EP4005000A1 - Ion exchange membrane - Google Patents

Ion exchange membrane

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Publication number
EP4005000A1
EP4005000A1 EP20746654.1A EP20746654A EP4005000A1 EP 4005000 A1 EP4005000 A1 EP 4005000A1 EP 20746654 A EP20746654 A EP 20746654A EP 4005000 A1 EP4005000 A1 EP 4005000A1
Authority
EP
European Patent Office
Prior art keywords
membrane
film
amyloid fibers
fuel cell
cells
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
EP20746654.1A
Other languages
German (de)
French (fr)
Inventor
Alan Le Goff
Yannig Nedellec
Patrice Rannou
Vincent FORGE
Michael Holzinger
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.)
Centre National de la Recherche Scientifique CNRS
Universite Grenoble Alpes
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique CEA
Universite Grenoble Alpes
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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 Centre National de la Recherche Scientifique CNRS, Commissariat a lEnergie Atomique CEA, Universite Grenoble Alpes, Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP4005000A1 publication Critical patent/EP4005000A1/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K14/00—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435—Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • C07K14/76—Albumins
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2462—Lysozyme (3.2.1.17)
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • H01M4/90—Selection of catalytic material
    • 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
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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 invention relates to the use of organic molecules, such as proteins, in the form of amyloid fibers in an ion exchange membrane, which membrane can be used in electrochemical devices such as fuel cells.
  • a fuel cell is a cell in which the generation of an electrical voltage is done through the oxidation on the anode (electron emitter) of a reducing fuel (for example dihydrogen: H2) coupled the reduction on the cathode (electron collector) of an oxidant, such as oxygen (O2) from the air.
  • a reducing fuel for example dihydrogen: H2
  • an oxidant such as oxygen (O2) from the air.
  • Proton exchange membrane fuel cells also known under the name of polymer electrolyte membrane fuel cells (or PEMFC according to the acronym of the English expressions "proton exchange membrane fuel cells” or “polymer electrolyte membrane fuel cells”
  • PEMFC polymer electrolyte membrane fuel cells
  • Specific characteristics include operation of the low pressure (typically atmospheric pressure at 10 bar) and temperature (typically 20-100 ° C) ranges and a specific electrolyte membrane.
  • the membrane For the battery to function, the membrane must be able to conduct the ions
  • hydroxonium H 3 CF
  • H + hydroxonium
  • the membrane must also meet a large number of additional criteria to be able to function. First of all, it must not allow the passage of any gas from one side of the cell to the other. This phenomenon is known as "gas crossover". The membrane must resist the reducing environment at the anode and, at the same time, an oxidizing environment at the cathode. It should also be capable of operating within the broadest possible operating humidity and temperature ranges of the PEMFC. Finally, a significant source of energy losses is the resistance of the membrane to the flow of protons. This resistance is minimized by making the membrane as thin as possible (on the order of 50-20 ⁇ m). Sulfonated polystyrene membranes were initially used for electrolytes, but were replaced in 1966 by the ionomer Nafion TM, superior in performance and durability. Polymers
  • organic materials, and in particular biological materials, comprising fibers of amyloid type are able to fully or partially meet these very specific needs.
  • Amyloid fibers are very stable fibrillar nanostructures formed by a mechanism of spontaneous self-assembly of proteins or polypeptides. These fibers share the same type of intermolecular b-sheet structure. An amyloid protein acquires a secondary structure rich in b-strands which combine via H-bonds to form these b-sheets. The formation of these b-sheets, then of fibers, spontaneously is dependent on external parameters, in particular the pH and the ionic strength of the medium, the concentration of proteins or polypeptides, the presence of other molecules or further temperature and agitation parameters, which can lead to different fibrillation kinetics and organizations. Functionalized amyloid fibers can be used as electronically conductive nanowires (cf. WO2012 / 120013).
  • Hydrogels comprising ⁇ -lactalbumin are considered for possible use in the biomedical field (dressings) or in paints (cf. WO2012 / 136909).
  • enzymatic proteins at the anode or at the cathode to catalyze oxidation and / or reduction reactions.
  • PCT application WO2008058165 describes such stacks.
  • PCT application W02009040362 for its part, describes fuel cell proton exchange membranes that are alternatives to membranes
  • proton exchangers already known as the National TM.
  • These alternative membranes include graft polymers comprising a main chain having a heterocyclic unit such as polypyrrol having side chains, or "grafts".
  • grafts can comprise peptides or polypeptides of 1 to 10 polypeptide units. Such molecules are not obviously amyloid fibers.
  • the subject of the invention is an ion exchange membrane, in particular protons, comprising an aqueous liquid and a film comprising amyloid fibers.
  • a film is a structure having lateral dimensions much greater than its thickness. By “much greater” it is generally understood that the lateral dimensions are at least 100 times greater than the thickness.
  • This thickness can be advantageously chosen in a range varying from 10 nm to 1 mm, preferably 100 nm to 150 ⁇ m, so as to prevent gas crossover while not limiting conduction substantially.
  • a thickness ranging from 1 to 75 ⁇ m, in particular 15 to 55 ⁇ m (for example 20 to 30 ⁇ m) makes it possible to obtain particularly satisfactory results.
  • the surface of the membrane can, when it, be chosen in a range going from 1 mm 2 to 10 cm 2 , preferably from 1 to 50 mm 2 .
  • a membrane is a type of film having a structure through which transfer can occur under various driving forces.
  • Another object of the invention is a film comprising, or consisting of, amyloid fibers.
  • the membrane according to the invention comprises such a film itself comprising, or consisting of, amyloid fibers, preferably in a network.
  • amyloid fibers are generally fibers which result from the self-assembly of proteins or polypeptides. This self-assembly has the characteristic of being self-propagating since the addition of a small quantity (seeding process) of a protein in the form of amyloid fibers in a suspension of this same protein accelerates the growth kinetics of amyloid fibers.
  • Amyloid fibers exhibit a characteristic intermolecular b-sheet structure and also have a characteristic X-ray diffraction profile.
  • Amyloid fibers therefore correspond to the stacking of polypeptides / proteins in linear and generally non-branched fibers. These fibers are stabilized by stacking strands b arranged perpendicular to the axis of the fiber and connected by a network of hydrogen bonds. They usually show Congo red staining associated with birefringence under polarized light (Sipe & Cohen, Journal of Structural Biology 130, 88-98 (2000) [2]) and cause a sharp increase in the fluorescence emitted by thioflavin-T at the wavelength of 480 nm (Sabaté et al., Journal of Structural Biology 162, 387-396 (2008) [3]). Amyloid fibers are generally
  • aspects ratio diameter from a few nanometers to a few tens of nanometers for a length of the order of a micron up to ten microns when the fibers are formed spontaneously
  • amyloid fiber a fiber comprising, or consisting essentially of at least one polypeptide or of at least one protein, said fiber comprising a stack of strands b of said protein or of said polypeptide, said strands being arranged perpendicular to the axis of the fiber being connected by a network of hydrogen bonds.
  • amyloid fibers used in the context of the invention can come from any origin, natural or synthetic.
  • they comprise, or consist, of at least one peptide or a protein, and preferably bio-based or of biological origin, for example ⁇ -lactalbumin, lysozyme, ⁇ -lactoglobulin, prion domain of Het-s and insulin.
  • bio-based or of biological origin for example ⁇ -lactalbumin, lysozyme, ⁇ -lactoglobulin, prion domain of Het-s and insulin.
  • amyloid fibers can also come from polypeptides, or even from peptides.
  • the film and / or the membrane according to the invention is made from a protein solution (which then forms a hydrogel in aqueous medium). After depositing and drying the hydrogel, a film is then obtained, the matrix of which comprises a fibrous network, which comprises, or consists of
  • amyloid fibers mainly, amyloid fibers.
  • the aqueous liquid allowing the preparation of the hydrogel or that present in the membrane essentially comprises water but may contain a small proportion of other compounds, such as salts in solution or other additives.
  • the expression "low proportion" may indicate that the liquid consists of at least
  • Such a hydrogel is generally referred to as a supramolecular gel.
  • the film and / or the membrane can advantageously be formed by depositing a solution of proteins, the concentration of which is typically from .1 g / L to 500 g / L.
  • concentration of this solution is typically between, or ranging from 1 g / L and 150 g / L (that is to say between, or ranging from, 0.1 and 15% in mass proportion relative to the solvent. aqueous).
  • concentration of the protein solution can advantageously range from 25 g / L to 100 g / L.
  • the film and / or the membrane according to the invention is self-supporting (or self-supporting), that is to say sufficiently rigid to be able to be handled and placed. in a device such as a battery according to the invention.
  • the film and / or the membrane can also be self-supporting (or self-supporting), that is to say sufficiently rigid to be able to be handled and placed. in a device such as a battery according to the invention.
  • the film and / or the membrane can also
  • additives can have one or more objectives and in particular be chosen from the group consisting of:
  • plasticizers to adjust the level of mechanical properties (Young's modulus E [MPa], Lowering of the glass transition) and to facilitate the use of membranes, for example polymers such as methylcellulose, organic and inorganic derivatives with silica base,
  • crosslinking agents for example glutaraldehyde (pentane-1, 5-dial), to chemically crosslink (irreversibly) the membrane in order to ensure chemical and dimensional stability,
  • antioxidants eg vitamin E (in its 8 natural forms: a-tocopherol, b-tocopherol, y-tocopherol, d -tocopherol, a- tocotrienol, b-tocotrienol, g-tocotrienol and d-tocotrienol, ascorbic acid, 3,4-dihydroxy-cinnamic acid) or metal cations such as cerium,
  • the method of manufacturing the film and / or the membrane can comprise a chemical crosslinking step.
  • the crosslinking agent can, for example, be a compound such as glutaraldehyde.
  • the crosslinking step can be carried out by bringing the crosslinking agent together with the film and / or the membrane already formed, for example by exposing said film or said membrane to vapors of the crosslinking agent.
