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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• 2019
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