 ° C, for example 22 to 200 ° C, preferably 25-150 ° C, more preferably 60-80 ° C, take place.
  • the powder reference may again be made to the statements above for the electrode according to the invention. With this method, in particular, as well as the other methods according to the invention, an electrode according to the invention can be produced.
  • Another aspect of the present invention is a process for the electrochemical conversion of carbon dioxide and / or carbon monoxide directed, wherein carbon dioxide and / or carbon monoxide in an electrolytic cell - comprising a he inventive electrode as a cathode - introduced at the cathode and is reduced.
  • the present invention also relates to a method and an electrolysis system for electrochemical carbon dioxide utilization.
  • Carbon dioxide (CCg) is introduced into an electrolytic cell and applied to a cathode by means of an electrode according to the invention, e.g. a Gasdiffusionselektro de (GDE), reduced on the cathode side.
  • GDEs are electrons in which liquid, solid and gaseous phases are present and where the conducting catalyst catalyzes the electrochemical reaction between the liquid and gaseous phases.
  • the introduction of the carbon dioxide and / or possibly Kohlenmo noxids at the cathode is not particularly limited, and can be done from the gas phase, from solution, etc.
  • an aqueous electrolyte in contact with the cathode contains a dissolved "conducting salt", which is not particularly limited.
  • the electrocatalyst used should ideally allow high wavelength efficiency at high current density for a corresponding target product.
  • Industrially relevant Elektrokataly catalysts should also be long-term stability.
  • For the selective production of the product carbon monoxide already pure silver catalysts are available, which meet industrial requirements.
  • the synthesis concept described here enables the production of low-voltage electrocatalysts as well an increased selectivity for ethylene and alcohols such as ethanol and / or propanol.
  • the electrochemical reaction for example an electrolysis, takes place at a current density of 200 mA / cm 2 or more, preferably 250 mA / cm 2 or more, more preferably 300 mA / cm 2 or more, even more preferably 350 mA / cm 2 or more, in particular at more than 400 mA / cm 2 .
  • this process according to the invention is also a process for the production of ethylene.
  • CU 4 O 3 for the reduction of CO 2 as well as the use of CU 4 O 3 in the electrolysis of CO 2 .
  • the synthesis of the CruCy phase was determined by a method described in the publication by Zhao et al. (Zhao et al., Chem. Mater. 2012, 24, p. 1136-1142) described in the synthesis route (mg range).
  • a typical synthesis involves a resolution of 50 mM
  • the product of the reaction precipitated in the glass insert. After cooling, the supernatant was removed from the glass insert and the remaining solid product was collected by centrifugation and washed three times with ethanol. The recovered powder was first dried under a stream of argon and then dried in vacuo. Finally, the powder was stored in a glove box under an inert atmosphere.
  • a gas diffusion electrode (GDE) containing CU 4 O 3 as a catalyst for CO 2 electroreduction was prepared as follows.
  • the previously synthesized powder containing CU 4 O 3 was poured onto a gas diffusion layer (GDL; Freudenberg H23C2 GDL) from solution as follows.
  • the binder used was an ionomer (eg AS4 from Tokuyama).
  • the ionomer solution is added to the powder containing Cu 4 O 3 catalyst particles previously dispersed in 1-propanol.
  • the amount of catalyst powder used depends on the ge desired catalyst loading, but is usually set for mass occupancy on the gas diffusion layer between 1 mg / cm 2 and 10 mg / cm 2 , for example 4.5 mg / cm 2 here, for example.
  • the dispersion was then left in an ultrasonic bath for 30 minutes, whereupon a uniform catalyst ink was formed. After sonication, the catalyst ink was poured and dried in an inert atmosphere (argon).
  • the electrochemical performance of the GDE containing CU 4 O 3 as a catalyst was tested in the electrolytes described below.
  • a stacked three-chamber flow cell was used.
  • the first chamber used as the gas supply chamber was separated from the second chamber by the GDE.
  • the second and third chambers each contained a catholyte and an anolyte and were separated by a Nafion 117 membrane.
  • the electrolytes were pumped through the cell in two separate cycles.
  • the anode compartment was filled with 2.5 M KOH and had an Ir0 2 _ containing anode.
  • the GDE was used as the cathode and 0.5 MK 2 SO 4 as the electrolyte.
  • a solid, Ir0 2- coated Ti plate was used ver.
  • the cell was equipped with an Ag / AgCl / 3M KC1 reference electrode.
  • the cathode was connected as a working electrode.
  • the GDE prepared above was compared to CU 4 O 3 with two other GDEs containing copper particles (Roth) and Cu 2 O particles as catalysts. All three GDLs were prepared by the same method as described above. Copper and CU 2 O were selected because they currently represent the state of the art for CO 2 reduction to higher hydrocarbons, including ethylene.
  • the experiments were carried out in the potentiostatic electrolysis mode, ie the cell potential was kept constant during the experiment. Gaseous products were analyzed on a Thermo Scientific Trace 1310 gas chromatograph.
  • the CU 4 O 3 -containing GDE showed a maximum selectivity of 27% Faradayeficiency (FE) over ethylene at 1.05 V (vs. Ag / AgCl) and 420 mA / cm 2 current density J.
  • the GDEs containing Cu and CU 2 O showed less than 2.5% FE for ethylene at a total current density of less than 20 mA / cm 2. This shows that a GDE containing CU 4 O 3 shows a 10-fold increase in the ethylene FE at significantly higher potential total densities (more than 20-fold) compared to GDEs with Cu and CU 2 O.
  • FIGS. 27 to 29 Other detected gaseous products are: CO, CH 4 , C 2 H 6 and H 2 .
  • the FE values for these products are shown in FIGS. 27 to 29, in which the FE values for all detected gaseous products are plotted against the cathode potential.
  • GDE was the only one capable of reducing CO 2 to C 2 H 6 (albeit in small amounts, less than 0.5% FE).
  • a GDE containing CU 4 O 3 as a catalyst was also tested in a double-membrane test setup according to FIG.
  • the GDE was made as described above. 0.5 MH 2 SO 4 was used as the electrolyte between the anion exchange membrane AEM (Sustainion x37-50 membrane) and the cathode exchange membrane CEM (Nafion 117 membrane) as well as the electrolyte circulating in the chamber behind the anode. The measurements were carried out in galvanostatic mode, ie the GDE was tested at different constant current values.
  • the counterelectrode used was a solid, IrO 2 -coated Ti plate. The cell was equipped with an Ag / AgCl / 3M KCl reference electrode. For galvano static measurements, the cathode was switched as a working electrode.
  • the Akti vity and selectivity of a gas diffusion electrode (GDE) containing CU 4 O 3 can be increased.
  • GDE gas diffusion electrode
  • the CU 4 O 3 copper oxide phase has never been investigated as a possible catalyst for CO 2 reduction.
  • the Cu 4 0 3 phase exhibits a higher stability and, as shown by X-ray diffractometry, can clearly be distinguished from CU 2 O and CuO due to the different crystal structure.
  • the oxidation state of copper is 1.5.