  • the membrane according to the invention does not allow the passage of electrons. It is also preferred that it does not allow the passage of gas.
  • the membrane should resist the reducing environment (eg a medium rich in hydrogen) and, at the same time, an oxidizing environment, such as air (oxygen).
  • said membrane can have an ability to exchange ions.
  • At low temperature for example from 0 ° C to 45 ° C, preferably from 10 ° C to 30 ° C, and in particular around 25 ° C; and or
  • At low relative humidity for example 45% to 75%, preferably 55% to 65%, and in particular around 60%.
  • the membrane allows ion exchange, and in particular the exchange of protons.
  • other ions, cations or anions can be exchanged and in particular hydroxide ions, OH.
  • Another object of the invention is a cell, preferably fuel cell, comprising:
  • said membrane comprising an aqueous liquid and a film comprising amyloid fibers.
  • the membrane comprises, or consists of, a membrane such as that described in the present application.
  • the membrane in the battery according to the invention acts as an electrolyte, since it contains the ions which can penetrate and circulate in the film matrix by diffusion. Together with the anode and the cathode, the membrane forms the heart of the cell.
  • the film comprising amyloid fibers is as described in the present application.
  • the basic device comprising an anode, a cathode and a membrane according to the invention can be described as an electrochemical cell, or simply a cell.
  • the anode and the cathode can be of any type but are generally chosen from the standard type in materials allowing the electrochemical reactions at the anode and at the cathode.
  • PEMFCs they generally consist of a catalyst, for example platinum particles of 2 to 4 nm, of ionic polymer and of a conductive material such as a fabric or a carbon powder.
  • These materials are generally associated with a gas diffusion layer (GDL according to the acronym of the English expression "Gaz Diffusion Layer"). This layer makes it possible to ensure a homogeneous distribution of the gases, possibly good management of the water in the cell, and a mechanical strength of the membrane and of the active layers containing the reactive materials of the anode and of the cathode.
  • Such a layer generally consists of a porous carbon fabric with a thickness which may be between 100 ⁇ m and 300 ⁇ m and coated with polymer, generally PTFE.
  • the carbon fibers of the fabric can be arranged in different ways, for example woven and non-woven.
  • the cell according to the invention can also include additional elements, in particular when the cell according to the invention is a fuel cell (PAC), and in particular of the "Proton-exchange membrane fuel celf” (PEMFC) type.
  • PAC fuel cell
  • PEMFC Proton-exchange membrane fuel celf
  • the battery according to the invention further comprises two plates:
  • a first plate to distribute a reducing fuel, for example dihydrogen, and
  • Each of these plates may be made of, or comprise, machined graphite, metallic materials and / or carbon / polymer or carbon / carbon composites.
  • the plates can provide a seal between the anode and cathode compartments, possibly manage the water produced at the cathode, collect electrons produced at the anode and redistributed at the cathode, to ensure the maintenance of the cell in its operating temperature range thanks to an integrated cooling system and / or to ensure the mechanical cohesion of the stack during tightening and
  • Another element of the battery according to the invention is the possible presence of sealing means, in particular seals.
  • the function of these is to ensure the airtightness of the cell necessary for the optimal and safe operation of the battery and can be made of PTFE, silicone and EPDM (ethylene propylene diene monomer).
  • Another object of the invention is also to stack cells to form a PAC according to the invention as described above.
  • Several cells are combined in series to form a stack, or "stack" to produce sufficient power for a particular desired application.
  • the plates are bipolar plates allowing this stacking.
  • Another object of the invention is the use of a material based on amyloid fibers in the manufacture of single-cell batteries, batteries using a stack of cells, and preferably PACs. These batteries are in particular the batteries described in the present application.
  • the fiber-based material amyloid is a film made up of a fibrous network of proteins, and particularly as described in the present application.
  • a preferred use according to the invention is the manufacture of membranes for batteries, and particularly for PACs. In particular, these batteries are those according to the invention.
  • Another object of the invention is a method of manufacturing a film or a membrane according to the invention, characterized in that a gel of amyloid fibers is formed and then spread and dried so as to form said film or said membrane.
  • the gel is formed by bringing protein (s) and water into contact under acidic conditions, for example pH 2 to 3, or neutral (for example pH 7 when the protein is insulin), with possibly a slight heating (temperature below 80 ° C).
  • Another object of the invention is a device comprising a membrane and / or a battery according to the invention and described in the present application.
  • Another object of the invention is the use of batteries according to the invention for the manufacture of emergency supply devices, portable technologies (computer, cell phone, charger, etc.) or devices requiring a required power of less than 100 kW.
  • Another object of the invention is an electrical device, such as those described above, comprising a cell or a stack of cells according to the invention.
  • FIG. 1 is a schematic and partial representation of the PEMFC type batteries of Examples 3 (example according to the invention) and 5 (comparative example).
  • Figure 2 shows the polarization and power curves for a conventional membrane-based PEMFC from Nafion TM and an ⁇ -lactalbumin (a-LAC) membrane based PEMFC.
  • Figure 3 shows the polarization curves and power curve for a PEMFC based on an ⁇ -lactalbumin ( ⁇ -LAC) membrane and for a PEMFC based on a 95/5 lysozyme / methylcellulose membrane. .
  • ⁇ -LAC ⁇ -lactalbumin
  • Example 1 production of an ⁇ -lactalbumin-based film according to the invention
  • ⁇ -lactalbumin (of bovine origin, CAS number 9051-29-0) was obtained from the company DAVISCO (US) with a purity greater than 90%. These proteins were diluted at a rate of 40 g / L in an aqueous solution of 50 mM hydrochloric acid HCl, to obtain a final pH equal to 2. This suspension was incubated for several days (typically 3 days) at 45 ° C under moderate agitation, until the formation of amyloid fibers which manifests itself in the case of ⁇ -lactalbumin by the formation of a thixotropic hydrogel. The presence of amyloid fibers was verified by electron microscopy.
  • Example 2 production of a lysozyme-based film according to the invention
  • the lysozyme (of avian origin, CAS number 12650-88-3) in chicken egg white was obtained from Sigma-Aldrich (ref. L-6876) with a purity of approximately 95%. These proteins were diluted at a rate of 40 g / L in an aqueous solution of hydrochloric acid HCl for a final pH of 2.7 containing 90 mM of NaCl. This suspension was incubated for several days (typically 3 days) at 60 ° C with moderate agitation, until the formation of amyloid fibers which is manifested in the case of lysozyme by the formation of a hydrogel. The presence of amyloid fibers was verified by electron microscopy. In this example, 5% by mass of a solution of methylcellulose in HCl (pH 3) is added to the lysozyme solution in order to improve the mechanical properties (stability, elasticity) of the film obtained after drying.
  • Example 3 production of fuel cells (fuel cell)
  • Cells according to the invention were each produced with the membranes of Examples 1 and 2.
  • a membrane 30 was detached from its respective support and was positioned between two electrodes 20 of a fuel cell (hydrogen). conventional test from the company Paxitech (France).
  • a hydrogen / air fuel cell having 5 cm 2 of active surface.
  • Commercial gas diffusion electrodes are arranged on a Sigracet 29 BC brand gas diffusion layer (purchased from Fuelcellstore (USA)). It is a non-woven carbon paper with a microporous layer (MPL) treated with 5% by weight PTFE. It has a total thickness of 235 ⁇ m (microns).
  • the electrodes themselves are positioned on outer graphite plates 10 machined with a serpentine gas flow. That is, the active surface comprises a serpentine-shaped recess 1 mm wide by 1 mm deep (not shown).
  • PTFE gaskets and sub-gaskets are used to prevent gas leakage and ensure adequate electrical insulation.
  • Example 4 Battery performance according to the invention
  • Figure 3 shows the polarization and power curves which were obtained by galvanostatic discharges of 30 s at room temperature under atmospheric pressure with humidified gases (minimum relative humidity of 60% RH) (H2 and air) with respective flow rates of 20 mL min-1 for a membrane based on lysozyme and ⁇ -lactalbumin.
  • Comparative Example 5 realization of a cell with Nafion TM membrane
  • a membrane 30 having the following characteristics (DUPONT Nafion TM NRE212, thickness 50 ⁇ m -CAS No. 31 175-20-9) instead of a membrane (30 ) according to the invention.
  • the tests were carried out under conditions identical to those described above except that the discharges were carried out at a humidity level of 100% and not of 60%.
  • Figure 2 shows the polarization curve (black) and the power curve (blue) the PEMFC cells based on a conventional membrane from Nafion TM and a PEMFC based on an ⁇ -lactalbumin membrane (a -LAKE).
  • the discharges were carried out at 1 atm in H2 and air at a humidity level of 60% for ⁇ -lactalbumin and 100% for Nafion TM.
  • Example 6 production of a crosslinked film based on ⁇ -lactalbumin and glutaraldehyde according to the invention
  • the self-supported protein membranes were also subjected to a chemical crosslinking step in the presence of glutaraldehyde vapor (Supplier Sigma-Aldrich, 50% (by mass) in water).
  • the protein film of Example 1 once dried, is subjected to vapors of glutaraldehyde for 30 min at 25 ° C.
  • this step therefore allows the battery to operate over a wide temperature range. Its temperature resistance goes from 35 ° C, without chemical crosslinking, to at least 60 ° C after chemical crosslinking, or even more.
  • a PEMFC comprising such a membrane does not lose its performance after several days of
  • the invention is not limited to the embodiments presented and other embodiments will be apparent to those skilled in the art. It is notably possible to consider the use of peptides which can form amyloid fibers which organize themselves into hydrogels. It is also possible to use the membranes according to the invention on any type of PEMFC. It can be used not only for hydrogen fuel cells but also direct methanol fuel cells (DMFC).
  • DMFC direct methanol fuel cells

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Abstract

Disclosed is a cell comprising an anode, a cathode and a membrane located between the anode and the cathode, wherein the membrane comprises an aqueous medium and a film comprising amyloid fibers. The invention further relates to said film, stacks of said cells, an electrolyte membrane, and the use of these various devices.

