EP3577256A1 - Électodes comprenant un métal incorporé dans des électrolytes solides - Google Patents

Électodes comprenant un métal incorporé dans des électrolytes solides

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Publication number
EP3577256A1
EP3577256A1 EP18706420.9A EP18706420A EP3577256A1 EP 3577256 A1 EP3577256 A1 EP 3577256A1 EP 18706420 A EP18706420 A EP 18706420A EP 3577256 A1 EP3577256 A1 EP 3577256A1
Authority
EP
European Patent Office
Prior art keywords
metal
solid electrolyte
electrode
germanium
electrolyte
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.)
Withdrawn
Application number
EP18706420.9A
Other languages
German (de)
English (en)
Inventor
Ralf Krause
Christian Reller
Bernhard Schmid
Günter Schmid
Dan Taroata
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens AG filed Critical Siemens AG
Publication of EP3577256A1 publication Critical patent/EP3577256A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • Electrodes comprising metal introduced into solid electrolyte
  • the present invention relates to an electrode comprising a solid electrolyte and a metal M, wherein the metal M is selected from Cu, Ag, Au, Pd, and mixtures and / or alloys thereof, a process for their preparation, and their use in the electrolysis of CO and / or CO2.
  • the present invention relates to solutions of metals M, preferably silver and / or copper, and mixtures and / or alloys thereof, in solid electrolytes as active additives or
  • Silver-containing gas diffusion electrodes are used as so-called oxygen-consuming cathodes in the chloralkali electrolysis in order to suppress the formation of hydrogen by supplying gaseous oxygen at the cathode.
  • This "built-in fuel cell” reduces the energy required for chlor-alkali electrolysis by about 30%.
  • these electrodes can also be used as gas diffusion electrodes for the one - step direct elect ⁇ rochemical reduction of CO2 to CO in a wide variety of cell concepts (eg trailing CO2, passing gas) CO2, PEM (polymer electrolyte membrane), semi-PEM, with or without Elektrolytspaltrichen be used.
  • ionic liquids are used to obtain a co-catalytic effect between silver electrode and ionic liquid, which lowers the overpotential of CO2 reduction and increases the overvoltage of HER.
  • the ionic liquids especially at high
  • CBRAM Conductive Bridging RAM
  • silver- or copper-containing solid state Electrode systems used in the semiconductor industry are known in CBRAM storage.
  • elemental silver - or slightly heavier copper - is present in glasses as a solid electrolyte matrix, e.g. of germanium chalcogenides such as germanium disulfide, germanium diselenide, germanium sulfide or germanium selenide, but also tungsten oxide, even at low heat or exposure to light at room temperature - for example, even normal room lighting is sufficient - dissolves.
  • germanium chalcogenides such as germanium disulfide, germanium diselenide, germanium sulfide or germanium selenide, but also tungsten oxide, even at low heat or exposure to light at room temperature - for example, even normal room lighting is sufficient - dissolves.
  • the present invention relates to egg ne electrode comprising a solid electrolyte and a metal M wherein the metal M is selected from Cu, Ag, Au, Pd, so ⁇ as mixtures and / or alloys thereof.
  • the present invention also relates to the use of the electrode according to the invention in the electrolysis of CO2 and / or CO.
  • the invention is directed to a process for producing an electrode comprising a solid electrolyte and a metal M wherein the metal M is selected from Cu, Ag, Au, Pd, and mixtures and / or alloys thereof, directed, wherein the metal M consulttra ⁇ gene and is diffused in the solid electrolyte, or wherein the solid electrolyte in a Salt solution of the metal M is given and the metal M is deposited by reduction on the solid electrolyte and is diffused, or wherein a solid electrolyte is deposited on an electrode comprising the metal M, or where ⁇ is deposited in the solid electrolyte on particles of the metal M, and the particles to an electrode discretionverarbei ⁇ tet.
  • FIG. 1 shows an exemplary representation of a possible efforts construction of an electrolysis cell according to one embodiment of the present invention ⁇ .
  • Figure 2 shows a further exemplary representation of a possible configuration of an electrolysis cell according to an exporting ⁇ approximate shape of the present invention.
  • Figure 3 shows a third exemplary illustration of a possible configuration of an electrolysis cell according to an exporting ⁇ approximate shape of the present invention.
