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
  • C25B13/00—Diaphragms; Spacing elements
  • C25B13/04—Diaphragms; Spacing elements characterised by the material
  • C25B13/05—Diaphragms; Spacing elements characterised by the material based on inorganic materials
  • C25B13/07—Diaphragms; Spacing elements characterised by the material based on inorganic materials based on ceramics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/14—Dynamic membranes
  • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
  • B01D69/148—Organic/inorganic mixed matrix membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/02—Inorganic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/30—Polyalkenyl halides
  • B01D71/32—Polyalkenyl halides containing fluorine atoms
  • B01D71/36—Polytetrafluoroethylene
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/52—Polyethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
  • B01D71/68—Polysulfones; Polyethersulfones
• • 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
  • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
  • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
  • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
  • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
  • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
  • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
  • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
  • C25B11/061—Metal or alloy
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
  • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
  • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
  • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
  • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
  • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
• • C—CHEMISTRY; METALLURGY
  • 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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2323/00—Details relating to membrane preparation
  • B01D2323/15—Use of additives
  • B01D2323/218—Additive materials
  • B01D2323/2181—Inorganic additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
  • B01D61/44—Ion-selective electrodialysis
• • 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

Definitions

• Ion-conductive membrane process for manufacturing such a membrane, cell comprising such a membrane and installation comprising such a cell
• the invention relates to ionic conductive membranes such as those used in particular, but not exclusively, in electrolysers.
• the invention proposes a new membrane, with improved ionic conduction properties, and with improved chemical, mechanical and conductive characteristics compared to the membranes described in document D1.
• the invention proposes an ion-conductive membrane for an electrochemical device, membrane comprising a layer of a material comprising a ceramic, characterized in that the said ceramic comprises boron carbide (B4C).
• Boron Carbide is a ceramic which has multipolar molecular bonds, thus making it possible to produce a membrane with good conductivity.
• the membrane comprising boron carbide also has greater chemical resistance, in particular in a basic medium.
• the longevity of the membrane is improved to reach a lifespan of the order of 4 to 5 years in a corrosive environment (for example in potassium hydroxide), in accordance with current requirements for electrolysis applications of water in an Alkaline medium in particular.
• a membrane comprising boron carbide the phenomenon of passage of the membrane by the H2 gases dissolved in the water (phenomenon known as "crossover") is less than with known membranes, which makes it possible to obtain purer gases.
• the material preferably comprises:
• the polymer binder provides the bond between the particles of the ceramic powder.
• the binder also makes it possible to obtain a membrane that is impermeable to gases, in particular to hydrogen. The "crossover" phenomenon is further reduced.
• the invention also relates to a process for manufacturing a membrane as well as an electrochemical cell comprising a membrane as described above.
• the invention finally relates to a water electrolysis installation comprising at least one electrochemical cell as described above.
• FIG. 1 shows a cell suitable for a water electrolysis application
• FIG. 2 shows a simplified diagram of a water electrolyser.
• the invention relates to an ion-conductive membrane for an electrochemical device, membrane comprising a layer of a material comprising a ceramic, characterized in that the said ceramic comprises boron carbide (B4C).
• the material preferably comprises:
• the ceramic powder can be pure boron carbide powder.
• the ceramic powder can also be a mixture of boron carbide powder and boron nitride powder.
• the presence of Boron Nitride improves the manufacturing process of a membrane because Boron Nitride has a greater bonding affinity with polymeric binders.
• Boron Nitride is also a dry lubricant which facilitates the implementation of the membrane and can give it more flexibility on the mechanical level.
• Boron Nitride must however be limited. Thus, among the membranes made from a mixture of powder, the most effective membranes were obtained for a greater quantity of boron carbide, by mass, than a quantity of boron nitride.
• the polymer binder used can be:
• PTFE polytetrafluoroethylene
• PES polyether sulfone
• polyether sulfone derivative such as a sulfonated polyether sulfone (PESS) or a chlorinated amine polyether sulfone (PESS-CI-NH2), or
• PTFE polytetrafluoroethylene
• PES polyether sulfone
• PES polyether sulfone
• PTFE polytetrafluoroethylene