Description

Description Description

Titre de l’invention : Membrane échangeuse d’ions Title of the invention: Ion exchange membrane

Domaine de l’invention Field of the invention

L’invention concerne l’utilisation de molécules organiques, telles que des protéines, se présentant sous forme de fibres amyloïdes dans une membrane échangeuse d’ions, cette membrane pouvant être utilisée dans des dispositifs électrochimiques tels que les piles à combustible. The invention relates to the use of organic molecules, such as proteins, in the form of amyloid fibers in an ion exchange membrane, which membrane can be used in electrochemical devices such as fuel cells.

Art antérieur Prior art

Une pile à combustible (PAC) est une pile dans laquelle la génération d'une tension électrique se fait grâce à l'oxydation sur l’anode (émettrice d’électron) d'un combustible réducteur (par exemple le dihydrogène : H2) couplée à la réduction sur la cathode (collectrice d’électron) d'un oxydant, tel que le dioxygène (O2) de l'air. Les piles à combustible à membrane d'échange de protons, connues aussi sous le nom de piles à combustible à membrane électrolyte polymère (ou PEMFC selon l'acronyme des expressions anglaises « proton exchange membrane fuel cells » ou « polymer electrolyte membrane fuel cells ») sont un type de piles à combustible développées pour des applications dans le domaine du transport (voiture, bus, aéronefs etc. ...) aussi bien que les ordinateurs portables, des téléphones cellulaires. Leurs A fuel cell (PAC) is a cell in which the generation of an electrical voltage is done through the oxidation on the anode (electron emitter) of a reducing fuel (for example dihydrogen: H2) coupled the reduction on the cathode (electron collector) of an oxidant, such as oxygen (O2) from the air. Proton exchange membrane fuel cells, also known under the name of polymer electrolyte membrane fuel cells (or PEMFC according to the acronym of the English expressions "proton exchange membrane fuel cells" or "polymer electrolyte membrane fuel cells" ) are a type of fuel cells developed for applications in the field of transport (car, bus, aircraft etc ...) as well as laptops, cell phones. Their

caractéristiques propres incluent un fonctionnement des gammes de basses pressions (typiquement pression atmosphérique à 10 bars) et températures (typiquement 20- 100°C) et une membrane électrolyte spécifique. Specific characteristics include operation of the low pressure (typically atmospheric pressure at 10 bar) and temperature (typically 20-100 ° C) ranges and a specific electrolyte membrane.

Pour que la pile fonctionne, la membrane doit pouvoir conduire les ions For the battery to function, the membrane must be able to conduct the ions

hydroxonium (H3CF), noté également dans une version simplifiée H+, mais non les électrons. La membrane doit de plus répondre à un grand nombre de critères additionnels pour pouvoir fonctionner. Tout d’abord, elle ne doit permettre le passage d'aucun gaz d'un côté à l'autre de la cellule. Ce phénomène est connu sous le nom de "gas crossover" (croisement de gaz). La membrane doit résister à l'environnement réducteur à l'anode et, en même temps, à un environnement oxydant à la cathode. Elle doit également être capable de fonctionner dans les gammes d’humidité et de température de fonctionnement de la PEMFC les plus larges possibles. Enfin, une source significative de pertes énergétiques est la résistance de la membrane au flux de protons. Cette résistance est minimisée en rendant la membrane aussi fine que possible (de l'ordre de 50-20 pm). Des membranes en polystyrène sulfonaté furent initialement utilisées pour les électrolytes, mais elles furent remplacées en 1966 par l'ionomère Nafion™, supérieur en performance et durabilité. Des polymères hydroxonium (H 3 CF), also noted in a simplified version H + , but not electrons. The membrane must also meet a large number of additional criteria to be able to function. First of all, it must not allow the passage of any gas from one side of the cell to the other. This phenomenon is known as "gas crossover". The membrane must resist the reducing environment at the anode and, at the same time, an oxidizing environment at the cathode. It should also be capable of operating within the broadest possible operating humidity and temperature ranges of the PEMFC. Finally, a significant source of energy losses is the resistance of the membrane to the flow of protons. This resistance is minimized by making the membrane as thin as possible (on the order of 50-20 µm). Sulfonated polystyrene membranes were initially used for electrolytes, but were replaced in 1966 by the ionomer Nafion ™, superior in performance and durability. Polymers

comprenant des motifs hétérocycliques à base de poly(pyrrole) et comprenant des groupements attracteurs et donneurs de protons sont décrit comme aptes à former de telles membranes dans W02009/040362. A ce jour le Nation™, un polymère perfluoré fabriqué par Dupont, reste encore le matériau de référence pour la fabrication de membranes échangeuses de protons. Cependant, d’autres groupes industriels (Aciplex, Flemion, 3M, SCC) ont développé des alternatives (voir Kusoglu & A.Z. comprising heterocyclic units based on poly (pyrrole) and comprising proton attracting and donor groups are described as capable of forming such membranes in WO2009 / 040362. To date, Nation ™, a perfluorinated polymer manufactured by Dupont, still remains the reference material for the manufacture of proton exchange membranes. However, other industrial groups (Aciplex, Flemion, 3M, SCC) have developed alternatives (see Kusoglu & AZ

Weber, Chemical Reviews 1 17, 987-1104 (2017) [1]). Weber, Chemical Reviews 1 17, 987-1104 (2017) [1]).

Le fonctionnement d'une pile dihydrogène-dioxygène est particulièrement propre puisqu'il ne produit que de l'eau et de la chaleur et consomme uniquement des gaz. Elles sont donc perçues comme ayant un impact très faible sur l’environnement. The operation of a hydrogen-dioxygen cell is particularly clean since it produces only water and heat and consumes only gases. They are therefore perceived as having a very low impact on the environment.

Cependant le coût des membranes échangeuses d'ions, et plus particulièrement de protons (ion HsO+) reste encore un facteur limitant important au développement de PAC de type PEMFC. Un autre problème provient de la nature inerte des matériaux perfluorés constituants les membranes comme le Nafion™, qui n’est pas However, the cost of ion exchange membranes, and more particularly of protons (HsO + ion) still remains a major limiting factor to the development of PACs of the PEMFC type. Another problem stems from the inert nature of the perfluorinated materials constituting the membranes such as Nafion ™, which is not

biodégradable. Enfin un problème supplémentaire réside dans les performances modérées à bas taux d’humidité (en dessous de 50%) et à basses températures (en dessous de 50°C). biodegradable. Finally, an additional problem lies in the moderate performance at low humidity (below 50%) and at low temperatures (below 50 ° C).

Il existe donc un besoin pour des membranes échangeuses d’ions, à faible coûts et/ou biodégradables et qui présentent de plus une ou plusieurs des caractéristiques ci-dessus mentionnées propres à de telles membranes et des performances similaires au Nafion™. L’invention a donc pour but de remédier à ce besoin. There is therefore a need for ion exchange membranes, at low cost and / or biodegradable and which also exhibit one or more of the above-mentioned characteristics specific to such membranes and performance similar to Nafion ™. The aim of the invention is therefore to remedy this need.

Description de l’invention Description of the invention

De manière surprenante il est établi par la présente demande que des matériaux organiques, et en particulier biologiques, comprenant des fibres de type amyloïde sont à même de répondre entièrement ou partiellement à ces besoins très spécifiques. Surprisingly, it is established by the present application that organic materials, and in particular biological materials, comprising fibers of amyloid type are able to fully or partially meet these very specific needs.