  • Figure 4 shows a fourth exemplary illustration of a possible configuration of an electrolysis cell according to an exporting ⁇ approximate shape of the present invention.
  • Figure 5 shows an exemplary embodiment of a Elect ⁇ rolysestrom to the C0 2 - eduction.
  • Figure 6 shows another exemplary embodiment of ei ⁇ ner electrolysis plant for C0 2 reduction.
  • Figure 7 shows schematically a section of a inventions to the invention gas diffusion electrode as an example of an OF INVENTION ⁇ to the invention electrode.
  • hydrophobic is understood as meaning water-repellent. Hydrophobic pores and / or channels according to the invention are therefore those which repel water. In particular, hydrophobic properties are associated according to the invention with substances or molecules with nonpolar groups. In contrast, hydrophilic is understood as the ability to interact with water and other polar substances. In the application, quantities are by weight. %, unless otherwise stated or obvious from the context.
  • a solid electrolyte (also called solid electrolyte or solid electrolyte) here is in particular a solid in which at least one type of ion is movable so that an electric current carried by these ions can flow.
  • the solid electrolyte is used in the context of the invention primarily as a matrix for the metal M. It is not excluded that the solid electrolyte in this case also electronic Leit ⁇ ability has, however, the solid electrolyte does not have electronic conductivity and has according to certain ⁇ embodiments essentially no electronic conductivity or even no electronic conductivity at a temperature of for example 200 ° C or less, for example 100 ° C or less, for example 50 ° C or less, for example at room temperature of 20-25 ° C, eg 22 ° C.
  • the solid electrolyte is hydrophilic, or at least its surface is hydrophilic. According to certain embodiments, the
  • preferably by the metal M can diffuse into the matrix of the solid electrolyte.
  • egg ne inventive electrode or electrolytic cell such that it does not substantially by the electrolytically ⁇ tables properties of the solid electrolyte use, similar to the above-mentioned CBRAMs.
  • the nature of the solid electrolyte here is not particularly be limited ⁇ .
  • the solid electrolyte when using the electrode, for example, in a reduction reaction in which the electrode is used as a cathode, is also implemented itself, for example ⁇ is reduced.
  • the solid electrolyte is selected from glasses, ceramics, ionic ⁇ crystals and / or polymers, preferably glasses and / or polymers, more preferably glasses.
  • the glasses, ceramics, ionic crystals and polymers here are not particularly be ⁇ limits, provided they are solid electrolytes. Examples of smoothing do ⁇ ser are here for example Germaniumsdisulfid,
  • Tungsten trioxide silicon dioxide, etc.
  • silicon dioxide silicon dioxide
  • Ceramic is yttrium-stabilized zirconium (IV) oxide, which is also used in lambda probes, for example.
  • ionic crystals are, for example AgI, as with ⁇ play as fast ion conductor such as Ag 2 HgI 4, RbAg 4 I 5,
  • polybenzoxazoles polyformaldehydes, polysulfones and / or polyimides, preferably polysulfone, polybenzoxazole and / or polyimide in question.
  • the solid electrolytes such as polymers or polymethyl ren systems as a solid electrolyte, coordinate and / or ioni ⁇ -specific bonds to the metal M, such as silver, ausbil ⁇ .
  • the solid electrolyte comprises a chalcogenide, for example, a compound such as germanium selenide, germanium diselenide, germanium sulfide,
  • Germanium disulfide, germanium telluride, silicon selenide Germanium disulfide, germanium telluride, silicon selenide
  • Germanium disulfide germanium diselenide, germanium sulfide, and / or germanium selenide, particularly preferred
  • Germanium disulfide, germanium diselenide, are germanium disulfide, germanium diselenide, and germanium diselenide.
  • Germanium sulfide and germanium selenide also tungsten trioxide, silver (I) sulfide, silica and / or
  • yttrium-stabilized zirconium (IV) oxide preferably yttrium-stabilized zirconium (IV) oxide, and / or an oxygen-containing polymer, preferably polysulfone, polybenzoxazole and / or polyimide. Particularly preferred
  • the solid electrolyte serves as a matrix for the metal M, said metal M, in particular silver, can diffuse into the solid electrolyte, and preferably "sucked up" of this is, that when necessary, a Ener ⁇ giezucht an active uptake of the metal M by the solid ⁇ electrolyte takes place.
