EP3529396A1 - Cellule électrochimique et son procédé d'utilisation - Google Patents

Cellule électrochimique et son procédé d'utilisation

Info

Publication number
EP3529396A1
EP3529396A1 EP18787405.2A EP18787405A EP3529396A1 EP 3529396 A1 EP3529396 A1 EP 3529396A1 EP 18787405 A EP18787405 A EP 18787405A EP 3529396 A1 EP3529396 A1 EP 3529396A1
Authority
EP
European Patent Office
Prior art keywords
electrode
oxygen
hydrogen
electrolyte
layer
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.)
Pending
Application number
EP18787405.2A
Other languages
German (de)
English (en)
Other versions
EP3529396A4 (fr
Inventor
Michael BEACHY
Christopher Holt
Minette OCAMPO
Paul Matter
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.)
pH Matter LLC
Original Assignee
pH Matter LLC
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 pH Matter LLC filed Critical pH Matter LLC
Priority to EP20190888.6A priority Critical patent/EP3757255A1/fr
Priority to EP20190887.8A priority patent/EP3757254A1/fr
Priority claimed from PCT/US2018/028300 external-priority patent/WO2018195275A1/fr
Publication of EP3529396A1 publication Critical patent/EP3529396A1/fr
Publication of EP3529396A4 publication Critical patent/EP3529396A4/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C25B13/02—Diaphragms; Spacing elements characterised by shape or form
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • 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
    • 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
    • C25B9/05—Pressure cells
    • 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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/186—Regeneration by electrochemical means by electrolytic decomposition of the electrolytic solution or the formed water product
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2459—Comprising electrode layers with interposed electrolyte compartment with possible electrolyte supply or circulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2465—Details of groupings of fuel cells
    • H01M8/2483—Details of groupings of fuel cells characterised by internal manifolds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure relates generally to an electrochemical cell and a method of using the same.
  • Energy storage is required to maintain reliable electricity delivery from energy producers to their customers. As electrical loads on the grid change throughout the day, stored energy supplies electricity during increased power demand periods. Further, as more renewable and alternative energy sources are added, energy storage will maximize the usefulness of these technologies. As energy demands continue to expand, and more renewable energy, i.e., wind and solar, is added to the grid, new distributed energy storage technologies will be needed that are not dependent on geographic features. Battery technologies can provide energy storage for some applications but are not economically well-suited for long-duration charge/discharge, such as load-leveling of renewable energy. Consequently, development of new energy storage devices will augment the existing grid and reduce the capital investment in construction upgrades. As ever- increasing renewable energy is implemented, lower-cost energy storage solutions for renewable energy will be necessary to keep electricity costs low for consumers.
  • Regenerative fuel cells offer a unique solution for grid energy storage. Unlike batteries, regenerative fuel cells can cost-effectively store a large amount of energy in the form of hydrogen. Energy in the form of hydrogen can be stored at a cost of about $35/kW-hr for steel tanks, significantly lower than the cost of batteries. Regenerative fuel cells or electrolysis systems could also provide an added benefit of hydrogen generation for fuel cell vehicles. Unfortunately, there are several limitations with existing technology for regenerative fuel cell and electrolysis systems.
  • Alkaline electrolyzers are an established technology that rely on two electrodes in a liquid electrolyte. These electrodes are typically separated by a non-electrically-conductive porous layer, called the separator. Through application of a voltage, hydrogen and oxygen are evolved from the cathode and anode, respectively. Due to the permeability of the separator, the hydrogen gas cannot be pressurized substantially through electrochemical means. Small differences in pressure between the two sides of the cell can cause catastrophic cell failures.
  • a mechanical compressor is typically used for hydrogen compression, requiring an additional system component that is exceedingly expensive for many scales and applications.
  • the second common method for water electrolysis is a proton exchange membrane (PEM) electrolyzer.
  • PEM proton exchange membrane
  • This technology uses a gas-impermeable polymer membrane as the electrolyte. Water vapor or liquid water is fed to at least one of the electrodes. The gases can be easily compressed electrochemically with a PEM electrolyzer, and the cells can operate with pressure differences greater than 100 bar. PEM electrolyzers can also be made to operate reversibly, producing electricity and water from hydrogen and oxygen.
  • the drawback of PEM electrolyzers and PEM reversible fuel cells is the cost of the components.
  • the acidic electrolyte and electrolysis operating voltages necessitate the selection of expensive components for long-term stability. Platinum and Iridium may be used as electrode catalysts. Additionally, electrode current collectors must be fabricated of corrosion-resistant materials. PEM electrolysis systems are consequently too expensive for wide-scale commercial adoption for many grid-scale energy storage applications.
  • AEMs that conduct hydroxide ions and other anions, low-cost cells that can produce pressurized hydrogen have become possible.
  • hydrocarbon-based AEMs have challenges with remaining conductive if operated in the absence of liquid water.
  • ionomers in the electrode layer are required to introduce ion conduction beyond the 2-dimensional electrolyte/electrode interface, a necessity for obtaining high areal current density.
  • United States Patent No. 7,943,258 discloses an AEM fuel cell design that illustrates the challenges found with AEM cell designs.
  • This patent uses an AEM as the electrolyte and ionomer in the electrode layers.
  • the membrane is kept in a constant hydrated state by delivery of water to the edge of the membrane, outside of the active electrode area, through several unique designs.
  • ionomers are required in the electrode layer of this cell design to enable ion conduction to permeate the electrode and operate at substantial current density. While the cell design would be expected to operate well as a fuel cell utilizing pure hydrogen and pure oxygen, it would be expected to slowly lose performance in the presence of carbon dioxide in the fuel or oxidant. Further, this cell design is not conducive to electrolysis operation for several reasons.