Les fibres amyloïdes sont des nanostructures fibrillaires très stables formées par un mécanisme d’autoassemblage spontané de protéines ou de polypeptides. Ces fibres partagent le même type de structure en feuillets-b intermoléculaires. Une protéine amyloïde acquiert une structure secondaire riche en brins-b qui s’associent via des liaisons-H pour former ces feuillets-b. La formation de ces feuillets-b, puis de fibres, de manière spontanée est dépendante de paramètres extérieurs, en particulier du pH et de la force ionique du milieu, de la concentration de protéines ou de polypeptides, de la présence d’autres molécules ou encore des paramètres de température et d’agitation, qui peuvent conduire à des cinétiques de fibrillation et des organisations différentes. Des fibres amyloïdes fonctionnalisées peuvent être utilisées comme des nanofils conducteurs électroniques ( cf . W02012/120013). Des hydrogels comprenant de l’a- lactalbumine sont considérés pour une utilisation éventuelle dans le domaine biomédical (pansements) ou dans des peintures {cf. WO2012/136909). Dans le domaine des piles il est également généralement connu d’utiliser des protéines enzymatiques à l’anode ou à la cathode pour catalyser les réactions d’oxydation et/ou de réduction. La demande PCT W02008058165 décrit de telles piles. La demande PCT W02009040362, quant à elle décrit des membranes échangeuse de protons de pile à combustible alternatives aux membranes Amyloid fibers are very stable fibrillar nanostructures formed by a mechanism of spontaneous self-assembly of proteins or polypeptides. These fibers share the same type of intermolecular b-sheet structure. An amyloid protein acquires a secondary structure rich in b-strands which combine via H-bonds to form these b-sheets. The formation of these b-sheets, then of fibers, spontaneously is dependent on external parameters, in particular the pH and the ionic strength of the medium, the concentration of proteins or polypeptides, the presence of other molecules or further temperature and agitation parameters, which can lead to different fibrillation kinetics and organizations. Functionalized amyloid fibers can be used as electronically conductive nanowires (cf. WO2012 / 120013). Hydrogels comprising α-lactalbumin are considered for possible use in the biomedical field (dressings) or in paints (cf. WO2012 / 136909). In the field of batteries, it is also generally known to use enzymatic proteins at the anode or at the cathode to catalyze oxidation and / or reduction reactions. PCT application WO2008058165 describes such stacks. PCT application W02009040362, for its part, describes fuel cell proton exchange membranes that are alternatives to membranes

échangeuses de protons déjà connues comme le Nation™. Ces membranes alternatives comprennent des polymères greffés comprenant une chaîne principale à motif hétérocyclique comme le polypyrrolle ayant des chaînes latérales, ou "greffons". Ces greffons peuvent comprendre des peptides ou des polypeptides de 1 à 10 motifs polypeptidiques. De telles molécules ne sont pas de manière évidente des fibres amyloïdes. proton exchangers already known as the Nation ™. These alternative membranes include graft polymers comprising a main chain having a heterocyclic unit such as polypyrrol having side chains, or "grafts". These grafts can comprise peptides or polypeptides of 1 to 10 polypeptide units. Such molecules are not obviously amyloid fibers.

L’invention a pour objet une membrane échangeuse de d’ions, notamment de protons, comprenant un liquide aqueux et un film comprenant des fibres amyloïdes. The subject of the invention is an ion exchange membrane, in particular protons, comprising an aqueous liquid and a film comprising amyloid fibers.

Un film est une structure ayant des dimensions latérales très supérieures à son épaisseur. Par "très supérieures" il est généralement compris que les dimensions latérales sont au moins 100 fois supérieures à l’épaisseur. Cette épaisseur peut être avantageusement choisie dans une gamme variant de 10 nm à 1 mm, de préférence 100 nm à 150 pm de manière à empêcher le gas crossover tout en ne limitant pas la conduction de manière substantielle. Une épaisseur allant de 1 à 75 pm, en particulier 15 à 55 pm (par exemple 20 à 30 pm) permet d’obtenir des résultats particulièrement satisfaisants. La surface de la membrane peut, quand elle, être choisie dans une gamme allant de 1 mm2 à 10 cm2, de préférence de 1 à 50 mm2. Une membrane est un type de film présentant une structure à travers laquelle un transfert peut se produire sous diverses forces motrices. A film is a structure having lateral dimensions much greater than its thickness. By "much greater" it is generally understood that the lateral dimensions are at least 100 times greater than the thickness. This thickness can be advantageously chosen in a range varying from 10 nm to 1 mm, preferably 100 nm to 150 μm, so as to prevent gas crossover while not limiting conduction substantially. A thickness ranging from 1 to 75 μm, in particular 15 to 55 μm (for example 20 to 30 μm) makes it possible to obtain particularly satisfactory results. The surface of the membrane can, when it, be chosen in a range going from 1 mm 2 to 10 cm 2 , preferably from 1 to 50 mm 2 . A membrane is a type of film having a structure through which transfer can occur under various driving forces.

Un autre objet de l’invention est un film comprenant des, ou constitué de, fibres amyloïdes. Another object of the invention is a film comprising, or consisting of, amyloid fibers.

La membrane selon l’invention comprend un tel film lui-même comprenant des, ou étant constitué de, fibres amyloïdes, de préférence en réseau. On rappelle que les fibres amyloïdes sont généralement des fibres qui résultent de l'autoassemblage de protéines ou de polypeptides. Cet autoassemblage a pour caractéristique de s'auto- propager puisque l'ajout d'une faible quantité (processus d’ensemencement) d'une protéine sous forme de fibres amyloïdes dans une suspension de cette même protéine accélère la cinétique de croissance de fibres amyloïdes. Les fibres amyloïdes présentent une structure caractéristique en feuillets b intermoléculaires et possèdent également un profil de diffraction des rayons X caractéristique. Les fibres amyloïdes correspondent donc à l’empilement de polypeptides/protéines dans des fibres linéaires et généralement non-branchées. Ces fibres sont stabilisées par l’empilement de brins b disposés perpendiculairement à l’axe de la fibre et reliés par un réseau de liaisons hydrogènes. Elles montrent habituellement une coloration au rouge Congo associée à une biréfringence sous lumière polarisée (Sipe & Cohen, Journal of Structural Biology 130, 88-98 (2000) [2]) et provoquent une forte augmentation de la fluorescence émise par la thioflavine-T à la longueur d'onde de 480 nm (Sabaté et al., Journal of Structural Biology 162, 387-396 (2008) [3]). Les fibres amyloïdes sont généralement The membrane according to the invention comprises such a film itself comprising, or consisting of, amyloid fibers, preferably in a network. It should be remembered that amyloid fibers are generally fibers which result from the self-assembly of proteins or polypeptides. This self-assembly has the characteristic of being self-propagating since the addition of a small quantity (seeding process) of a protein in the form of amyloid fibers in a suspension of this same protein accelerates the growth kinetics of amyloid fibers. . Amyloid fibers exhibit a characteristic intermolecular b-sheet structure and also have a characteristic X-ray diffraction profile. Amyloid fibers therefore correspond to the stacking of polypeptides / proteins in linear and generally non-branched fibers. These fibers are stabilized by stacking strands b arranged perpendicular to the axis of the fiber and connected by a network of hydrogen bonds. They usually show Congo red staining associated with birefringence under polarized light (Sipe & Cohen, Journal of Structural Biology 130, 88-98 (2000) [2]) and cause a sharp increase in the fluorescence emitted by thioflavin-T at the wavelength of 480 nm (Sabaté et al., Journal of Structural Biology 162, 387-396 (2008) [3]). Amyloid fibers are generally

caractérisées par un facteur de forme ("aspect ratio") élevé : diamètre de quelques nanomètres à quelques dizaines de nanomètres pour une longueur de l’ordre du micron jusqu’à la dizaine de microns lorsque les fibres sont formées spontanément (Doussineau et al., Angewandte Chemie International Edition 55, 2340-2344 (2016) [4]). characterized by a high form factor ("aspect ratio"): diameter from a few nanometers to a few tens of nanometers for a length of the order of a micron up to ten microns when the fibers are formed spontaneously (Doussineau et al. , Angewandte Chemie International Edition 55, 2340-2344 (2016) [4]).

Dans le contexte de l’invention on entend donc par "fibre amyloïde" une fibre comprenant, ou étant essentiellement constituée, d'au moins un polypeptide ou d'au moins une protéine, ladite fibre comprenant un empilement de brins b de ladite protéine ou dudit polypeptide, lesdits brins étant disposés perpendiculairement à l’axe de la fibre étant reliés par un réseau de liaisons hydrogènes. Avantageusement une ou plusieurs caractéristiques structurelles additionnelle suscitées sont présentes, par exemple leurs tailles et/ou leur rapport de forme. Les fibres amyloïdes utilisées dans le cadre de l’invention peuvent provenir de toute origine, naturelle ou synthétique. De préférence, elles comprennent, ou sont constituées, d’au moins un peptide ou une protéine, et de préférence biosourcé(e) ou d’origine biologique, par exemple l’a- lactalbumine, le lysozyme, la b-lactoglobuline, le domaine prion de Het-s et l’insuline. L’utilisation de mélanges de fibres d’origine différente est également envisagée, bien que l’utilisation d’une seul type de fibre ait l’avantage de la simplicité. In the context of the invention is therefore meant by "amyloid fiber" a fiber comprising, or consisting essentially of at least one polypeptide or of at least one protein, said fiber comprising a stack of strands b of said protein or of said polypeptide, said strands being arranged perpendicular to the axis of the fiber being connected by a network of hydrogen bonds. Advantageously one or more additional structural characteristics mentioned are present, for example their sizes and / or their aspect ratio. The amyloid fibers used in the context of the invention can come from any origin, natural or synthetic. Preferably, they comprise, or consist, of at least one peptide or a protein, and preferably bio-based or of biological origin, for example α-lactalbumin, lysozyme, β-lactoglobulin, prion domain of Het-s and insulin. The use of mixtures of fibers of different origin is also envisioned, although the use of a single type of fiber has the advantage of simplicity.

Avantageusement elles sont choisies dans le groupe des molécules peu coûteuses et/ou disponibles en grande quantités telles que Ga-lactalbumine ou le lysozyme. Il est possible d’utiliser une seule protéine ou un mélange de protéines pour la réalisation de l’invention. Les fibres amyloïdes peuvent également provenir de polypeptides, voire de peptides. Advantageously, they are chosen from the group of molecules that are inexpensive and / or available in large quantities, such as Ga-lactalbumin or lysozyme. It is possible to use a single protein or a mixture of proteins for the realization of the invention. The amyloid fibers can also come from polypeptides, or even from peptides.

