Classifications

• • 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
  • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
  • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
• • 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
  • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• • 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
  • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
• • 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
• • 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
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to a method for producing a solid proton conductive fluoropolymer membrane for a fuel cell and more particularly for a fuel micropile.
• PEMFC Proton Exchange Membrane Fuel CeII
• the fluorinated polymers such as the sulfonated tetrafluoroethylene copolymer are, by their performances, the most widespread in PEMFC cells.
• the technique for manufacturing fluoropolymer membranes such as the sulfonated tetrafluoroethylene copolymer is not satisfactory. Indeed, the polymer is generally dissolved in solution before being manually deposited on a support using a syringe. A drying step then makes it possible to form a solid electrolyte membrane. Such a technique is not very precise and is not industrializable for the purpose of high volume production.
• the printing techniques are known as described in documents US2002 / 134501 A1 and US2005100776A1.
• the sulfonated tetrafluoroethylene copolymer the latter is, in general, dissolved in water, propanol, ethanol and certain ethers in a small amount. Solutions comprising the sulfonated tetrafluoroethylene copolymer are, for example, marketed by Du Pont de Nemours, under the name of Nafion® range.
• the proportions of sulfonated tetrafluoroethylene copolymer, water and propanol, in the solution are, in general, respectively between 5% and 50%, between 30% and 90% and between 0 and 48% while the proportions ethanol and various ethers remain less than 4% and less than 1%, respectively.
• the invention aims to overcome the disadvantages of the prior art. More particularly, the object of the invention is to propose a manufacturing method making it possible, in an industrializable manner, to obtain a uniform solid membrane made of proton conductive fluorinated polymer for a fuel cell.
• the invention introduces a method for manufacturing a fuel cell element, of the type comprising the following steps: a) preparing a first electrode, able to form a support, b) depositing on the first electrode a membrane solid electrolyte in proton conductive fluorinated polymer, and c) depositing a second electrode, opposite the first, on the solid electrolyte membrane, characterized in that step b) comprises the following substeps: b1) preparing a proton-conducting fluorinated polymer-based mixture, of at least one solvent, and at least one polyol, b2) by means of an ink-jet printing head, depositing drops of the mixture obtained in b1) on the first electrode, as electrolyte, and b3) solidify said deposited drops, before proceeding to step c).
• the manufacturing method uses an inkjet printing head which is controlled by a piezoelectric element.
• said print head comprises one or more injection nozzles, each nozzle preferably being controlled individually by a piezoelectric element.
• the piezoelectric element can be controlled by an electrical signal of frequency between 1 Hz and 2OkHz.
• the drops mentioned above have a diameter that varies according to the electrical signal emitted by the piezoelectric element, the pressure of the mixture in the tank of the print head, and the output diameter of the print head.
• This diameter may be about 60 .mu.m, for example between 20 .mu.m and 100 .mu.m.
• the drops also have a diameter of about 60 .mu.m, for example between 20 .mu.m and 100 .mu.m.
• the drops may have a volume of between 1 ⁇ L and approximately 10 ⁇ L.
• step b2) and step b3) are repeated 1 to 10 times before step c).
• the deposition of the drops in step b2) can be carried out in a chosen pattern.
• This pattern may be for example a mesh whose centers of the different cells are spaced from each other by a predetermined distance, which may for example be between 10 .mu.m and 100 .mu.m.
• the mixture obtained during step b1) of the manufacturing process can comprise between 5% and 50%, preferably between 5% and 35%, and even more preferably between 10% and 35% by volume of polyol.
• the fluoropolymer used in the process according to the invention may for example be a sulfonated tetrafluoroethylene copolymer or a perfluoroalkoxy.
• the solvent in the mixture obtained in step b1) of the process according to the invention may comprise water.
• This solvent may further comprise propanol and / or ethanol and / or ethers.
• the support of the process can be maintained at a temperature between 0 0 C and 100 0 C.
• This support can be secured to a moving part and moves at a predetermined speed relative to the print head.
• step b3) of the manufacturing process the solidification of the drops is done by evaporation of the polyol and the solvent.
• the polyol may be ethylene glycol.
• the invention also relates to a fuel micropile comprising at least one element manufactured according to the method described above.
• the PEMFC (Proton Exchange Membrane Fuel CeII) fuel cells can be manufactured from a silicon substrate in the following sequence: 1. anisotropic etching of the silicon substrate for the formation of the hydrogen passage channels;
• Electrochemical deposition of a conductive polyaniline polymer on the hydrogen diffusion layer serves as a support for the catalyst deposited on its surface;
• the electrolyte used in step 8 may be in the form of a solid proton conductive polymer membrane.
• a solid proton conductive fluoropolymer membrane, for a fuel cell and more particularly for a PEMFC fuel micropile, is obtained by depositing, on a support, drops of a mixture comprising a polyol and a fluoropolymer-based solution. proton conductor.