• a polymer binder of the polyether sulfone (PES) type of the polyether sulfone derivative type such as a sulfonated polyether sulfone (PESS) or a chlorinated amine polyether sulfone (PESS-CI-NH2), or a mixture of polymers comprising polytetrafluoroethylene (PTFE), polyether sulfone (PES) and/or a derivative of polyether sulfone
• PES and its derivatives are chosen for their best suitability for large-scale membrane fabrication processes.
• an activation step by dispersing a quantity of ceramic powder in a basic solution, for example a KOFI potassium hydroxide solution, and
• a step of adding a binder polymer to the solution in an amount of between 5 and 40% by mass.
• the solution is stirred for 1 hour to 24 hours.
• the activation step by soaking in a basic solution makes it possible to eliminate the polluting molecular bonds on the pendant bonds of the molecules of the ceramic powder particles.
• the use of a medium basic makes it possible to obtain a more chemically resistant membrane, thus with a longer useful life of the membrane, more compatible with the current resistance requirements of 4 to 5 years in a corrosive environment for applications such as the hydrolysis of 'water.
• binder polymer makes it possible to bind the powder particles to form a membrane without open porosity, impermeable to the H2 gas dissolved in the water of the electrolyte.
• the polymer binder can be mixed by stirring for a few minutes to a few hours. Also, the mixing can be carried out under a temperate atmosphere around 40° to 60° to facilitate mixing.
• the method may also comprise a step of shaping the mixture.
• the shaping step may comprise a step of pouring the mixture onto a support, for example a glass plate.
• the pouring step can be preceded by a step for adding a solvent such as water or ethanol, to adjust the viscosity of the mixture and make the mixture sufficiently liquid. to allow casting.
• the shaping step can then be followed by a drying step to remove the solvent and form the polymer network (crosslinking).
• This embodiment is particularly suitable for the manufacture of membranes on a large scale.
• the shaping step may comprise one or more laminating steps, each laminating step comprising a rolling step and a folding step carried out successively.
• the lamination step(s) make it possible to fold and connect the long carbon chains of the PTFE polymer binder so as to form a network inside which the ceramic powder particles are trapped.
• the puffing step(s) can be preceded by a filtering step and/or a drying step to obtain a paste that is soft but not liquid.
• the step of shaping the mixture can comprise a step of hot extrusion of the mixture, at a temperature of the order of 120° to 180°, preferably 150°. If necessary, the extrusion step can be followed by a laminating step. Finally, in particular if a flat membrane is desired, the process may include a final rolling step.
• the membranes used in water electrolysis installations generally have a thickness of the order of 0.2 mm to 0.4 mm.
• the membrane according to the invention as described above can be used to produce an electrochemical cell comprising in particular
• FIG 1 shows a diagram of a known cell for water electrolysis installation for the production of Hydrogen H2 and Oxygen O2 gas.
• Figure 2 shows a block diagram of a membrane water electrolysis installation.
• the membrane 10 shares a bath in two, a bath comprising a mixture of water and electrolyte.
• the cathode 20 and the anode 30 are positioned on either side of the membrane and are respectively connected to the negative and positive terminals of a source of electrical energy.
• the membrane 10 allows a good separation of the hydrogen gas produced on the cathode and of the oxygen gas produced on the anode.
• the cathode and the anode are metallic, for example nickel, stainless steel or metallic oxides, in particular on the anode side. Nickel and stainless steel form oxides on the surface which are catalysts for the release of oxygen. 316L stainless steel is particularly effective thanks to its molybdenum content.
• layers 40, 50 of catalysts can be deposited on both sides of the membrane, between the cathode and the membrane on the one hand, between the anode and the membrane on the other hand.
• layers of catalyst can be deposited on the anode and/or the cathode.
• the catalyst layers can include nickel powder.
• the catalyst materials used can also be different for the membrane and for the electrodes.
• FIG. 1 A single cell is represented in FIG. 1. However, in practice, an industrial installation can comprise several cells, even a hundred cells.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Electrochemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Ceramic Engineering (AREA)
• Water Supply & Treatment (AREA)
• Manufacturing & Machinery (AREA)
• Dispersion Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Urology & Nephrology (AREA)
• Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
• Separation Using Semi-Permeable Membranes (AREA)
• Conductive Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

Applications Claiming Priority (2)

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• 2021
  • 2021-05-04 FR FR2104716A patent/FR3122778B1/fr active Active
  • 2021-05-27 WO PCT/IB2021/054663 patent/WO2022234327A1/fr not_active Ceased
  • 2021-05-27 KR KR1020237041766A patent/KR20240005858A/ko active Pending
  • 2021-05-27 CA CA3217407A patent/CA3217407A1/fr active Pending
  • 2021-05-27 JP JP2023568522A patent/JP7839808B2/ja active Active
  • 2021-05-27 AU AU2021444451A patent/AU2021444451A1/en active Pending
  • 2021-05-27 CN CN202180099144.5A patent/CN117425750A/zh active Pending
  • 2021-05-27 IL IL308218A patent/IL308218A/en unknown
  • 2021-05-27 EP EP21728322.5A patent/EP4334509A1/de active Pending
  • 2021-05-27 US US18/559,042 patent/US20240218541A1/en active Pending

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