  • the solid electrolyte that it serves the READY ⁇ development of an environment with a negative charge character, such as an oxide environment, which cations of the metal M, for example, in the states +1 and / or + 11 may, preferably, M + ions stabilize.
  • the solid electrolyte comprises a material or consists of, having the negative partial charges, which are preferably cations of the metal M, for example, in the states +1 and / or +11, preferably M + ions
  • oxides may stabilize the solid electrolyte t is a cation of the metal M, preferably M + .
  • a first aspect of the present invention relates to an electrode comprising a solid electrolyte and a metal M, wherein the metal M is selected from Cu, Ag, Au, Pd, as well as mixtures and / or alloys thereof.
  • the metal M is selected from Cu, Ag, and mixtures and / or alloy coins ⁇ approximations thereof, particularly Ag and / or alloys thereof.
  • the metal M in the present invention serves according to certain embodiments both as a catalyst and as an electron conductor in the electrode according to the invention.
  • the metal M is selected according to the invention from Cu, Ag, Au, Pd, and mixtures and / or alloys thereof.
  • the metal M is selected from Cu, Ag and mixtures and / or alloys thereof, in particular Ag and / or alloys thereof.
  • concentration of metal in the electrode according to the invention can amount to from a few parts per thousand, for example 1, 5 or 10 parts per thousand, up to the saturation limit of the metal M in Festelektroly ⁇ th. High concentrations of metal M are preferred because it forms the active catalyst.
  • the metal M in the electrode according to the invention is both elemental metal M, preferably in the form of conductor tracks, as well as in cationic form, preferably as M + and / or M 2+ (in particular Pd) , special ⁇ DERS preferably M + is present, in particular during operation of the electrode, eg for the reduction of CO 2 and / or CO.
  • the metal is usually diffused in order to maintain the electroneutrality 0-valent.
  • the metal may also be partially dissociated, eg as M + + e ⁇ .
  • Integral the charge on the metal is in such cases also re 0.
  • the metal M in the solid electrolyte or the solid electrolyte matrix averages overall as a whole, in particular a chalcogenide Festelektroly ⁇ th, for example a glass, for example an oxide matrix by activation are thus stabilized in an oxidation state between 0 and the valence of the cation, for example +1 and / or +2 in ⁇ play example for copper and / or silver between 0 and +1.
  • a corresponding activation of the metal M in the electrode for the production of cations, as well as for the production of conductor tracks can be done for example by applying a corresponding voltage after the metal M is applied to the solid electrolyte and diffused, or
  • Solid electrolyte placed in a salt solution of the metal M and the metal M is by reduction on the solid electrolyte dealt ⁇ secreted and is diffused, or a fixed electric ⁇ lyt comprising the metal M is deposited on an electrode or the solid electrolyte particles of the metal M from ⁇ is divorced and the particles were further processed ⁇ to an electrode ⁇ .
  • the metal M in particular elemental silver or slightly heavier elementa ⁇ res copper, particularly in glasses of
  • Germanium chalcogenides such as germanium disulfide
  • solid electrolytes especially chalcogenide matrix materials or mixtures thereof.
  • These solid-state electrolytes can be the oxidation states of metal M (0), eg Ag (0) or Cu (0), and metal M (+ l) and / or (+2), eg Ag (+1) or Cu (+1 ), stabilize. Both are particularly necessary and important for the catalytic cycle of single-stage electrochemical reduction of CO 2 , if, for example, the The electrode according to the invention is designed as a gas diffusion electrode.
  • the electrode according to the invention is a gas diffusion electrode.
  • the gas diffusion ⁇ electrode here is not particularly limited as long as gas diffusion electrodes common three states - solid, liquid and gaseous - with each other may be in contact and the solid electrode comprising at least one elec- Ronen conductive catalyst which an electrochemical reaction between the liquid and can catalyze the gaseous phase.
  • hydrophobic electrolytes are present in the gas diffusion electrode (GDE)
  • catalyst centers may be located in the hydrophilic regions.
  • these may comprise hydrophobic channels and / or pores.
  • the gas diffusion electrode can comprise at least two sides, a hydro ⁇ hydrophilic and hydrophobic regions and, if necessary, with a hydrophobins ⁇ ben areas.
  • Particularly active catalyst centers are liquid, solid, gaseous in a three-phase GDE.
  • An ideal GDE thus has a maximum permeation of the bulk material with hydrophilic and hydrophobic channels and / or pores in order to obtain as many three-phase regions as possible for active catalyst centers.