Selon un aspect préférentiel de l’invention le film et/ou la membrane selon l’invention est fabriqué à partir d’une solution de protéines (qui forme alors un hydrogel en milieu aqueux). Après dépôt et séchage de l’hydrogel, un film est alors obtenu dont la matrice comprend un réseau fibreux, qui comprend des, ou est constitué According to a preferred aspect of the invention, the film and / or the membrane according to the invention is made from a protein solution (which then forms a hydrogel in aqueous medium). After depositing and drying the hydrogel, a film is then obtained, the matrix of which comprises a fibrous network, which comprises, or consists of

essentiellement de, fibres amyloïdes. mainly, amyloid fibers.

Bien entendu le liquide aqueux permettant la réalisation de l’hydrogel ou celui présent dans la membrane comprend essentiellement de l’eau mais peut contenir une faible proportion d’autres composés, tels que des sels en solution ou d’autres additifs. L’expression «faible proportion» peut indiquer que le liquide est constitué d’au moinsOf course, the aqueous liquid allowing the preparation of the hydrogel or that present in the membrane essentially comprises water but may contain a small proportion of other compounds, such as salts in solution or other additives. The expression "low proportion" may indicate that the liquid consists of at least

80% en masse d’eau par rapport à la masse total de liquide, de préférence d’au moins80% by mass of water relative to the total mass of liquid, preferably at least

90% en masse d’eau par rapport à la masse total de liquide et en particulier d’au moins90% by mass of water relative to the total mass of liquid and in particular at least

95% en masse d’eau par rapport à la masse total de liquide. Un tel hydrogel est généralement désigné comme étant un gel supramoléculaire. 95% by mass of water relative to the total mass of liquid. Such a hydrogel is generally referred to as a supramolecular gel.

Le film et/ou la membrane peut avantageusement être formé par dépôt d’une solution de protéines, dont la concentration est typiquement de, 1 g/L à 500 g/L. De préférence la concentration de cette solution est typiquement comprise entre, ou allant de1 g/L et 150 g/L (c’est-à-dire entre, ou allant de, 0,1 et 15% en proportion massique par rapport au solvant aqueux). La concentration de la solution de protéines peut avantageusement aller de 25 g/L à 100 g/L. The film and / or the membrane can advantageously be formed by depositing a solution of proteins, the concentration of which is typically from .1 g / L to 500 g / L. Preferably, the concentration of this solution is typically between, or ranging from 1 g / L and 150 g / L (that is to say between, or ranging from, 0.1 and 15% in mass proportion relative to the solvent. aqueous). The concentration of the protein solution can advantageously range from 25 g / L to 100 g / L.

Il est également préféré que le film et/ou la membrane selon l’invention soit autoportant(e) (ou autosupporté(e)), c’est-à-dire suffisamment rigide pour pouvoir être manipulé(e) et disposé(e) dans un dispositif tel qu’une pile selon l’invention. Cependant selon une variante de l’invention, le film et/ou la membrane peut également It is also preferred that the film and / or the membrane according to the invention is self-supporting (or self-supporting), that is to say sufficiently rigid to be able to be handled and placed. in a device such as a battery according to the invention. However, according to a variant of the invention, the film and / or the membrane can also

comprendre un renfort mécanique et/ou un ou plusieurs additifs. Ces additifs peuvent avoir un ou plusieurs objectifs et notamment être choisis dans le groupe constitué par :include a mechanical reinforcement and / or one or more additives. These additives can have one or more objectives and in particular be chosen from the group consisting of:

- des ions pour moduler la conduction ionique, - ions to modulate ionic conduction,

- des plastifiants pour ajuster le niveau des propriétés mécaniques (Module d’Young E [MPa], Abaissement de la transition vitreuse) et faciliter la mise en œuvre des membranes, par exemple des polymères tels que la méthylcellulose, des dérivés organiques et inorganiques à base de silice, - plasticizers to adjust the level of mechanical properties (Young's modulus E [MPa], Lowering of the glass transition) and to facilitate the use of membranes, for example polymers such as methylcellulose, organic and inorganic derivatives with silica base,

- des agents de réticulation, par exemple du glutaraldéhyde (pentane-1 ,5-dial), pour réticuler chimiquement (de manière irréversible) la membrane afin d’assurer une stabilité chimique et dimensionnelle, - crosslinking agents, for example glutaraldehyde (pentane-1, 5-dial), to chemically crosslink (irreversibly) the membrane in order to ensure chemical and dimensional stability,

- des antioxydants et des pièges à radicaux pour limiter les processus de dégradation chimique de la membrane, tel que des antioxydants naturels (par ex. vitamine E (sous ses 8 formes naturelles : a-tocophérol, b-tocophérol, y-tocophérol, d-tocophérol, a- tocotriénol, b-tocotriénol, g-tocotriénol et d-tocotriénol, ascorbic acid, 3,4-dihydroxy- cinnamic acid) ou des cations métalliques tel que le cérium, - antioxidants and radical scavengers to limit the chemical degradation processes of the membrane, such as natural antioxidants (eg vitamin E (in its 8 natural forms: a-tocopherol, b-tocopherol, y-tocopherol, d -tocopherol, a- tocotrienol, b-tocotrienol, g-tocotrienol and d-tocotrienol, ascorbic acid, 3,4-dihydroxy-cinnamic acid) or metal cations such as cerium,

- des anti-UV pour limiter une éventuelle photo-dégradation. - UV stabilizers to limit any photo-degradation.

De manière préférée, la méthode de fabrication du film et/ou de la membrane peut comprendre une étape de réticulation chimique. L’agent réticulant peut, par exemple, être un composé tel que du glutaraldéhyde. L’étape de réticulation peut être mise en œuvre par la mise en présence de l’agent de réticulation et du film et/ou de la membrane déjà formée, par exemple en l’exposant ledit film ou ladite membrane à des vapeurs de l’agent réticulant. De manière avantageuse, la membrane selon l’invention ne permet pas le passage des électrons. Il est également préféré qu’elle ne permette pas le passage de gaz. De manière avantageuse, la membrane doit résister à l'environnement réducteur (par ex. un milieu riche en dihydrogène) et, en même temps, à un environnement oxydant, tel que l’air (dioxygène). Enfin il est également préféré que ladite membrane puisse présenter une capacité à échanger des ions Preferably, the method of manufacturing the film and / or the membrane can comprise a chemical crosslinking step. The crosslinking agent can, for example, be a compound such as glutaraldehyde. The crosslinking step can be carried out by bringing the crosslinking agent together with the film and / or the membrane already formed, for example by exposing said film or said membrane to vapors of the crosslinking agent. Advantageously, the membrane according to the invention does not allow the passage of electrons. It is also preferred that it does not allow the passage of gas. Advantageously, the membrane should resist the reducing environment (eg a medium rich in hydrogen) and, at the same time, an oxidizing environment, such as air (oxygen). Finally, it is also preferred that said membrane can have an ability to exchange ions.

à basse température, par exemple de 0°C à 45°C, de préférence de 10°C à 30°C, et notamment aux environs de 25°C ; et/ou at low temperature, for example from 0 ° C to 45 ° C, preferably from 10 ° C to 30 ° C, and in particular around 25 ° C; and or

à bas taux d’humidité relative, par exemple de 45% à 75%, de préférence de 55% à 65%, et notamment aux environs de 60%. at low relative humidity, for example 45% to 75%, preferably 55% to 65%, and in particular around 60%.

De préférence, elle doit également être capable de fonctionner aux températures de fonctionnement les plus courantes des PEMFC (45°C à 95°C) et 60 à 100% d’humidité relative, le taux d’humidité étant déterminé de la manière usuelle. Preferably, it should also be capable of operating at the most common PEMFC operating temperatures (45 ° C to 95 ° C) and 60 to 100% relative humidity, the humidity level being determined in the usual manner.

La membrane permet l’échange ionique, et en particulier l’échange de protons. Cependant d’autres ions, cations ou anions, peuvent être échangés et notamment des ions hydroxydes, OH . The membrane allows ion exchange, and in particular the exchange of protons. However, other ions, cations or anions can be exchanged and in particular hydroxide ions, OH.

Un autre objet de l’invention est une pile, de préférence à combustible, comprenant : Another object of the invention is a cell, preferably fuel cell, comprising:

- une anode ; - an anode;

- une cathode ; et - a cathode; and

- une membrane située entre l’anode et la cathode, - a membrane located between the anode and the cathode,

ladite membrane comprenant un liquide aqueux et un film comprenant des fibres amyloïdes. said membrane comprising an aqueous liquid and a film comprising amyloid fibers.

De préférence la membrane comprend, ou est constituée de, une membrane telle que celle décrite dans la présente demande. La membrane dans la pile selon l’invention fait fonction d’électrolyte, puisqu’elle contient les ions qui peuvent pénétrer et circuler dans la matrice du film par diffusion. Avec l’anode et la cathode, la membrane constitue le cœur de la pile. Preferably the membrane comprises, or consists of, a membrane such as that described in the present application. The membrane in the battery according to the invention acts as an electrolyte, since it contains the ions which can penetrate and circulate in the film matrix by diffusion. Together with the anode and the cathode, the membrane forms the heart of the cell.

Il est également préféré que le film comprenant des fibres amyloïdes soit tel que décrit dans la présente demande. Le dispositif de base comprenant une anode, une cathode et une membrane selon l’invention peut être décrit en tant que cellule électrochimique, où simplement cellule. It is also preferred that the film comprising amyloid fibers is as described in the present application. The basic device comprising an anode, a cathode and a membrane according to the invention can be described as an electrochemical cell, or simply a cell.