  • hydrocarbon ionomers used in the oxygen electrode would not be stable under typical electrolysis voltages.
  • the wicking mechanism used to deliver water to hydrate the membrane would not deliver water to the cell at a sufficient rate to match the water consumption during high current electrolysis.
  • anode catalysts such as platinum or nickel
  • carbon dioxide could similarly precipitate as carbonates, blocking gas flow in the anode.
  • the cell designs would not permit significant pressurization of the product gases during electrolysis, because of the need for a porous separator. Consequently, while liquid electrolyte alkaline fuel cells and reversible alkaline fuel cells may work for many ideal cases, they have significant limitations.
  • a common design for electrolysis cells is the combination of a gas-impermeable membrane separator with electrodes flooded by water and/or electrolyte.
  • United States Patent No. 4,909,912 discloses such a design. This design is not practical for fuel cell operation because gas cannot be fed to catalysts in the flooded electrodes at a sufficient rate to generate high current density. Beyond not being useful as a fuel cell design, limitations with this cell design for electrolysis are that additional water and product gas separation steps are required to recover the product. Further, corrosion on the anode, i.e., the oxygen evolving electrode for water electrolysis, can be severe for any components in contact with the electrolyte. In this cell design, current collectors and bi-polar plates would be in contact with the electrolyte, exposing them to potentially corrosive electrochemical reactions.
  • the instant invention as disclosed in multiple embodiments, all meant by way of example only and not limitation, and includes a cell design that solves the limitations of existing liquid electrolyte cells and AEM cell designs.
  • the design in multiple embodiments, enables much lower cost components than PEM electrolyzers and reversible fuel cells.
  • the design in multiple embodiments, may utilize a combination of at least one gas-impermeable AEM in contact with a liquid electrolyte, with at least one electrode not flooded by liquid, thus allowing gas flow at a high rate in to and/or out of the electrode.
  • the gas-impermeable AEM can be any AEM material that is substantially gas-impermeable and conducts anions, including any membrane material that is impermeable to gas and conducts hydroxide anions.
  • liquid electrolytes may include any aqueous salt solution with a pH>7.
  • two AEMs separated by a porous layer may be permeated with aqueous liquid electrolyte that may be used to separate the electrodes.
  • the electrodes can be any layer in which an electrochemical reaction takes place.
  • the electrodes would consist of a hydrogen electrode in which hydrogen evolution and hydrogen oxidation can occur, and an oxygen electrode in which oxygen evolution and oxygen reduction can occur. In other embodiments these electrodes may be useful for oxygen reduction, oxygen evolution, hydrogen reduction, hydrogen evolution, fluorine evolution, chlorine evolution, bromine evolution, iodine evolution, and a number of other electrochemical reactions.
  • a porous matrix, placed between two AEM layers, may be conductive or non- conductive.
  • the porous layer may be nickel metal foam, and may be permeated with aqueous potassium hydroxide.
  • at least one electrode uses an ionomer to achieve optimal performance.
  • a hydrogen electrode uses an anion-conducting ionomer.
  • the oxygen electrode uses a fluorinated binder and/or a fluorinated ionomer.
  • At least one electrode uses a mixture of hydrophilic and hydrophobic fluorinated binder.
  • both electrodes are not flooded with liquid but the membrane may be in contact with aqueous electrolyte, allowing operation as a fuel cell and/or electrolyzer.
  • the liquid electrolyte may be stored in an external reservoir and circulated through the electrode separator layer.
  • the cell operates as a fuel cell with air as the oxidant.
  • the liquid electrolyte in contact with the AEM prevents the AEM from being converted to its carbonate form.
  • the hydrogen electrode contains a non-Ni and non-Pt catalyst that is not severely poisoned by small quantities of carbon monoxide.
  • the anode operates on a hydrogen-containing fuel that also contains carbon monoxide and carbon dioxide.
  • the cell operates as fuel cell. In another embodiment the cell operates as an electrolyzer. In another embodiment the cell operates as both a fuel cell and electrolyzer. In another embodiment the cell operates as an electrolyzer with an oxygen depolarized cathode.
  • FIG. 1 shows an embodiment of the instant invention
  • FIG. 2 shows another embodiment of the instant invention
  • FIG. 3 shows exemplary current-voltage curves obtained for water electrolysis and fuel cell currents
  • FIG. 4 shows exemplary accelerated degradation cycling for a reversible fuel cell embodiment
  • FIG. 5 shows exemplary steady-state cycling for a reversible fuel cell embodiment
  • FIG. 6 shows exemplary steady-state voltage for an oxygen-flooded electrode embodiment
  • FIG. 7 shows exemplary oxygen electrode voltage for an electrode with a hydrocarbon-based anion-conducting ionomer at 45° C in humidified oxygen (25° C dew point); 200 cycles at 40mA/cm 2 oxygen evolution, 200mA/cm 2 oxygen reduction with 1 minute relaxation; and
  • FIG. 8 shows exemplary oxygen electrode voltage for an electrode with a sulfonated tetrafluoroethylene based fluoropolymer-copolymer (hereafter, " NAFION® ,” E. I. Dupont de Nemours and Co., Wilmington, DE, USA) ionomer/binder at 45° C in humidified oxygen ( 25° C dew point); 200 cycles at 40mA/cm 2 oxygen evolution, 200mA/cm 2 oxygen reduction with 1 minute relaxation.
  • NAFION® sulfonated tetrafluoroethylene based fluoropolymer-copolymer
  • the instant invention as disclosed in multiple embodiments, all meant by way of example only and not limitation, and includes a cell design that solves the limitations of existing liquid electrolyte cells and AEM cell designs.
  • the design in multiple embodiments, enables much lower cost components than PEM electrolyzers, reversible fuel cells and conventional liquid electrolyte electrolyzers.
  • the design in multiple embodiments, may utilize a combination of at least one gas-impermeable AEM in contact with a liquid electrolyte, with at least one electrode not flooded by liquid, thus allowing gas flow at a high rate in to and/or out of the electrode.
  • the gas-impermeable AEM can be any AEM material that is substantially gas-impermeable and conducts anions, including any membrane material that is impermeable to gas and conducts hydroxide anions.
  • cationic polymer membranes include cationic polymer membranes, anion-conducting ceramic membranes, cationic polymer membranes mechanically supported by a mesh or porous substrate, polymer membranes with a cation functional group, polymers with N+H3R functional group, polymers with N+H2R2 functional group, polymers with N+HR3 functional group, polymers with N+R4 functional group, polymers with P+ functional group, and mixtures thereof.