  • the dung OF INVENTION ⁇ proper electrode may also further constituents umfas ⁇ sen, for example, a substrate may be applied to the solid electrolyte and the metal M, and / or at least one binder.
  • the substrate is not particularly limited and may include, for example, a metal such as silver, platinum, nickel, lead, titanium, nickel, iron, manganese, copper or chromium or their alloys such as stainless steels, and / or at least one non-metal such as carbon , Si, boron nitride (BN), boron ⁇ doped diamond, etc., and / or at least one conductive oxide, such as indium tin oxide (ITO), aluminum zinc oxide (AZO), or fluorinated tin oxide (FTO) - for example for the production of photoelectrons and / or at least a polymer are based on rend polyacetylene, polyethoxythiophene, polyaniline or polypyrrole, such as in polymer-based electric ⁇ .
  • the substrate may be formed substantially by the solid electrolyte and the metal M, optionally with at least one binder.
  • the binder or binder for the electrode according to the invention is not particularly limited, and comprises, for example, a hydrophilic and / or hydrophobic polymer, for example a hydrophobic polymer, in particular PTFE (polytetrafluoroethylene).
  • a hydrophilic and / or hydrophobic polymer for example a hydrophobic polymer, in particular PTFE (polytetrafluoroethylene).
  • PTFE polytetrafluoroethylene
  • particles may for producing the gas diffusion electric ⁇ de PTFE with a particle diameter between 5 and 95 .mu.m, preferably 8-70 .mu.m used.
  • Suitable PTFE powders include, for example, Dyneon® TF 9205 and
  • 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 from devisflä ⁇ -active substances. The particle size may in this case at ⁇ play, according to ISO 13321 or D4894-98a be determined and can for example correspond to the manufacturer's instructions (for example, TF 9205: Medium Pumblegrö8e 8ym according to ISO 13321; TF 1750: average Pellegrö8e 25ym according to ASTM D4894-98a).
  • the erfindungsge ⁇ zeße electrode in particular as a gas diffusion electrode, solid electrolyte, metal M and binder comprises or consists thereof.
  • Fig. 7 shows schematically a section of an electrode according to the invention in the form of a gas diffusion electrode, in particular in a hydrophilic region.
  • the electrode in this case comprises the solid electrolyte 1, for example
  • Germanium disulfide and / or germanium diselenide as a matrix in which as a result of activation, for example by applying a voltage, conductor tracks of the metal M, for example in the form of silver (Ag) 2 have formed.
  • the GDE still has pores 3 and channels 4 through which electrolyte and / or gas, for example CO 2 , can penetrate.
  • the silver 2 can also be located on pores 3 and / or channels 4, where it can be stabilized in the form of cations as a result of the solid electrolyte matrix 1 and is thus catalytically activated.
  • the metal M in the solid electrolyte has a solubility of at least 0.1 mol / l, preferably greater than 1 mol / l, at a temperature of 25 ° and normal pressure.
  • the present invention relates to a method for the electrolysis of CO 2 and / or CO, wherein the electrode according to the invention is used as a cathode, in particular as a gas diffusion electrode ⁇ .
  • the method of the Elect ⁇ rolyse of CO 2 and / or CO is not particularly limited, in particular with regard to the second half-cell of the electrolysis, the feed of starting materials, the supply and discharge of electrolyte, the discharge of products, the structure of the electrolytic cell or beyond Electrolysis system, etc.
  • the present invention is directed in a third aspect to the use of the electrode according to the invention in the electrolysis of CO 2 and / or CO.
  • a method for producing an electrode comprising a solid electrolyte and a metal M is where selected for the metal M ⁇ from Cu, Ag, Au, Pd, and Mi ⁇ mixtures and / or alloys thereof, is disclosed wherein the Me or the solid electrolyte is placed in a salt solution of the metal M and the metal M is deposited by reduction on the solid electrolyte and is diffused, or wherein a solid electrolyte is deposited on an electrode comprising the metal M. or wherein the solid electrolyte is deposited on particles of the metal M and the Parti ⁇ kel be further processed to an electrode.
  • the metal M can be diffused into the solid electrolyte.
  • Diffusion is adapted to the particular solid electrolyte and the metal M and not further limited.