L’anode et la cathode peuvent être de tous types mais sont généralement choisies du type standard dans des matériaux permettant les réactions électrochimiques à l’anode et à la cathode. Dans le cas de PEMFCs elles sont généralement constituées d’un catalyseur, par exemple de particules de platine de 2 à 4 nm, de polymère ionique et d’un matériau conducteur tel qu’un tissu ou une poudre de carbone. Ces matériaux sont généralement associés à une couche de diffusion des gaz (GDL selon l'acronyme de l’expression anglaise "Gaz Diffusion Layer"). Cette couche permet d’assurer une répartition homogène des gaz, éventuellement une bonne gestion de l’eau dans la pile, et une tenue mécanique de la membrane et des couches actives contenant les matériaux réactifs de l’anode et de la cathode. Une telle couche est généralement constituée d’un tissu carboné poreux d’épaisseur pouvant être comprise entre 100 pm et 300 pm et enduit de polymère, généralement du PTFE. Les fibres de carbone du tissu peuvent être arrangées de façon différente, par exemple tissées et non tissées. The anode and the cathode can be of any type but are generally chosen from the standard type in materials allowing the electrochemical reactions at the anode and at the cathode. In the case of PEMFCs, they generally consist of a catalyst, for example platinum particles of 2 to 4 nm, of ionic polymer and of a conductive material such as a fabric or a carbon powder. These materials are generally associated with a gas diffusion layer (GDL according to the acronym of the English expression "Gaz Diffusion Layer"). This layer makes it possible to ensure a homogeneous distribution of the gases, possibly good management of the water in the cell, and a mechanical strength of the membrane and of the active layers containing the reactive materials of the anode and of the cathode. Such a layer generally consists of a porous carbon fabric with a thickness which may be between 100 μm and 300 μm and coated with polymer, generally PTFE. The carbon fibers of the fabric can be arranged in different ways, for example woven and non-woven.

La pile selon l’invention peut également comprendre des éléments supplémentaires, en particulier lorsque la pile selon l’invention est une pile à combustible (PAC), et en particulier du type " Proton-exchange membrane fuel celf' (PEMFC). The cell according to the invention can also include additional elements, in particular when the cell according to the invention is a fuel cell (PAC), and in particular of the "Proton-exchange membrane fuel celf" (PEMFC) type.

Ainsi selon un aspect préféré, la pile selon l’invention comprend en outre deux plaques : Thus, according to a preferred aspect, the battery according to the invention further comprises two plates:

- une première plaque pour distribuer un combustible réducteur, par exemple le dihydrogène, et - a first plate to distribute a reducing fuel, for example dihydrogen, and

- une deuxième plaque pour distribuer l'oxydant et, éventuellement, évacuer l'eau.- a second plate to distribute the oxidant and, possibly, to evacuate the water.

Chacune de ces plaques peut-être être en, ou comprendre du, graphite usiné, des matériaux métalliques et/ou des composites carbone/polymère ou carbone/carbone.Each of these plates may be made of, or comprise, machined graphite, metallic materials and / or carbon / polymer or carbon / carbon composites.

En plus de leur fonction de distribution, les plaques peuvent permettre d’assurer l’étanchéité entre les compartiments anodique et cathodique, éventuellement d’assurer la gestion de l’eau produite à la cathode, de collecter des électrons produits à l’anode et redistribués à la cathode, d’assurer le maintien de la pile dans son domaine de température de fonctionnement grâce à un système de refroidissement intégré et/ou d’assurer la cohésion mécanique de l’empilement lors du serrage et du In addition to their distribution function, the plates can provide a seal between the anode and cathode compartments, possibly manage the water produced at the cathode, collect electrons produced at the anode and redistributed at the cathode, to ensure the maintenance of the cell in its operating temperature range thanks to an integrated cooling system and / or to ensure the mechanical cohesion of the stack during tightening and

fonctionnement. operation.

Un autre élément de la pile selon l’invention est la présence éventuelle de moyens d’étanchéité, en particulier de joints. Ceux-ci ont pour fonction d’assurer l’étanchéité de la cellule nécessaire au fonctionnement optimal et sans danger de la pile et peuvent être constitués de PTFE, de silicone et d’EPDM (Ethylène propylène diène monomère). Another element of the battery according to the invention is the possible presence of sealing means, in particular seals. The function of these is to ensure the airtightness of the cell necessary for the optimal and safe operation of the battery and can be made of PTFE, silicone and EPDM (ethylene propylene diene monomer).

Un autre objet de l’invention est également d’empiler des cellules pour former une PAC selon l’invention telle que décrite ci-dessus. Plusieurs cellules sont combinées en série pour former un empilement, ou "stack" afin de produire une puissance suffisante vis à vis d’une application particulière souhaitée. Dans ce cas, les plaques sont des plaques bipolaires permettant d’effectuer cet empilement. Another object of the invention is also to stack cells to form a PAC according to the invention as described above. Several cells are combined in series to form a stack, or "stack" to produce sufficient power for a particular desired application. In this case, the plates are bipolar plates allowing this stacking.

Un autre objet de l’invention est l’utilisation d’un matériau à base de fibres amyloïdes dans la fabrication de piles à simple cellule, de piles recourant à un empilement de cellules, et de préférence de PACs. Ces piles sont notamment les piles décrites dans la présente demande. Avantageusement le matériau à base de fibres amyloïdes est un film constitué d’un réseau fibreux de protéines, et particulièrement tel que décrit dans la présente demande. Une utilisation préférée selon l’invention est la fabrication de membranes pour piles, et particulièrement pour PACs. Notamment ces piles sont celles selon l’invention. Another object of the invention is the use of a material based on amyloid fibers in the manufacture of single-cell batteries, batteries using a stack of cells, and preferably PACs. These batteries are in particular the batteries described in the present application. Advantageously, the fiber-based material amyloid is a film made up of a fibrous network of proteins, and particularly as described in the present application. A preferred use according to the invention is the manufacture of membranes for batteries, and particularly for PACs. In particular, these batteries are those according to the invention.

Un autre objet de l’invention est une méthode de fabrication d’un film ou d’une membrane selon l’invention caractérisée en ce qu’un gel de fibres amyloïdes est formé puis étalé et séché de manière à former ledit film ou ladite membrane. De manière préférentielle le gel est formé par la mise en contact de protéine(s) et d’eau dans des conditions acides, par exemple pH 2 à 3, ou neutre (par ex. pH 7 lorsque la protéine est l'insuline), avec éventuellement un léger chauffage (température inférieure à 80°C). Another object of the invention is a method of manufacturing a film or a membrane according to the invention, characterized in that a gel of amyloid fibers is formed and then spread and dried so as to form said film or said membrane. . Preferably, the gel is formed by bringing protein (s) and water into contact under acidic conditions, for example pH 2 to 3, or neutral (for example pH 7 when the protein is insulin), with possibly a slight heating (temperature below 80 ° C).

Un autre objet de l’invention est un dispositif comprenant une membrane et/ou une pile selon l’invention et décrite dans la présente demande. Another object of the invention is a device comprising a membrane and / or a battery according to the invention and described in the present application.

Un autre objet de l’invention est l’utilisation de piles selon l’invention pour la fabrication de dispositifs d’approvisionnement de secours, de technologies portables (ordinateur, téléphone portable, chargeur...) ou dispositifs nécessitant une puissance requise inférieure à 100 kW. Another object of the invention is the use of batteries according to the invention for the manufacture of emergency supply devices, portable technologies (computer, cell phone, charger, etc.) or devices requiring a required power of less than 100 kW.

Un autre objet de l’invention est un dispositif électrique, tel que ceux décrits ci- dessus, comprenant une pile ou un empilement de piles selon l’invention. Another object of the invention is an electrical device, such as those described above, comprising a cell or a stack of cells according to the invention.

Brève description des figures Brief description of the figures

L'invention sera mieux comprise à la lecture de la description qui va suivre donnée uniquement à titre d'exemple et faite en se référant aux dessins annexés dans lesquels : The invention will be better understood on reading the description which will follow, given solely by way of example and made with reference to the appended drawings in which:

[Fig. 1] la figure 1 est une représentation schématique et partielle des piles de type PEMFC des exemples 3 (exemple selon l’invention) et 5 (exemple comparatif). [Fig. 1] Figure 1 is a schematic and partial representation of the PEMFC type batteries of Examples 3 (example according to the invention) and 5 (comparative example).

[Fig. 2] la figure 2 représente les courbes de polarisation et de puissance pour une PEMFC à base d’une membrane conventionnelle de Nafion™ et une PEMFC à base d’une membrane à base d’a-lactalbumine (a-LAC). [Fig. 2] Figure 2 shows the polarization and power curves for a conventional membrane-based PEMFC from Nafion ™ and an α-lactalbumin (a-LAC) membrane based PEMFC.

[Fig. 3] la figure 3 représente les courbes de polarisation et courbe de puissance pour une PEMFC à base d’une membrane d’a-lactalbumine (a-LAC) et pour une PEMFC à base d’une membrane de lysozyme/méthylcellulose 95/5. [Fig. 3] Figure 3 shows the polarization curves and power curve for a PEMFC based on an α-lactalbumin (α-LAC) membrane and for a PEMFC based on a 95/5 lysozyme / methylcellulose membrane. .