  • cationic polymer membranes include anion-conducting ceramic membranes, cationic polymer membranes mechanically supported by a mesh or porous substrate, polymer membranes with a cation functional group, polymers with N+H3R functional group, polymers with N+H2R2 functional group, polymers with N+HR3 functional group, polymers with N+R4 functional group, polymers with P+ functional group, and mixtures thereof.
  • electrolytes may include any aqueous salt solution with a pH>7;
  • Group I, Group II, and Transition Metal Hydroxides including, Group I, Group II, and Transition Metal Hydroxides, Group I, Group II, and
  • the liquid electrolyte can be any high pH aqueous solution, including those noted above, again by way of example only and not limitation.
  • two AEMs may be separated by a porous matrix layer that may be permeated with aqueous liquid electrolyte.
  • the AEMs and porous matrix are used to separate the electrodes.
  • the electrodes can be any layer in which an electrochemical reaction takes place.
  • the electrodes would consist of a hydrogen electrode in which hydrogen evolution and hydrogen oxidation can occur, and an oxygen electrode in which oxygen evolution and oxygen reduction can occur.
  • electrode layers may include gas diffusion electrodes or may include flooded electrodes. Examples of electrodes may include catalyst coatings on a backing support, and metallic electrodes.
  • Examples of metallic electrodes further include stainless steel mesh, nickel mesh, titanium mesh, platinum mesh, coated meshes, metallic foams, metallic sponges, and mixtures thereof.
  • Examples of a backing supports include carbon cloth, carbon paper, metallic foam, metallic meshes, expanded metal mesh, and mixtures thereof.
  • Examples of electrode catalysts may include transition metals, such as group 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 transition metals, alloys of these transition metals, and mixtures thereof. Specifically, Ti, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Zn, Ru, Os, Rh, Pd, Ag, Ir, Pt, Au, and Hg are well-known as electrode catalysts to those skilled in the art.
  • Carbides, borides, nitrides, oxides, sulfides, and phosphides of transition metals are also well-known as electrode catalysts to those skilled in the art. Additional catalysts well-known to those skilled in the art include B, Al, Ga, In, Sn, Pb, Sb, Bi, and C. Elemental forms, carbide forms, boride forms, nitride forms, oxide forms, sulfide forms, phosphide forms, and mixtures thereof of catalysts are well-known as electrode catalysts to those skilled in the art.
  • Carbon catalysts may come in a number of forms, including graphite, graphene, single-walled nano-tubes, multi-walled nano-tubes, nano-fibers, spherical particles, amorphous particles, core-shell particles, and mixtures thereof. Carbon catalysts may be doped with a number of elements, including transition metal atoms, B, N, P, O, S, F, CI, Br, and mixtures thereof.
  • Electrode catalyst examples also include metal-organic frameworks, conductive polymers, pyrolysis products of hydrocarbons, pyrolysis products of polymers, and mixtures thereof. Catalysts often consist of mixtures of known catalysts. These electrode catalysts may be useful for oxygen reduction, oxygen evolution, hydrogen reduction, hydrogen evolution, fluorine evolution, chlorine evolution, bromine evolution, iodine evolution, and a number of other electrochemical reactions. Electrode catalysts for any gas-evolving or gas-consuming electrochemical reaction may be useful in the instant invention.
  • the porous matrix placed in contact with at least one AEM or between two AEM layers, may be conductive or non-conductive.
  • the porous matrix include: Any open-cell porous material, porous polypropylene, porous polyethylene, asbestos, porous PTFE, metal foam, ceramic foam, nickel metal foam, carbon paper, carbon cloth, carbon sponge, carbon fabric, metal cloth, ceramic cloth, metal sponge, polymer sponge, ceramic sponge, natural sponge, ceramic fabric, metal fabric, polymer fabric, multi-layer etched polymer membrane with flow-through channels, etched or cut channels in a thin sheet, woven mesh, non-woven mesh, and combinations thereof.
  • One skilled in the art will readily visualize other possible materials and combinations of the same.
  • the porous layer may be nickel metal foam, and may be permeated with aqueous potassium hydroxide.
  • at least one electrode uses an ionomer to achieve optimal performance.
  • ionomers include any dispersible polymeric material that conducts ions, including anionic polymers, cationic polymers, ani on-conducting ceramic particles, polymers with N+H3R functional group, polymers with N+H2R2 functional group, polymers with N+HR3 functional group, polymers with N+R4 functional group, polymers with P+ functional group, anionic polysiloxanes, and mixtures thereof.
  • AEM ionomers which are dissolved molecules of similar structure to a polymer used to make a corresponding AEM, may be utilized.
  • a hydrogen electrode uses an anion-conducting ionomer.
  • the oxygen electrode uses a fluorinated binder and fluorinated ionomer.
  • fluorinated ionomers include any dispersible polymeric material that conducts ions and includes a fluorinated backbone, including anionic polymers, cationic polymers, NAFION®, polymers with N+H3R functional group, polymers with N+H2R2 functional group, polymers with N+HR3 functional group, polymers with N+R4 functional group, polymers with P+ functional group, fluorinated anionic polysiloxanes, and mixtures thereof.
  • examples of fluorinated binder may include: any dispersible polymeric material that can be used to bind particles within an electrode and includes a fluorinated backbone, including PTFE dispersions, PTFE particles, PTFE-coated particles, anionic polymers, cationic polymers, NAFION®, polymers with N+H3R functional group, polymers with N+H2R2 functional group, polymers with N+HR3 functional group, polymers with N+R4 functional group, polymers with P+ functional group, fluorinated polysiloxanes, and mixtures thereof.
  • any dispersible polymeric material that can be used to bind particles within an electrode and includes a fluorinated backbone
  • PTFE dispersions including PTFE particles, PTFE-coated particles, anionic polymers, cationic polymers, NAFION®, polymers with N+H3R functional group, polymers with N+H2R2 functional group, polymers with N+HR3 functional group, polymers with N+R4 functional group
  • At least one electrode uses a mixture of hydrophilic and hydrophobic fluorinated binder.
  • both electrodes are not flooded with liquid but the membrane may be in contact with aqueous electrolyte, allowing operation as a fuel cell and/or electrolyzer.
  • the liquid electrolyte may be stored in an external reservoir and circulated through the electrode separator layer.
  • the cell operates as a fuel cell with air as the oxidant.
  • the liquid electrolyte in contact with the AEM prevents the AEM from being converted to its carbonate form.