  • the diffusion is at a temperature of 20-100 ° C, preferably 20-50 ° C, eg room temperature, eg 20-25 ° C, for example about 22 ° C, for example by normal room lighting, and / or for example with a mercury vapor lamp, etc., for example with -S 1000 lux, preferably -S 500 lux, carried out, for example, when a solid electrolyte based on chalcogen as a solid electrolyte, in particular ⁇ a special glass of germanium chalcogenides such
  • Germanium disulphide or germanium diselenide or else from
  • Tungsten oxide is used, and in particular when the metal M is silver, or when the solid electrolyte is silica and the metal M is copper.
  • the diffusion can also be effected by the application of temperature at a temperature of 30-100 ° C, preferably 40-70 ° C.
  • the solid electrolytes in particular chalcogenide-containing solid electrolytes, for example Germanium chalcogenides, prepared directly from the elements.
  • germanium chalcogenide germanium and the chalcogenide are melted together at 700-1000 ° C. in a quartz glass ampoule. After cooling, the solid is ground and the body coated with the metal in a Wirbel Anlagenre ⁇ actuator.
  • a preparation for other solid electrolytes can be carried out by known methods.
  • the solid electrolyte is deposited on particles of the metal M and the particles are further processed into an electrode. According to certain embodiments, the solid electrolyte is deposited on particles of the metal M, and the particles are further processed into an electrode, wherein the particles of the metal M nano and or microparticles, preferably with a
  • Particle size of 10 nm to 500 ym are.
  • the particle size may here, for example by means of microscopic Stammanaly ⁇ se, be determined by laser diffraction and / or dynamic light scattering.
  • the particles on which the solid electrolyte has been deposited are annealed, for example at a temperature between 20 and 350 ° C, for example between 40 and 300 ° C.
  • the solid electrolyte is placed in a salt solution of the metal M and the metal M is deposited by reduction on the solid electrolyte.
  • the metal M is in this case not particularly limited insofar as it is soluble in the solvent used, for example on the basis of water or water, or on the basis of an organic solvent.
  • silver from a ammoniakalka ⁇ intermetallic solution with the aid of formaldehyde or glucose as Re ⁇ dutechnischsstoff can be deposited.
  • the metal M is applied to the solid electrolyte and diffused, or the solid ⁇ electrolyte is added to a salt solution of the metal M and the metal M by reduction on the solid electrolyte dealt- separated and diffused, whereby the diffusion takes place by the action of heat and / or light.
  • the metal M preferably silver and / or copper
  • the solid electrolyte powder is not particularly limited.
  • the solid electrolyte powder may comprise, for example, particles having a particle diameter between 0.1 and 200 ⁇ m, preferably between 1 and 10 ⁇ m, or consist of these.
  • the particle size can be determined, for example, microscopically by means of image analysis, laser diffraction and / or dynamic light scattering.
  • a solid electrolyte is deposited on an electrode comprising the metal M, to ⁇ particular if the electrode is a gas diffusion electrode.
  • the deposition of the solid electrolyte is not particularly limited here and can be carried out, for example, from the gas phase or from solution, for example in an organic solvent.
  • the metal M in the electrode according to the invention is at least partially activated.
  • a corresponding activation of the metal M in the electrode for the production of cations, as well as for the production of printed conductors can be effected for example by applying a corresponding voltage after the metal M is applied to the solid electrolyte and diffused, or the solid electrolyte in a salt solution of the metal M was added and the metal M is by reduction on the solid electrolyte dealt ⁇ secreted and is diffused, or a fixed electric ⁇ lyt comprising the metal M is deposited on an electrode, or M is deposited, the solid electrolyte on particles of the metal and the particles in a Electrode ⁇ further processed.
  • the correspondingly applied voltage can in this case be adapted, for example, to the solid electrolyte and / or the metal M.
  • the produced solid electrolyte catalysts comprising solid electrolyte and metal M can then be further processed into an electrode by the usual methods, for example by preparing a powder with suitable
  • the present invention ⁇ an electrolytic cell comprising an electrode according to the invention, which is preferably used as the cathode.
  • the electrode in this electrolytic cell is a gas diffusion electrode.
  • the other components of the electrolytic cell such as the anode, possibly a membrane, supply line (s) and discharge (s), the voltage source, etc., and other optional Vorrich ⁇ lines such as cooling or heating devices according to the invention are not particularly limited, as well not anolyte and / or catholyte used in such an electrolytic cell, the electrolytic cell according to certain Ausure ⁇ tion forms 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.