Exemples de mise en œuvre Examples of implementation

Exemple 1 : réalisation d’un film à base d’a-lactalbumine selon l’invention L'a-lactalbumine (d’origine bovine, numéro CAS 9051-29-0) a été obtenue de la société DAVISCO (US) avec une pureté supérieure à 90%. Ces protéines ont été diluées à raison de 40 g/L dans une solution aqueuse d’acide chlorhydrique HCl 50 mM, pour obtenir un pH final égal à 2. Cette suspension a été incubée plusieurs jours (typiquement 3 jours) à 45°C sous agitation modérée, jusqu’à la formation de fibres amyloïdes qui se manifeste dans le cas de l'a-lactalbumine par la formation d’un hydrogel thixotrope. La présence de fibres amyloïdes a été vérifiée par microscopie électronique. 0,8 g de la solution a été coulé goutte à goutte sur un support constitué de fibres de verre revêtue de PTFE (Techniflon 208 A, d’épaisseur 80 pm, 53% de PTFE en masse, 107 g/m2). Le séchage a été effectué à température ambiante sous air, pendant 24 heures pour former un film autosupporté (20 pm d’épaisseur). Example 1: production of an α-lactalbumin-based film according to the invention Α-lactalbumin (of bovine origin, CAS number 9051-29-0) was obtained from the company DAVISCO (US) with a purity greater than 90%. These proteins were diluted at a rate of 40 g / L in an aqueous solution of 50 mM hydrochloric acid HCl, to obtain a final pH equal to 2. This suspension was incubated for several days (typically 3 days) at 45 ° C under moderate agitation, until the formation of amyloid fibers which manifests itself in the case of α-lactalbumin by the formation of a thixotropic hydrogel. The presence of amyloid fibers was verified by electron microscopy. 0.8 g of the solution was poured dropwise onto a support made of glass fibers coated with PTFE (Techniflon 208 A, 80 μm thick, 53% PTFE by mass, 107 g / m 2 ). The drying was carried out at room temperature in air, for 24 hours to form a self-supporting film (20 μm thick).

Exemple 2 : réalisation d’un film à base de lysozyme selon l’invention Example 2: production of a lysozyme-based film according to the invention

Le lysozyme (d’origine aviaire, numéro CAS 12650-88-3) du blanc d’œuf de poule a été obtenu de Sigma-Aldrich (ref. L-6876) avec une pureté de 95% environ. Ces protéines ont été diluées à raison de 40 g/L dans une solution aqueuse d’acide chlorhydrique HCl pour un pH final de 2.7 contenant 90 mM de NaCI. Cette suspension a été incubée plusieurs jours (typiquement 3 jours) à 60°C sous agitation modérée, jusqu’à la formation de fibres amyloïdes qui se manifeste dans le cas du lysozyme par la formation d’un hydrogel. La présence de fibres amyloïdes a été vérifiée par microscopie électronique. Dans cet exemple, 5% en masse d’une solution de méthylcellulose dans HCl (pH 3) sont ajoutés à la solution de lysozyme afin d’améliorer les propriétés mécaniques (stabilité, élasticité) du film obtenu après séchage. The lysozyme (of avian origin, CAS number 12650-88-3) in chicken egg white was obtained from Sigma-Aldrich (ref. L-6876) with a purity of approximately 95%. These proteins were diluted at a rate of 40 g / L in an aqueous solution of hydrochloric acid HCl for a final pH of 2.7 containing 90 mM of NaCl. This suspension was incubated for several days (typically 3 days) at 60 ° C with moderate agitation, until the formation of amyloid fibers which is manifested in the case of lysozyme by the formation of a hydrogel. The presence of amyloid fibers was verified by electron microscopy. In this example, 5% by mass of a solution of methylcellulose in HCl (pH 3) is added to the lysozyme solution in order to improve the mechanical properties (stability, elasticity) of the film obtained after drying.

0,8 g de la solution a été coulé goutte à goutte sur un support constitué de fibres de verre revêtue de PTFE (Techniflon 208 A, d’épaisseur 80 pm, 53% de PTFE en masse, 107 g/m2). Le séchage a été effectué à température ambiante sous air, pendant 24 heures pour former un film autosupporté (20 pm d’épaisseur). 0.8 g of the solution was poured dropwise onto a support made of glass fibers coated with PTFE (Techniflon 208 A, 80 μm thick, 53% PTFE by mass, 107 g / m 2 ). The drying was carried out at room temperature in air, for 24 hours to form a self-supporting film (20 μm thick).

Exemple 3 : réalisation de piles à combustibles (fuel cell) Example 3: production of fuel cells (fuel cell)

Des piles selon l’invention ont été réalisées avec chacune les membranes des exemples 1 et 2. Pour chaque pile, une membrane 30 a été détachée de son support respectif et a été positionnée entre deux électrodes 20 d’une pile à combustible (hydrogène) test conventionnelle provenant de la société Paxitech (France). En résumé, une pile à combustible à hydrogène/air ayant 5 cm2 de surface active. Les électrodes à diffusion de gaz commerciales sont disposées sur une couche à diffusion de gaz de marque Sigracet 29 BC (achetée chez Fuelcellstore (USA)). Il s’agit d’un papier carbone non tissé avec une couche microporeuse (MPL) traitée au PTFE à 5% en poids. Il a une épaisseur totale de 235 pm (microns). Les électrodes Cells according to the invention were each produced with the membranes of Examples 1 and 2. For each cell, a membrane 30 was detached from its respective support and was positioned between two electrodes 20 of a fuel cell (hydrogen). conventional test from the company Paxitech (France). In summary, a hydrogen / air fuel cell having 5 cm 2 of active surface. Commercial gas diffusion electrodes are arranged on a Sigracet 29 BC brand gas diffusion layer (purchased from Fuelcellstore (USA)). It is a non-woven carbon paper with a microporous layer (MPL) treated with 5% by weight PTFE. It has a total thickness of 235 µm (microns). Electrodes

comprennent ainsi une charge de platine 0,5 mg.cm 2 sur un support en poudre de carbone de type Vulcan déposés sur papier de fibres de carbone (Sigracet 29BC).thus comprise a 0.5 mg.cm 2 platinum filler on a Vulcan-type carbon powder support deposited on carbon fiber paper (Sigracet 29BC).

Les électrodes sont elles-mêmes positionnées sur des plaques externes en graphite 10 usinées avec un écoulement de gaz serpentin. C’est-à-dire que la surface active comprend un évidement de forme serpentine de 1 mm de large par 1 mm de profondeur (non représenté). The electrodes themselves are positioned on outer graphite plates 10 machined with a serpentine gas flow. That is, the active surface comprises a serpentine-shaped recess 1 mm wide by 1 mm deep (not shown).

Des joints et des sous-joints en PTFE sont utilisés pour éviter toute fuite de gaz et assurer une isolation électrique adéquate. PTFE gaskets and sub-gaskets are used to prevent gas leakage and ensure adequate electrical insulation.

Exemple 4 : Performances de piles selon l’invention Example 4: Battery performance according to the invention

En fonctionnement, le dihydrogène (H2) entre par la plaque 10 à gauche sur la figure 1. Arrivé à l'anode, le dihydrogène se dissocie (oxydation) en ions H+ et en électrons selon : 2H2 = 4FT + 4e . Les ions traversent alors la membrane 30, mais les électrons, bloqués, sont contraints d'emprunter le circuit extérieur, ce qui est générateur de courant. À la cathode, les ions hydrogène, les électrons, et du dioxygène (pur ou provenant de l'air) se rencontrent pour former de l'eau selon la réaction : 4FT + 4e + 02 = 2H2O. L'eau et le dioxygène passent par la plaque 10 droite. Cette réaction va produire également de la chaleur pouvant être récupérée.In operation, the dihydrogen (H2) enters through plate 10 on the left in FIG. 1. Arrived at the anode, the dihydrogen dissociates (oxidation) into H + ions and into electrons according to: 2H 2 = 4FT + 4th. The ions then pass through the membrane 30, but the electrons, blocked, are forced to take the external circuit, which generates current. At the cathode, hydrogen ions, electrons, and oxygen (pure or from air) meet to form water according to the reaction: 4FT + 4e + 02 = 2H2O. Water and oxygen pass through the right plate 10. This reaction will also produce heat which can be recovered.

La Figure 3 montre les courbes de polarisation et de puissance qui ont été obtenues par des décharges galvanostatiques de 30 s à température ambiante sous pression atmosphérique avec des gaz humidifiés (Humidité relative minimum de 60% HR) (H2 et air) avec des débits respectifs de 20 mL min-1 pour une membrane à base de lysozyme et d’a-lactalbumine. Figure 3 shows the polarization and power curves which were obtained by galvanostatic discharges of 30 s at room temperature under atmospheric pressure with humidified gases (minimum relative humidity of 60% RH) (H2 and air) with respective flow rates of 20 mL min-1 for a membrane based on lysozyme and α-lactalbumin.

Ces résultats montrent qu’une membrane comprenant un film de fibres amyloïdes est également un bon conducteur protonique. La membrane à base de lysozyme comparé à l’a-lactalbumine entraîne des performances un peu plus faibles (7 mW cm 2 à 0.4 V). Courbe de polarisation et courbe de puissance pour une PEMFC à base d’une membrane d’a-lactalbumine (a-LAC) et pour une PEMFC à base d’une membrane de lysozyme/méthylcellulose 95/5. Les décharges ont été réalisées à 1 atm en H2 et air à un taux d’humidité de 60%. These results show that a membrane comprising a film of amyloid fibers is also a good proton conductor. The lysozyme-based membrane compared to α-lactalbumin leads to slightly lower performance (7 mW cm 2 at 0.4 V). Polarization curve and power curve for a PEMFC based on an α-lactalbumin (α-LAC) membrane and for a PEMFC based on a 95/5 lysozyme / methylcellulose membrane. The discharges were carried out at 1 atm in H2 and air at a humidity of 60%.