  • the hydrogen electrode contains a non-Ni and non-Pt catalyst that is not severely poisoned by small quantities of carbon monoxide.
  • the anode operates on a hydrogen-containing fuel that also contains carbon monoxide and carbon dioxide.
  • Example 1 Fuel Cell or Reversible Fuel Cell.
  • FIGS. 1 and 2 show embodiments of the invention.
  • the layers need not all be of the same thickness, and in fact, there may be a wide variation in layer thicknesses.
  • the end plates may be as much as 10 cm thick, while the membrane layers may be as thin as 1 micron.
  • This cell design may consist of a series of layers that are stacked to form the invention.
  • Some layers may be combined, removed, and/or modified while still maintaining the functionality of the instant invention.
  • the first layer may be the hydrogen electrode end plate (100).
  • the plate may be made of stainless steel.
  • the hydrogen end plate (100) may contain hydrogen inlet (110) and outlet ports (120), and a tab for current collection.
  • the hydrogen end plate (100) may only require a hydrogen outlet port (120).
  • the next layer may be the first hydrogen seal (200).
  • the seals are made of thin PTFE sheets. Seal layers could also be made of epoxy, glue(s), sealant(s), other polymers, or a combination thereof. Voids in the seal may extend to the hydrogen port(s) (210, 220) to allow gas in and/or out of the electrode.
  • the ports (210, 220) could be co- extant with current collector mesh and flow field (250). This seal may frame the hydrogen electrode current collector (250), and the hydrogen flow field.
  • the hydrogen electrode current collector (250) may be stainless steel mesh.
  • the second hydrogen seal frames a hydrogen electrode (350).
  • the hydrogen electrode (350) may be porous carbon paper coated with a mixture of catalyst and AEM ionomer.
  • a preferred catalyst for the hydrogen electrode (350) may be 50-wt% ruthenium supported by Vulcan carbon.
  • the hydrogen-side AEM layer (400) may sit on top of the second hydrogen seal (300) and the framed hydrogen electrode (350) layer.
  • the next layer may be the electrolyte layer (500).
  • the electrolyte layer (500) may consist of a thin separator seal that frames a porous matrix (550).
  • the porous matrix may be nickel foam compressed to the thickness of the separator seal.
  • the separator seal also contains inlet (510) and exit ports (520) for aqueous electrolyte, preferably aqueous KOH. Channels (530, 540) in the electrolyte layer seal allow the electrolyte to flow into the bottom of the porous matrix (550) and out the top of the porous matrix (550).
  • the oxygen-side AEM layer (600) may sit on top of the electrolyte layer (500) and the framed porous matrix layer (550).
  • the first oxygen seal (700) may sit on top of the oxygen-side AEM (600). This seal may frame the oxygen electrode (750).
  • the oxygen electrode (750) may be porous carbon paper coated with a mixture of catalyst and fluorinated ionomer/binder.
  • a preferred catalyst for the oxygen electrode (750) may be a mixture of nitrogen-doped carbon and Fe/Co metal particles, including oxide and carbide phases.
  • the fluorinated ionomer/binder may be a mixture of NAFION® and dispersed PTFE binder.
  • a second oxygen seal (800) seals the oxygen electrode current collector (850).
  • the oxygen electrode current collector (850) may be stainless steel mesh.
  • the oxygen-side seal may also contain through-ports (810, 820) for the electrolyte. Voids in the second seal (800) extend to the oxygen inlet (830) and/or outlet port(s) (840) to allow gas in and/or out of the electrode.
  • the ports (830, 840) could be co-extant with current collector mesh and flow field (850).
  • the final layer may be the oxygen end plate (900).
  • the oxygen end plate (900) may contain oxygen inlet (930) and outlet (940) ports. In some instances, such as an electrolysis cell, the plate may only require an oxygen outlet port (940).
  • the end plate (900) may also contain ports (910, 920) for aqueous electrolyte to enter (910) and exit (920) the cell, and a tab for current collection.
  • One skilled in the art could also appreciate how the design could be modified to enable a number or cell repeat units to be stacked in series. In such a design, the interior layers could use through-ports for the oxygen, hydrogen, and electrolyte. The oxygen and hydrogen ports could be offset in such an embodiment.
  • Conductive interconnect plates could be used between cell repeat units to connect cells in series.
  • an AEM could be mechanically supported by a porous layer or other mechanical support to stabilize a thin AEM.
  • a porous separator such as a porous polypropylene.
  • That cell design could be part of a larger system. That system could include a return line for the exhausted liquid electrolyte to feed it back into an electrolyte reservoir. Liquid return lines from condensation collectors on the gas exits could also be connected in fluid communication with an electrolyte reservoir. One or both of the electrode gases could be in fluid communication with the electrolyte reservoir to maintain similar pressure between layers.
  • the electrolyte could be fed to the cell either through the electrolyte layer or one of the electrode chambers. Dry gas could be evolved from one of the electrodes.
  • an electrolyzer could utilize an oxygen depolarized cathode, wherein oxygen is fed to an electrode and oxygen reduction occurs in an electrode.
  • at least one of the current collectors could not be in contact with the electrolyte, and thus not be as susceptible to electrochemical degradation as flooded electrodes.
  • the first layer may be the hydrogen electrode end plate (100).
  • the hydrogen end plate (100) may be made of stainless steel.
  • the hydrogen end plate (100) may contain hydrogen inlet (110) and outlet ports (120), and a tab for current collection. In some instances, the hydrogen end plate (100) may only require the hydrogen outlet port (120).
  • the next layer may be the first hydrogen seal (200).
  • the seals may be made of thin PTFE sheets. Seal layers could also be made of epoxy, glue(s), sealant(s), other polymers, or a combination thereof. Voids in the seal extend to the hydrogen port(s) (110, 120) to allow gas in and/or out of the electrode.
  • This seal may frame the hydrogen electrode current collector (250). In this embodiment, the hydrogen electrode current collector (250) may be stainless steel mesh.
  • the next layer may be the second hydrogen seal (300), which frames the hydrogen electrode (350).
  • the hydrogen electrode (350) may be porous carbon paper coated with a mixture of catalyst and AEM ionomer. A preferred catalyst for the hydrogen electrode (350) may be 50-wt% ruthenium supported by Vulcan carbon.
  • An AEM layer (400) may sit on top of the second hydrogen seal (300) and the framed hydrogen electrode layer (350).
  • the AEM may be further mechanically supported by a porous matrix filled with aqueous electrolyte.