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Abstract

La présente invention concerne une électrode comprenant du Cu4O3, un procédé de fabrication de cette électrode, une cellule d'électrolyse comprenant cette électrode et un procédé de conversion électrochimique de dioxyde de carbone au moyen de cette électrode.
EP18793627.3A 2017-11-16 2018-10-19 Électrode à sélectivité pour l'éthylène comprenant un catalyseur cu4o3 à valence mixte Withdrawn EP3673099A1 (fr)

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Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
CN110817929B (zh) * 2019-12-03 2021-04-20 吉林大学 一种简单高效合成CsAgBr2钙钛矿的方法
DE102020204224A1 (de) * 2020-04-01 2021-10-07 Siemens Aktiengesellschaft Vorrichtung und Verfahren zur Kohlenstoffdioxid- oder Kohlenstoffmonoxid-Elektrolyse
US11788022B1 (en) * 2022-03-22 2023-10-17 Dioxycle Augmenting syngas evolution processes using electrolysis
US11965260B2 (en) 2022-03-22 2024-04-23 Dioxycle Augmenting syngas evolution processes using electrolysis
US20240076787A1 (en) * 2022-09-02 2024-03-07 Giner, Inc. Gas diffusion electrode suitable for use in carbon dioxide electrolyzer and methods for making the same