  • FIGS. 1 to 4 Exemplary embodiments for an exemplary construction of a typical electrolysis cell and of possible anode and cathode compartments are shown in FIGS. 1 to 4.
  • An electrochemical reduction of, for example, CO 2 and / or CO takes place in an electrolysis cell, which usually consists of an anode and a cathode compartment.
  • an electrolysis cell which usually consists of an anode and a cathode compartment.
  • an electrode according to the invention verwen ⁇ det, for example as a cathode.
  • the cathode compartment II in FIG. 1 is designed such that a catholyte is supplied from below, wherein it may contain a dissolved gas such as carbon dioxide and / or CO, and then leaves the cathode compartment II upwards.
  • the catholyte can also be supplied from above, as for example with falling film electrodes.
  • the anode A which is electrically connected to the cathode K by a current source for providing Stel ⁇ development of the voltage for the electrolysis, the oxidation of a substance found in the anode chamber I instead, which is supplied ⁇ introduced from below for example with an anolyte, and Anolyte with the product of the oxidation then leaves the anode compartment.
  • This 2-chamber structure differs from the 3-chamber structure in Figure 2 in that a reaction gas such as carbon dioxide or CO can be promoted through a porous cathode such as a gas diffusion electrode in the cathode space II for reduction.
  • a reaction gas such as carbon dioxide or CO
  • a porous cathode such as a gas diffusion electrode in the cathode space II for reduction.
  • porö ⁇ ser anode conceivable.
  • the spaces I and II are separated by a membrane M.
  • the PEM (proton or ion finder- membrane) structure of Figure 3 is a porous cathode and a porous anode K A directly to the membrane M, whereby the anode chamber I is separated from the cathode compartment II.
  • the structure in Figure 4 corresponds to a mixed form of the construction of Figure 2 and the structure of Figure 3, wherein a structure is provided with gas diffusion electrode to catholyte, as shown in Figure 2, whereas on anolyte side, a structure is provided as shown in Fi ⁇ gur 3 ,
  • a structure is provided with gas diffusion electrode to catholyte, as shown in Figure 2
  • a structure is provided as shown in Fi ⁇ gur 3
  • mixed forms or other embodiments of the exemplary dargestell ⁇ th electrode spaces are conceivable.
  • the cathode-side electrolyte and the anode-side electrolyte may thus be identical and the Elektrolysezel ⁇ le / electrolysis unit can dispense with the membrane.
  • a membrane or more membranes for example, 2, 3, 4, 5, 6 or more membranes, which may be the same or different, but this is associated with additional effort in terms of the membrane as well as the applied voltage.
  • Catholyte and anolyte can be mixed outside the electrolytic cell optionally again ⁇ to.
  • FIGS. 1 to 4 are schematic representations.
  • the electrolysis cells of FIGS. 1 to 4 can also be combined to form mixed variants.
  • the Ano ⁇ denraum can PEM than half cell may be as performed in Figure 3, while the cathode compartment consists of a half-cell, the tains a certain volume of electrolyte between the membrane and electrode loading, as shown in FIG. 1
  • the distance between the electrode and the membrane is very small or 0 if the membrane is made porous and contains a supply of the electrolyte.
  • the membrane can also be multi-layered, so that separate supply of anolyte or catholyte is made possible.
  • the membrane may be an ion-conducting membrane, or a separator, which causes only a mechanical separation and is permeable to cations and anions.
  • a particularly preferred form of electric ⁇ de invention is a so-called gas diffusion electrode, which made it possible ⁇ light to build a three-electrode. For example, a gas can be guided from the rear to the electrically active front side of the electrode in order to carry out the electrochemical reaction there. According to certain embodiments, the gas diffusion electrode may also only
  • a gas such as CO 2 and / or CO is at the rear of the gas diffusion electrode in relation to Passed electrolyte, wherein the gas can then penetrate through the Po ⁇ ren of the gas diffusion electrode and the product can be removed behind.
  • a gas such as CO 2 does not "bubble" through the electrolyte, high Faraday efficiencies (FE) are still found on products, for example, the backflow gas flow is also inverse to the flow of the electrolyte, possibly through ⁇ compressed fluid can be removed. Again ⁇ at a gap between the gas diffusion electrode and the membrane as the electrolyte reservoir advantageous.