Exemple Comparatif 5 : réalisation d’une pile avec membrane Nafion™ Pour démontrer les avantages des membranes selon l’invention, des tests comparatifs ont été menés. La seule différence entre les dispositifs est l’utilisation d’une membrane 30 ayant les caractéristiques suivantes (DUPONT Nafion™ NRE212, épaisseur de 50 pm -CAS N°. 31 175-20-9) à la place d’une membrane (30) selon l’invention. Les tests ont été menés dans des conditions identiques à celles décrites ci- dessus à l’exception que les décharges ont été réalisées à un taux d’humidité de 100% et non de 60%. La figure 2 montre la courbe de polarisation (noir) et la courbe de puissance (bleu) les piles PEMFC à base d’une membrane conventionnelle de Nafion™ et une PEMFC à base d’une membrane à base d’a-lactalbumine (a-LAC). Les décharges ont été réalisées à 1 atm en H2 et air à un taux d’humidité de 60% pour l’a-lactalbumine et 100% pour le Nafion™. Comparative Example 5: realization of a cell with Nafion ™ membrane To demonstrate the advantages of the membranes according to the invention, comparative tests were carried out. The only difference between the devices is the use of a membrane 30 having the following characteristics (DUPONT Nafion ™ NRE212, thickness 50 µm -CAS No. 31 175-20-9) instead of a membrane (30 ) according to the invention. The tests were carried out under conditions identical to those described above except that the discharges were carried out at a humidity level of 100% and not of 60%. Figure 2 shows the polarization curve (black) and the power curve (blue) the PEMFC cells based on a conventional membrane from Nafion ™ and a PEMFC based on an α-lactalbumin membrane (a -LAKE). The discharges were carried out at 1 atm in H2 and air at a humidity level of 60% for α-lactalbumin and 100% for Nafion ™.

Les performances obtenues à 25 °C (22 mW cm-2 à 0.4 V) montrent que la membrane à base d’a-LAC est un excellent conducteur de protons et est capable d’approcher les performances du Nafion™ (32 mW cm-2 à 0.4 V) dans ces conditions (25°C, HR 60%). The performances obtained at 25 ° C (22 mW cm-2 at 0.4 V) show that the a-LAC-based membrane is an excellent proton conductor and is capable of approaching the performances of Nafion ™ (32 mW cm- 2 to 0.4 V) under these conditions (25 ° C, RH 60%).

Exemple 6 : réalisation d’un film réticulé à base d’a-lactalbumine et de glutaraldéhyde selon l’invention Example 6: production of a crosslinked film based on α-lactalbumin and glutaraldehyde according to the invention

Les membranes de protéines autosupportées ont également été soumises à une étape de réticulation chimique en présence de vapeur de glutaraldéhyde (Fournisseur Sigma-Aldrich, 50% (en masse) dans l'eau). Le film de protéine de l’exemple 1 , une fois séché, est soumis 30 min à des vapeurs de glutaraldéhyde à 25°C. The self-supported protein membranes were also subjected to a chemical crosslinking step in the presence of glutaraldehyde vapor (Supplier Sigma-Aldrich, 50% (by mass) in water). The protein film of Example 1, once dried, is subjected to vapors of glutaraldehyde for 30 min at 25 ° C.

Cette étape de réticulation permet au film autosupporté d'être résistant en solution dans l'eau à pH acide (pH testé = 3) et jusqu'à 80°C. En fonctionnement en PEMFC, cette étape permet donc à la pile de fonctionner sur une large gamme de température. Sa résistance à la température passe de 35°C, sans réticulation chimique, à au moins 60°C après réticulation chimique, voire plus. De plus, une PEMFC comprenant une telle membrane ne perd pas ses performances après plusieurs jours de This crosslinking step allows the self-supported film to be resistant in solution in water at acidic pH (tested pH = 3) and up to 80 ° C. When operating in PEMFC, this step therefore allows the battery to operate over a wide temperature range. Its temperature resistance goes from 35 ° C, without chemical crosslinking, to at least 60 ° C after chemical crosslinking, or even more. In addition, a PEMFC comprising such a membrane does not lose its performance after several days of

fonctionnement. operation.

L'invention n'est pas limitée aux modes de réalisation présentés et d'autres modes de réalisation apparaîtront clairement à l'homme du métier. Il est notamment possible de considérer l’utilisation de peptides pouvant former des fibres amyloïdes qui s’organisent en hydrogels. Il est également possible d’utiliser les membranes selon l’invention sur tout type de PEMFC. Elle peut être non seulement utilisée pour les piles à hydrogène mais également les piles à méthanol direct (DMFC). The invention is not limited to the embodiments presented and other embodiments will be apparent to those skilled in the art. It is notably possible to consider the use of peptides which can form amyloid fibers which organize themselves into hydrogels. It is also possible to use the membranes according to the invention on any type of PEMFC. It can be used not only for hydrogen fuel cells but also direct methanol fuel cells (DMFC).

Claims

Revendications Claims 1. Une pile à combustible comprenant : 1. A fuel cell comprising: - une anode ; - an anode; - une cathode ; et - a cathode; and - une membrane située entre l’anode et la cathode, ladite membrane comprenant un liquide aqueux et un film comprenant des fibres amyloïdes. - a membrane located between the anode and the cathode, said membrane comprising an aqueous liquid and a film comprising amyloid fibers. 2. La pile à combustible selon la revendication 1 , où ladite membrane est une membrane échangeuse de protons. 2. The fuel cell according to claim 1, wherein said membrane is a proton exchange membrane. 3. La pile à combustible selon la revendication 1 ou 2, où ledit film a une épaisseur choisie dans une gamme variant de 10 nm à 1 mm. 3. The fuel cell according to claim 1 or 2, wherein said film has a thickness chosen from a range varying from 10 nm to 1 mm. 4. La pile à combustible selon l’une quelconque des revendications 1 à 3, où les fibres amyloïdes comprennent, ou sont constituées d’, au moins une protéine telle que Ga- lactalbumine ou le lysozyme. 4. The fuel cell according to any one of claims 1 to 3, wherein the amyloid fibers comprise, or consist of, at least one protein such as Ga-lactalbumin or lysozyme. 5. La pile à combustible selon l’un quelconque des revendications 1 à 4, où ledit film comprend en outre un additif choisi dans le groupe constitué par des ions, des plastifiants, des agents de réticulation, par exemple du glutaraldéhyde, des antioxydants, des pièges à radicaux et des anti-UV. 5. The fuel cell according to any one of claims 1 to 4, wherein said film further comprises an additive selected from the group consisting of ions, plasticizers, crosslinking agents, for example glutaraldehyde, antioxidants, radical traps and anti-UV. 6. La pile à combustible selon l’une quelconque des revendications 1 à 5, où ladite pile comprend en outre deux plaques : 6. The fuel cell according to any one of claims 1 to 5, wherein said cell further comprises two plates: - une première plaque pour distribuer un combustible réducteur, par exemple le - a first plate for distributing a reducing fuel, for example dihydrogène, et hydrogen, and - une deuxième plaque pour distribuer l'oxydant et, éventuellement, évacuer de l'eau. - a second plate to distribute the oxidant and, possibly, to evacuate water. 7. Une membrane échangeuse de protons telle que décrite à l’une quelconque des revendications 2 à 6. 7. A proton exchange membrane as described in any one of claims 2 to 6. 8. Un film tel que décrit à l’une quelconque des revendications 1 à 6. 8. A film as described in any one of claims 1 to 6. 9. Une pile à combustible comprenant un empilement d’au moins deux piles telles que décrites aux revendications 1 à 6. 9. A fuel cell comprising a stack of at least two cells as described in claims 1 to 6. 10. Utilisation d’un matériau à base de fibres amyloïdes pour la fabrication de piles à simple cellule, ou de piles comprenant un empilement de cellules, et de préférence de piles à combustible. 10. Use of a material based on amyloid fibers for the manufacture of single cell cells, or cells comprising a stack of cells, and preferably fuel cells. 11. Un dispositif électrique comprenant une pile décrite à l’une quelconque des revendications 1 à 6 ou un empilement de piles tel que décrit à la revendication 9. 11. An electrical device comprising a battery described in any one of claims 1 to 6 or a stack of batteries as described in claim 9. 12. Une méthode de fabrication d’un film ou d’une membrane à base de fibre amyloïdes caractérisée en ce qu’un gel de fibres amyloïdes est formé puis étalé et séché, de préférence sur un support solide, de manière à former ledit film ou ladite membrane. 12. A method of manufacturing a film or a membrane based on amyloid fibers characterized in that a gel of amyloid fibers is formed and then spread and dried, preferably on a solid support, so as to form said film. or said membrane. 13. La méthode selon la revendication 12, où ledit gel de fibres amyloïdes est obtenu par la mise en contact de protéine(s) et/ou de polypeptides, et d’eau dans des conditions permettant la formation des fibres amyloïdes. 13. The method of claim 12, wherein said gel of amyloid fibers is obtained by contacting protein (s) and / or polypeptides, and water under conditions allowing the formation of amyloid fibers. 14. La méthode selon la revendication 12, ou ladite protéine est l’a-lactalbumine ou le lysozyme. 14. The method of claim 12, wherein said protein is α-lactalbumin or lysozyme.
EP20746654.1A 2019-07-30 2020-07-29 Ion exchange membrane Pending EP4005000A1 (en)

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