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3711382A (en) * 1970-06-04 1973-01-16 Ppg Industries Inc Bimetal spinel surfaced electrodes
NL7603185A (nl) * 1975-04-30 1976-11-02 Max Planck Gesellschaft Elektrische elementen en werkwijze voor de ver- vaardiging daarvan.
DE19544323A1 (de) * 1995-11-28 1997-06-05 Magnet Motor Gmbh Gasdiffusionselektrode für Polymerelektrolytmembran-Brennstoffzellen
US6753109B2 (en) 2002-05-06 2004-06-22 The Gillette Company Alkaline cell with improved cathode
DE102005023615A1 (de) * 2005-05-21 2006-11-23 Bayer Materialscience Ag Verfahren zur Herstellung von Gasdiffusionselektroden
US9481939B2 (en) 2010-07-04 2016-11-01 Dioxide Materials, Inc. Electrochemical device for converting carbon dioxide to a reaction product
CN101820087B (zh) * 2010-03-26 2013-06-12 瑞科稀土冶金及功能材料国家工程研究中心有限公司 组合型双效氧催化剂和含该催化剂的电极以及电池
US10047446B2 (en) 2010-07-04 2018-08-14 Dioxide Materials, Inc. Method and system for electrochemical production of formic acid from carbon dioxide
CN102320645B (zh) * 2011-08-24 2014-01-15 中国科学院过程工程研究所 一种实心或空心Cu4O3微球的制备方法
JPWO2013047379A1 (ja) * 2011-09-26 2015-03-26 日本電気株式会社 リチウム二次電池及びその製造方法
JP5807909B2 (ja) * 2011-11-14 2015-11-10 国立研究開発法人産業技術総合研究所 被膜形成方法
JP5912549B2 (ja) * 2012-01-11 2016-04-27 出光興産株式会社 電極材料、電極及びそれを用いた電池
WO2013111586A1 (fr) * 2012-01-24 2013-08-01 Ｊｘ日鉱日石エネルギー株式会社 Dispositif de réduction électrochimique et procédé de production d'un composé aromatique hétérocyclique contenant de l'hydrure d'azote ou un composé d'hydrocarbure aromatique
WO2013122868A1 (fr) * 2012-02-14 2013-08-22 Ut-Battelle, Llc Composition d'électrode à base de microsphères d'oxyde métallique mésoporeuses et leurs procédés de fabrication
EP2631954A1 (fr) * 2012-02-21 2013-08-28 Justus-Liebig-Universität Gießen Hétérojonctions contenant un oxyde de cuivre (Cu2O, Cu4O3 ou CuO), en particulier pour cellules solaires et cellules en tandem
US10553871B2 (en) * 2012-05-04 2020-02-04 Zenlabs Energy, Inc. Battery cell engineering and design to reach high energy
EP2918699A1 (fr) * 2014-03-14 2015-09-16 Justus-Liebig-Universität Gießen Procédé de fabrication de couches semi-conducteurs de l'oxyde métallique et utilisation de ces couches dans des composants électroniques
DE102015201132A1 (de) 2015-01-23 2016-07-28 Siemens Aktiengesellschaft Verfahren und Elektrolysesystem zur Kohlenstoffdioxid-Verwertung
DE102015202258A1 (de) * 2015-02-09 2016-08-25 Siemens Aktiengesellschaft Reduktionsverfahren und Elektrolysesystem zur elektrochemischen Kohlenstoffdioxid-Verwertung
DE102015203245A1 (de) 2015-02-24 2016-08-25 Siemens Aktiengesellschaft Abscheidung eines kupferhaltigen, Kohlenwasserstoffe entwickelnden Elektrokatalysators auf Nicht-Kupfer-Substraten
DE102015209509A1 (de) 2015-05-22 2016-11-24 Siemens Aktiengesellschaft Elektrolysesystem zur elektrochemischen Kohlenstoffdioxid-Verwertung mit Protonenspender-Einheit und Reduktionsverfahren
DE102015212504A1 (de) 2015-07-03 2017-01-05 Siemens Aktiengesellschaft Elektrolysesystem und Reduktionsverfahren zur elektrochemischen Kohlenstoffdioxid-Verwertung, Alkalicarbonat- und Alkalihydrogencarbonaterzeugung
DE102015215309A1 (de) 2015-08-11 2017-02-16 Siemens Aktiengesellschaft Präparationstechnik von kohlenwasserstoffselektiven Gasdiffusionselektroden basierend auf Cu-haltigen-Katalysatoren
KR101774154B1 (ko) 2016-04-26 2017-09-13 세종대학교산학협력단 스피넬 결정형 물질과 페로브스카이트 결정형 물질을 함유하는 복합체 및 이를 구비하는 전기화학소자
US11352705B2 (en) * 2016-08-12 2022-06-07 California Institute Of Technology Hydrocarbon oxidation by water oxidation electrocatalysts in non-aqueous solvents
DE102017208610A1 (de) 2017-05-22 2018-11-22 Siemens Aktiengesellschaft Zwei-Membran-Aufbau zur elektrochemischen Reduktion von CO2
DE102017211930A1 (de) 2017-07-12 2019-01-17 Siemens Aktiengesellschaft Membran gekoppelte Kathode zur Reduktion von Kohlendioxid in säurebasierten Elektrolyten ohne mobile Kationen

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WO2019096985A1 (fr) 2019-05-23
US20200385877A1 (en) 2020-12-10
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CN111433392A (zh) 2020-07-17
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US20210172079A1 (en) 2021-06-10
US11846031B2 (en) 2023-12-19

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