  • the porous matrix may be in contact with the flooded electrode, in this embodiment the oxygen electrode (750).
  • the porous matrix may thus be located between the hydrogen side membrane (400) and the oxygen electrode (750).
  • the first oxygen seal (700) sits on top of the hydrogen side membrane (AEM) (400).
  • This first oxygen seal (700) may frame the oxygen electrode (750).
  • the second oxygen seal (800) may sit on top of the first seal (700), and the second oxygen seal (800) may frame the oxygen electrode current collector (850).
  • the oxygen electrode current collector (850) may be nickel mesh and the oxygen electrode (750) may be nickel foam, coated with a mixture of catalyst and binder.
  • the oxygen electrode (750) may be flooded with an aqueous electrolyte. The electrolyte may be fed to the cell through the oxygen ingress (830) and egress (840) ports.
  • a preferred catalyst for the oxygen electrode (850) may be a mixture of Fe/Co metal particles (including oxide and carbide phases).
  • the binder may be a mixture of NAFION® and dispersed PTFE binder.
  • the oxygen-side seal (800) may also contain inlet (810) and outlet (820) ports for the electrolyte and could also serve as an egress port for any gaseous product.
  • the final layer may be the oxygen end plate (900).
  • the oxygen end plate (900) may include an inlet port (930) and an oxygen outlet port (940).
  • the oxygen end plate (900) may also contain ports for aqueous electrolyte to enter (930) and exit (940) the cell, and a tab for current collection.
  • One skilled in the art could also appreciate how the design could be modified to enable a number or cell repeat units to be stacked in series. In such a design, the interior layers could use through-ports for the oxygen, hydrogen, and electrolyte.
  • Conductive interconnect plates could be used between cell repeat units to connect cells in series. To minimize crosstalk effects through the electrolyte between cells at the top and bottom of the series, a tortuous electrolyte flow path would be preferred. Isolation of conductive materials from electrolyte would be preferred, such as coating the interconnect electrolyte through- ports.
  • FIG. 1 shows the layers used in this embodiment, however, layers 500 and 600 would not be included in this embodiment.
  • the first layer may be the hydrogen electrode end plate (100).
  • the hydrogen end plate (100) may be made of nickel.
  • the hydrogen end plate (100) may contain hydrogen inlet (110) and outlet ports (120), and a tab for current collection. In some instances, the hydrogen end plate (100) may only require the hydrogen outlet port (120).
  • the hydrogen end plate (100) may also contain ports for aqueous electrolyte to enter (110) and exit (120) the cell.
  • the next layer may be the first hydrogen seal (200).
  • the seals may be made of thin PTFE sheets. Seal layers could also be made of epoxy, glue(s), sealant(s), other polymers, or a combination thereof.
  • Voids in the seal (200) may extend to the hydrogen port(s) (210, 220) to allow gas in (210) and/or out (220) of the cell and electrolyte in (210) and/or out (220) of the cell.
  • This seal (200) may frame the hydrogen electrode current collector (250).
  • the hydrogen electrode current collector (250) may be nickel mesh.
  • the next layer may be the second hydrogen seal (300). The second hydrogen seal (300) may frame the hydrogen electrode (350).
  • the hydrogen electrode (350) may be porous carbon paper coated with a mixture of catalyst and AEM ionomer.
  • a preferred catalyst for the hydrogen electrode (350) may be 50-wt% ruthenium supported by Vulcan carbon.
  • the hydrogen electrode (350) may be flooded with an aqueous electrolyte.
  • a hydrogen side membrane (AEM) layer (400) may sit on top of the second hydrogen seal (300) and the framed hydrogen electrode layer (350).
  • the hydrogen side membrane (AEM) layer (400) may be mechanically supported by a porous matrix that is filled with electrolyte. This porous matrix may be located between the solid hydrogen side membrane (AEM) layer (400) and the flooded hydrogen electrode (350).
  • the first oxygen seal (700) sits on top of the hydrogen side membrane (AEM) (400). This seal (700) may frame the oxygen electrode (750).
  • the second oxygen seal (800) frames the oxygen current collector and flow field (850).
  • the oxygen electrode current collector (850) may be nickel mesh and the oxygen electrode (750) may be carbon paper coated with a mixture of catalyst and binder.
  • a preferred catalyst for the oxygen electrode (750) may be a mixture of Fe/Co metal particles (including oxide and carbide phases).
  • the binder may be a mixture of NAFION® and dispersed PTFE binder.
  • the final layer may be the oxygen end plate (900).
  • the oxygen end plate (900) may include an oxygen outlet port (940).
  • the end plate (900) may also include a tab for current collection.
  • One skilled in the art could also appreciate how the design could be modified to enable a number or cell repeat units to be stacked in series. In such a design, the interior layers could use through-ports for the oxygen, hydrogen, and electrolyte. Conductive interconnect plates would be used between cell repeat units to connect cells in series. To minimize crosstalk effects through the electrolyte between cells at the top and bottom of the series, a tortuous electrolyte flow path would be preferred. Isolation of conductive materials from electrolyte would be preferred, such as coating the interconnect electrolyte through- ports.
  • Example 1 A cell with the design described in Example 1 was tested for reversible fuel cell and electrolysis operation.
  • the cell had an active electrode area of 25 cm 2 . Pure hydrogen and oxygen was sent to the respective electrodes at a flow rate of 300 seem each, both humidified to a 25°C dew point.
  • Aqueous 5 M KOH electrolyte was circulated through the electrolyte layer at 3 cc/min. After purging trapped air, the gases and electrolyte were pressurized to 3 bar.
  • the cell was initially heated to 60°C using an external heater. Current-voltage curves were obtained at electrolysis and fuel cell voltages, as shown in FIG. 3. The same cell may be capable of excellent operation as either a fuel cell or an electrolyzer.
  • Example 5 Steady-State Electrolysis Tests.
  • a cell with the design described in Example 2 was tested for steady-state electrolysis operation.
  • the cell had an active electrode area of 25 cm2. Nitrogen at 3 bar was sent to the hydrogen electrode (cathode) at a flow rate of 30 seem.
  • Aqueous 5 M KOH electrolyte was circulated through the oxygen electrode chamber at 3 cc/min. After purging trapped air, the gases and electrolyte were pressurized to 3 bar.
  • the cell was initially heated to 60°C using an external heater.
  • the cell was operated under steady-state electrolysis for 18 hours at 50 mA/cm 2 (see FIG. 6). The voltage was steady throughout the operation.