  • the supply of a liquid or solution containing a gas or a gas feed can be accomplished onselektrode moreover in other ways for the embodiment illustrated in Figure 3 gas diffusion, such as a supply of CO 2 ⁇
  • gas diffusion such as a supply of CO 2 ⁇
  • the electrolytic cell on a diaphragm which separates the cathode chamber and the anode chamber of the electrolytic cell to prevent a mixing of the electric ⁇ LYTEN.
  • the membrane is not particularly limited here, as long as it separates the cathode space and the anode space. In particular, it essentially prevents one
  • a preferred membrane is an ion exchange membrane, for example polymer based.
  • a preferred material of an ion exchange membrane is a sulfonic fonATORs tetrafluoroethylene polymer, such as Nafion ®, Example ⁇ as Nafion ® 115.
  • polymeric membranes can be used, for example those mentioned in EP 1685892 Al and / or loaded with zirconium oxide polymers, such as polysulfones, ceramic membranes ,
  • the material of the anode is not particularly limited and depends primarily on the desired reaction.
  • exemplary anode materials include platinum or platinum. alloys, palladium or palladium alloys and glassy carbon. More Anodenmaterailien are also conductive Oxi ⁇ de such as doped or undoped Ti0 2, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), iridium oxide, etc. If necessary, these catalytic acti ⁇ ven compounds may be deposited on the surface even in thin-film technology, for example on a titanium and / or carbon support. Also disclosed is an electrolysis system comprising an electrode according to the invention or an electrolysis cell according to the invention.
  • FIG. 1 An abstract representation of an exemplary device of an electrolysis system is shown in FIG. 1
  • FIG. 5 shows, by way of example, an electrolysis in which carbon dioxide is reduced on the cathode side and water is oxidized on the anode A side, although other reactions take place, for example on the anode side.
  • a reaction of chloride to chlorine, bromide to bromine, sulfate to peroxodisulfate (with or without gas evolution), etc. could take place.
  • anode A for example, is suitable platinum or
  • Iridium oxide on a titanium support and as a cathode K he ⁇ inventive electrode.
  • the two electrode spaces of the electrolysis cell are separated by a membrane M, for example from Nafion®.
  • the integration of the cell into a system with anolyte circulation 10 and catholyte circulation 20 is shown schematically in FIG.
  • Anodenseits water is supplied with electrolyte additives via an inlet 11 according to this exemplary embodiment in an electrolyte reservoir 12.
  • the electrolyte reservoir 12 is also used for gas separation.
  • the water is pumped by the pump 13 in the anode compartment, where it is oxidized.
  • the product is then pumped back to the electrolyte reservoir 12, where it can be removed into the product gas container 14.
  • the product gas can be taken from the product gas tanks ⁇ 14 via a product gas 15th
  • the separation of the product gas can also take place elsewhere, for example, in the anode compartment. This results in an anolyte circuit 10, since the electrolyte is also circulated on the anode side.
  • Catholyte circuit 20 indicated wherein the individual Vorrich ⁇ tion components of the catholyte circuit 20 can also be arranged differently ⁇ order, for example by the gas separation is already in the cathode compartment.
  • the gas separation and the gas saturation are carried out separately ie in one of the containers, the electrolyte is saturated with CO 2 and then pumped as Lö ⁇ solution without gas bubbles through the cathode compartment.
  • the gas exiting the cathode compartment can then, according to certain embodiments, consist predominantly of product gas, since CO 2 itself remains dissolved since it has been consumed and thus the concentration in the electrolyte is slightly lower.
  • the electrolysis takes place in Figure 5 by the addition of electricity via a power source, not shown.
  • valves 30 are in the figure before the inlet in the
  • Provision of the anolyte or catholyte circuit may be provided.
  • a valve 30 may lie in the anolyte circuit in front of the inlet into the electrolysis cell, while the Ven ⁇ til in the catholyte cycle is behind the electrolytic cell, or vice versa.
  • FIG. 6 A further abstract representation of an exemplary device of an electrolysis system is shown in FIG.
  • the device in Figure 6 corresponds to that of Figure 5, wherein the addition of the carbon dioxide does not have a CO 2 - is introduced inlet 22 into an electrolyte reservoir 21, but directly on the cathode, which is designed here as a Gasdiffu ⁇ diffusion electrode.