  • the current was increased in 50 mA/cm 2 increments every 2 hours up to 250 mA/cm 2 while testing the purity of the hydrogen and oxygen with a gas chromatograph. Greater than 99.99% selectivity to hydrogen and oxygen versus other permanent gases was detected.
  • Reversible oxygen electrode operation was tested for a cell using the design embodiment described in Example 3.
  • a nickel mesh was used for the hydrogen electrode, and the hydrogen electrode was flooded with 5 M KOH.
  • the active electrode area was 2-cm 2 .
  • the oxygen flow rate was 50 seem.
  • the cell was tested at 45°C for reversible fuel cell and electrolysis operation.
  • a reference electrode was placed in the electrolyte and compared to the oxygen electrode.
  • the voltage of the oxygen electrode is graphed in FIGS. 7 and 8 versus a reversible hydrogen electrode reference for two different embodiments, respectively.
  • FIG. 7 shows oxygen electrode performance using a commercial hydrocarbon AEM ionomer in the electrode.
  • FIG. 8 shows the oxygen electrode performance using a mixture of NAFION® (functionalized fluorocarbon) ionomer/binder and PTFE in the electrode.
  • NAFION® functionalized fluorocarbon
  • the electrode loaded with hydrocarbon AEM ionomer degrades as current is cycled between fuel cell and electrolysis operation. This could be explained by oxidation of the hydrocarbon ionomer under electrolysis operation, and a resulting loss in ion conductivity.
  • the electrode with NAFION® fluorocarbon ionomer/binder, and all other catalysts, components, and operating conditions being identical, does not degrade rapidly. Some spikes in electrolysis voltage were observed during cycling, but this was likely due to humidity control in the electrode, and only lasts for a few seconds before the voltage returns to typical operating values.
  • the excellent oxygen reduction performance of the electrode indicates that gas is still accessible to the electrode catalyst, and thus the electrode is not fully flooded. Inspection of the electrode after testing confirmed that the membrane side of the oxygen electrode was wetted and the current collector and flow field side of the electrode was dry.
  • the electrochemical cell (10) may have at least one electrode (350, 750) substantially free of liquid water and in electrochemical contact with an electrolyte layer (400, 500)(500, 600).
  • the electrochemical cell (10) may further have at least one gas impermeable anion-conducting membrane (400, 600) having a first side and a second side, and be in electrochemical contact with the electrode (350, 750) on the first side, and in electrochemical contact with a porous non-electrode layer (550) permeated with aqueous liquid on the second side of the membrane (400, 600).
  • the aqueous liquid may be a liquid electrolyte having a pH equal to or greater than 7.0.
  • the electrolyte layer (400, 500)(500, 600) may include a second gas-impermeable membrane (400, 600).
  • the porous non-electrode layer (550) may have an opposing first side and a second side, wherein each membrane (400, 600) may be located on one of the opposing sides of the porous non-electrode layer (550) that is permeated by a high pH aqueous liquid.
  • the electrochemical cell (10) may have a second electrode
  • the second electrode (350, 750) where the second electrode (350, 750) is equal to or more than 50% filled with liquid electrolyte.
  • the second electrode (350, 750) may be an anode, while in other embodiments, the second electrode (350, 750) may be a cathode.
  • the electrochemical cell (10) may be a fuel cell, and/or a fuel cell and water electrolyzer. In some further embodiments, the electrochemical cell (10) may be an electrolyzer with an oxygen depolarized cathode.
  • the electrolyte layer (400,500)(500,600) may include a porous non-electrode layer (550) that is electrically conductive.
  • evolved gas may be electrochemically pressurized within the electrochemical cell (10).
  • the electrochemical cell (10) may use hydrophilic fluorinated binder in a gas-evolving evolving electrode (750), while in others, may use hydrophilic fluorinated binder in an oxygen-evolving electrode (750).
  • the electrochemical cell (10) may use hydrophilic fluorinated binder in an oxygen-evolving electrode (750).
  • the electrochemical cell (10) may use a mixture of hydrophilic fluorinated binder and hydrophobic fluorinated binder in a gas-evolving electrode (750), and in some embodiments, the electrochemical cell (10) may use a mixture of hydrophilic fluorinated binder and hydrophobic fluorinated binder in an oxygen-evolving electrode (750). In still others, the electrochemical cell (10) may use a mixture of hydrophilic fluorinated binder and hydrophobic fluorinated binder in a gas-evolving electrode (750).
  • an electrochemical cell (10) may have multiple layers, including a hydrogen end plate (100) further having a hydrogen ingress port (110) and a hydrogen egress port (120). Such a layer may be in electrochemical contact with a first hydrogen seal layer (300) further having a hydrogen electrode (350), in electrochemical contact with; a hydrogen side membrane (400). Such a layer may then be in electrochemical contact with an electrolyte layer (500) further having an electrolyte ingress port (510), an electrolyte egress port (520), an electrolyte inlet channel (530), and electrolyte outlet channel (540), and a porous non-electrode layer (550).
  • This layer may be in electrochemical contact with an oxygen side membrane (600), and then be in electrochemical contact with a first oxygen seal layer (700) having an oxygen electrode (750). The above may then be in electrochemical contact with an oxygen end plate (900) further comprising an oxygen ingress port (930) and an oxygen egress port (940).
  • the electrochemical cell (10) may further include a second hydrogen seal layer (200) having a hydrogen ingress port (210), a hydrogen egress port (220), and an hydrogen current collector and flow field (250) in electrochemical contact with both the hydrogen seal layer (300) and the hydrogen end plate (100).
  • a second oxygen seal layer (800) may further include an electrolyte ingress port (810), an electrolyte egress port (820), an oxygen ingress port (830), an oxygen egress port (840) and a current collector mesh and flow field (850), in electrochemical contact with both the oxygen seal layer (700) and the hydrogen end plate (900).
  • the hydrogen seal layers (200, 300) may be formed as a unitary structure, while equally well, the oxygen seal layers (700, 800). may be formed as a unitary structure.
  • a method of using an electrochemical cell (10) to generate gas from an electrolyte could include the step of feeding electrolyte to a non-electrode porous layer in
  • Such a method could include that the substantially non-flooded gas-evolving electrode layer may be less than 50% flooded with electrolyte.
  • Having a substantially non-flooded gas-evolving electrode layer facilitate gas flow within the cell (10) and minimizes corrosion caused by having electrolyte in fluid contact with the current collector.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

De multiples modes de réalisation de l'invention concernent une nouvelle cellule électrochimique. La présente invention concerne un modèle de cellule électrochimique. Dans un mode de réalisation, le modèle de cellule peut électrolyser de l'eau en hydrogène sous pression à l'aide de matériaux à bas coût. Dans un autre mode de réalisation, le modèle de cellule peut convertir l'hydrogène et l'oxygène en électricité. Dans un autre mode de réalisation, le modèle de cellule peut électrolyser de l'eau en hydrogène et en oxygène pour le stockage, puis reconvertir ultérieurement l'hydrogène et l'oxygène stockés en électricité et en eau.
EP18787405.2A 2017-04-19 2018-04-19 Cellule électrochimique et son procédé d'utilisation Pending EP3529396A4 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20190888.6A EP3757255A1 (fr) 2017-04-19 2018-04-19 Cellule électrochimique
EP20190887.8A EP3757254A1 (fr) 2017-04-19 2018-04-19 Procédé d'utilisation d'une cellule électrochimique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762487134P 2017-04-19 2017-04-19
PCT/US2018/028300 WO2018195275A1 (fr) 2017-04-19 2018-04-19 Cellule électrochimique et son procédé d'utilisation

Related Child Applications (4)

Application Number Title Priority Date Filing Date
EP20190888.6A Division EP3757255A1 (fr) 2017-04-19 2018-04-19 Cellule électrochimique
EP20190888.6A Division-Into EP3757255A1 (fr) 2017-04-19 2018-04-19 Cellule électrochimique
EP20190887.8A Division-Into EP3757254A1 (fr) 2017-04-19 2018-04-19 Procédé d'utilisation d'une cellule électrochimique
EP20190887.8A Division EP3757254A1 (fr) 2017-04-19 2018-04-19 Procédé d'utilisation d'une cellule électrochimique

Publications (2)

Publication Number Publication Date
EP3529396A1 true EP3529396A1 (fr) 2019-08-28
EP3529396A4 EP3529396A4 (fr) 2020-10-14

Family

ID=67346402

Family Applications (3)

Application Number Title Priority Date Filing Date
EP20190887.8A Pending EP3757254A1 (fr) 2017-04-19 2018-04-19 Procédé d'utilisation d'une cellule électrochimique
EP18787405.2A Pending EP3529396A4 (fr) 2017-04-19 2018-04-19 Cellule électrochimique et son procédé d'utilisation
EP20190888.6A Pending EP3757255A1 (fr) 2017-04-19 2018-04-19 Cellule électrochimique

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20190887.8A Pending EP3757254A1 (fr) 2017-04-19 2018-04-19 Procédé d'utilisation d'une cellule électrochimique

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP20190888.6A Pending EP3757255A1 (fr) 2017-04-19 2018-04-19 Cellule électrochimique

Country Status (2)

Country Link
EP (3) EP3757254A1 (fr)
CN (1) CN110168142A (fr)

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU535261B2 (en) 1979-11-27 1984-03-08 Asahi Glass Company Limited Ion exchange membrane cell
US4732660A (en) * 1985-09-09 1988-03-22 The Dow Chemical Company Membrane electrolyzer
US6541159B1 (en) * 1999-08-12 2003-04-01 Reveo, Inc. Oxygen separation through hydroxide-conductive membrane
US6793711B1 (en) * 1999-12-07 2004-09-21 Eltron Research, Inc. Mixed conducting membrane for carbon dioxide separation and partial oxidation reactions
US6649299B2 (en) * 2000-02-11 2003-11-18 The Texas A&M University System Gas diffusion electrode with nanosized pores and method for making same
US6447942B1 (en) 2000-03-13 2002-09-10 Energy Conversion Devices, Inc. Alkaline fuel cell
US6838205B2 (en) * 2001-10-10 2005-01-04 Lynntech, Inc. Bifunctional catalytic electrode
US6933072B2 (en) * 2002-02-28 2005-08-23 Energy Conersion Devices, Inc. Parallel flow fuel cell
EP1573846A2 (fr) 2002-09-23 2005-09-14 Protonex Technology Corporation Empilements de piles electrochimiques a liquide et leur procedes de production
US7862921B2 (en) * 2003-03-28 2011-01-04 Sumitomo Chemical Company, Limited Process for continuously producing polymer electrolyte membrane and producing apparatus therefor
WO2007121336A2 (fr) * 2006-04-14 2007-10-25 Applied Materials, Inc. Conception d'electrode de pile a combustible fiable
JP5151063B2 (ja) * 2006-04-19 2013-02-27 トヨタ自動車株式会社 燃料電池用電解質膜用多孔質材料、その製造方法、固体高分子型燃料電池用電解質膜、膜−電極接合体（ｍｅａ）、及び燃料電池
EP1928049A1 (fr) * 2006-11-23 2008-06-04 Technical University of Denmark Pile à combustible à oxyde solide mince
JP5194569B2 (ja) * 2007-05-31 2013-05-08 トヨタ自動車株式会社 燃料電池
WO2009015129A1 (fr) * 2007-07-24 2009-01-29 Rovcal, Inc. Dispositif de génération de gaz hydrogène à la demande
CA2763147C (fr) 2008-06-04 2018-07-24 Cellera, Inc. Piles a combustible a membrane alcaline et appareil et procede d'introduction d'eau a l'interieur de celles-ci
FR2969179B1 (fr) * 2010-12-20 2013-02-08 Commissariat Energie Atomique Cellule de production d'hydrogene comprenant une cellule d'electrolyseur de la vapeur d'eau a haute temperature.
ITMI20110500A1 (it) * 2011-03-29 2012-09-30 Industrie De Nora Spa Cella per l elettrodialisi depolarizzata di soluzioni saline
CN102361088A (zh) * 2011-11-02 2012-02-22 中国科学院长春应用化学研究所 直接甲醇燃料电池的膜电极复合体及其制备方法和直接甲醇燃料电池
JP2014012889A (ja) * 2012-06-08 2014-01-23 Nitto Denko Corp イオン透過性隔膜
JP2014148708A (ja) * 2013-01-31 2014-08-21 Nitto Denko Corp 電解用隔膜
KR20170128434A (ko) * 2015-03-10 2017-11-22 제네럴 일렉트릭 컴퍼니 다층형 지지 기재를 지닌 이온 교환 막
EP3280833B1 (fr) * 2015-04-08 2020-12-02 Stojadinovic, Jelena Voile tissé ou non tissé
CN106552497B (zh) * 2016-11-25 2019-02-01 东南大学 一种用于二氧化碳捕集和提纯的装置及方法
CN107171010A (zh) * 2017-05-11 2017-09-15 厦门大学 一种复合型的双极膜及其制备方法