  • the supply of CO 2 for example, by trailing or flowing through ei ⁇ ner porous cathode done.
  • composition of a liquid or solution for example, an electrolyte solution, which is supplied to the electrolysis device is not particularly limited, and may include all sorts of liquids or solvents, such as water, in which optionally additionally electrolytes such as conductive salts, ionic liquids, substances for include electrolytic reaction as carbon dioxide, which may be examples of play dissolved in water, additives for verb ⁇ provement the solubility and / or the wetting behavior, defoamers, etc..
  • carbon dioxide may be included in the catholyte.
  • liquids or solvents optionally additional electrolytes such as conductive salts, ionic liquids, substances for electrolytic conversion, additives for improving the solubility and / or the wetting behavior, defoamers, etc. may be present at least in one electrode space or in both electrode spaces. It is also possible for two or more of the stated substances or mixtures thereof to be included in each case. These are not particularly limited according to the invention and can be used on the anode side and / or on the cathode side.
  • the electrolysis cell of the invention or the erfindungsge ⁇ Permitted electrolysis plant may, for example at an electrical analysis of carbon dioxide and / or CO are used.
  • Germanium disulfide is first synthesized in a quartz ampule at 1100 ° C from germanium and sulfur in the stoichiometric ratio 1: 2. Typical laboratory batches are in the range of 10 - 30g. 2 B
  • Germanium disulphide powder is ground in a mill in the range of 1 - 20 ym, with Ag powder with a
  • Polytetrafluoroethylene as a binder (1 - 20 wt.%) Processed to a gas diffusion electrode. Here, the powder obtained is rolled on a silver mesh.
  • gas diffusion electrodes are made by replacing portions (5-80 wt.%) Of the Ag + catalyst with silver powder to adjust the conductivity and Faraday efficiencies with respect to CO in C0 2 electrolysis.
  • Electrification of the chemical industry means processes that were previously carried out by classical thermal processes, to be replaced by electrochemical.
  • aqueous media CO 2 CO can be efficiently produced on silver-based electrodes with silver as metal M on the novel catalysts according to the invention.
  • the competing hydrogen formation can be suppressed by admixing metal cations such as Ag + to the gas diffusion electrode.
  • metal cations such as Ag + to the gas diffusion electrode.
  • silver oxide or corresponding compounds of the metal M are reduced to silver or metal M under operating conditions. This corresponds in principle to the standard procedure of activation of a gas diffusion electrode.
  • the metal catalysts e.g. Silver or copper catalysts embedded in a solid electrolyte matrix. These solid-state electrolyte catalysts are then further processed by conventional methods into a gas diffusion electrode, or gas diffusion electrodes already produced can be modified in this way.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

L'invention concerne une électrode comprenant un électrolyte solide et un métal M, le métal M étant sélectionné parmi Cu, Ag, Au, Pd, et des mélanges de ces derniers et/ou leurs alliages, leur procédé de fabrication, et leur utilisation lors de l'électrolyse de CO et/ou de CO2.
EP18706420.9A 2017-03-09 2018-02-02 Électodes comprenant un métal incorporé dans des électrolytes solides Withdrawn EP3577256A1 (fr)

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DE102017203900.0A DE102017203900A1 (de) 2017-03-09 2017-03-09 Elektroden umfassend in Festkörperelektrolyten eingebrachtes Metall
PCT/EP2018/052656 WO2018162156A1 (fr) 2017-03-09 2018-02-02 Électodes comprenant un métal incorporé dans des électrolytes solides

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US11244722B2 (en) 2019-09-20 2022-02-08 Arizona Board Of Regents On Behalf Of Arizona State University Programmable interposers for electrically connecting integrated circuits
US11935843B2 (en) 2019-12-09 2024-03-19 Arizona Board Of Regents On Behalf Of Arizona State University Physical unclonable functions with silicon-rich dielectric devices
WO2021222742A1 (fr) * 2020-04-30 2021-11-04 Arizona Board Of Regents On Behalf Of Arizona State University Dispositifs à cellules de métallisation programmable latérale

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US20200036037A1 (en) 2020-01-30
DE102017203900A1 (de) 2018-09-13
CN110392749A (zh) 2019-10-29
AU2018232301B2 (en) 2020-01-23
AU2018232301A1 (en) 2019-07-04
WO2018162156A1 (fr) 2018-09-13

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