Also Published As

Publication number Publication date
EP3757255A1 (fr) 2020-12-30
EP3529396A4 (fr) 2020-10-14
EP3757254A1 (fr) 2020-12-30
CN110168142A (zh) 2019-08-23

Similar Documents

Publication Publication Date Title
US10844497B2 (en) Electrochemical cell and method of using same
US9574276B2 (en) Production of low temperature electrolytic hydrogen
US20200083541A1 (en) Electrochemical cells for use with gas mixtures
WO2003021006A1 (fr) Procede et systeme de production d'hydrogene haute pression
WO2005014468A2 (fr) Procede et systeme pour produire de l'hydrogene a haute pression
EP1986264A1 (fr) Système pour la génération d'énergie électrique comprenant un reformeur électrochimique et une pile à combustible
JP2016527396A (ja) アルカリ溶液の電解セル
CN101809791B (zh) 燃料电池体系
JP6799368B2 (ja) 改質器のない燃料電池と組み合わせた装置および方法
US11888196B2 (en) Self-refueling power-generating systems
KR20230066332A (ko) 수전해조
KR20220051161A (ko) 수소 생산 장치
JP2009503254A (ja) 複数の圧縮可能な層を含む流動場部材を備えた電気化学セル
JP6998797B2 (ja) 有機ハイドライド製造装置、有機ハイドライドの製造方法およびエネルギー輸送方法
US11228051B2 (en) Electrochemical cell and method of using same
EP3757255A1 (fr) Cellule électrochimique
EP3040448A1 (fr) Dispositif de réduction électrochimique
WO2022086845A1 (fr) Cellule électrochimique et son procédé d'utilisation
US20150114842A1 (en) Electrochemical reduction device and method of manufacturing hydride of aromatic hydrocarbon compound or nitrogen-containing heterocyclic aromatic compound
US20240158924A1 (en) Electrochemical cell including solution infused layer
Kushner et al. Hydrogen‐Based Flow Batteries
US20230178781A1 (en) Alkaline membrane fuel cell assembly comprising a thin membrane and method of making same
WO2024034444A1 (fr) Appareil de production d'hydrure organique
US20240072264A1 (en) Hot pressed, binder-including membrane-electrode assemblies
EP4350045A2 (fr) Électrode, ensemble électrode à membrane, cellule électrochimique, empilement et électrolyseur

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20190522

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 8/083 20160101ALI20200527BHEP

Ipc: C25B 1/10 20060101ALI20200527BHEP

Ipc: C25B 13/02 20060101AFI20200527BHEP

Ipc: C25B 1/12 20060101ALI20200527BHEP

Ipc: H01M 8/2455 20160101ALI20200527BHEP

Ipc: H01M 8/08 20160101ALI20200527BHEP

Ipc: H01M 8/18 20060101ALI20200527BHEP

Ipc: C25B 1/04 20060101ALI20200527BHEP

Ipc: H01M 8/24 20160101ALI20200527BHEP

Ipc: C25B 13/08 20060101ALI20200527BHEP

Ipc: C25B 9/08 20060101ALI20200527BHEP

Ipc: H01M 4/86 20060101ALI20200527BHEP

Ipc: H01M 8/2483 20160101ALI20200527BHEP

Ipc: H01M 8/0289 20160101ALI20200527BHEP

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Free format text: PREVIOUS MAIN CLASS: C25B0001040000

Ipc: C25B0013020000

A4 Supplementary search report drawn up and despatched

Effective date: 20200911

RIC1 Information provided on ipc code assigned before grant

Ipc: C25B 13/08 20060101ALI20200907BHEP

Ipc: C25B 9/08 20060101ALI20200907BHEP

Ipc: C25B 1/04 20060101ALI20200907BHEP

Ipc: H01M 4/86 20060101ALI20200907BHEP

Ipc: C25B 13/02 20060101AFI20200907BHEP

Ipc: H01M 8/2483 20160101ALI20200907BHEP

Ipc: H01M 8/0289 20160101ALI20200907BHEP

Ipc: C25B 1/12 20060101ALI20200907BHEP

Ipc: H01M 8/2455 20160101ALI20200907BHEP

Ipc: H01M 8/08 20160101ALI20200907BHEP

Ipc: H01M 8/18 20060101ALI20200907BHEP

Ipc: H01M 8/083 20160101ALI20200907BHEP

Ipc: H01M 8/24 20160101ALI20200907BHEP

Ipc: C25B 1/10 20060101ALI20200907BHEP

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230518

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20231012