• the support is, for example, a thin layer forming the electrode of a fuel cell, a second electrode can then be deposited directly on said membrane.
• the proton conducting fluorinated polymer is preferably selected from a sulfonated tetrafluoroethylene copolymer and a perfluoroalkoxy and is dissolved.
• the proton conducting fluorinated polymer solution preferably comprises a solvent comprising water with optionally propanol, ethanol and various ethers.
• the proportion of solvent in the solution is preferably between 15% and 50%, the remainder being preferably the pure fluorinated polymer.
• the solution is, for example, a solution of the type marketed under the name of Nafion® by the company Du Pont de Nemours or of the type marketed under the name of Hyflon® by Solvay Solexis.
• an additional amount of water may be added to said commercial solution.
• a polyol for example with ethylene glycol, also called glycol
• ethylene glycol also called glycol
• the ink jet printing makes it possible to form, by ejection, drops and more particularly micro-drops of mixture depositing on the support, before drying and forming the membrane.
• the volume proportion of polyol in the mixture is more particularly between 5% and 50%, preferably between 5% and 35% and more preferably between 10% and 35%.
• a solid membrane constituted by the proton conductive fluorinated polymer and for example tetrafluoroethylene copolymer is formed from drops of said mixture deposited on the support, via at least one jet printing head.
• ink and more particularly of the piezoelectric type. More particularly, several drops are deposited successively, in various places on the surface of the support. The successive deposition of the drops is, for example, carried out using one or more print heads.
• the one or more printheads may comprise one or more injection nozzles, each nozzle being preferably controlled individually by a piezoelectric element.
• the volume of each drop depends, more particularly, on the diameter of the orifice of the injection nozzle, the parameters that control the pressure of the mixture in the reservoir of the print head, and the parameters of the electrical signal controlling the piezoelectric element. , when it controls the inkjet print head.
• a drop generated by an inkjet printing head may have a volume ranging from about 1 picolitre to about ten nanoliters.
• the frequency of the electrical signal controlling the piezoelectric element is between 1 Hz and 20 kHz and more particularly between 1 and 10 kHz.
• the carrier secured to a moving part of the printing equipment, preferably moves in two X and Y directions relative to said print head, with a predetermined movement speed, so that the different drops are spaced from each other by a predetermined distance. In other words, the drops are therefore uniformly deposited in a mesh.
• the drops spread, then, on the support.
• the spreading of the drops can be controlled by heating to a predetermined temperature of the support and / or by a modification of the wettability of the surface of the support vis-à-vis the deposited solution and / or by the predetermined distance, center center, between two adjacent drops (also called no). This corresponds substantially to the distance between the centers of two adjacent cells of the mesh defined above, at which the drops are deposited.
• the pitch depends in particular on the speed of movement and the frequency of ejection of the drops. For example, the pitch between two adjacent drops may be between 10 .mu.m and 100 .mu.m and the temperature of the support may be between 0 0 C and 100 ° C.
• the thermalization of the support must be done beforehand during the deposition of the drops.
• Such a technique makes it possible to quickly and efficiently make electrolytic membranes for fuel cells, directly on a fuel cell electrode.
• steps of manufacturing the fuel cell can be carried out using the inkjet technique, for example: deposition of the lower electrode material, deposition of the electrolyte membrane, deposition of the electrode material higher.
• deposition of the lower electrode material deposition of the electrolyte membrane, deposition of the electrode material higher.
• solvent and polyol to the proton conductive fluoropolymer makes it possible, in fact, to reduce the viscosity of the polymer to a value allowing the formation of drops from an inkjet printing head.
• the polyol makes it possible to increase the drying time of the solution based on fluoropolymer. Indeed, without polyol, the solution may dry before being deposited on the support and in particular in the print head.
• tests were carried out using a mixture comprising 1 third by volume of a solution of Nafion® comprising 20% by weight of fluoropolymer, 34% by weight of water and 46% by weight of water. alcohol, 1 third by volume of ethylene glycol and 1 third by volume of water.
• the mixture is deposited on a support in the form of drops, using a piezoelectric type inkjet printing head.
• the output diameter of said print head is 60 ⁇ m and the electrical parameters used to control the piezoelectric element of the print head are as follows:
• the drops are deposited on a square section of 10mm x 10mm of a support such as a wafer type plate having a diameter of 100 mm.
• the drops are deposited on a square section of 10mm x 10mm of a support such as a "wafer” type plate having a diameter of 100mm (4 inches). As shown in the table below, 5 tests were carried out, with a support temperature of 35 ° C and varying the pitch between the drops and the number of layers deposited.
• the tests were performed with a higher proportion of National® solution compared to the tests of the first example.
• the fact of being able to increase the proportion of the National® solution in the mixture can be interesting, since a greater quantity of polymer is deposited on the support, once the solvents have been evaporated and the deposition time also called cycling time can to be diminished,
• the drops remain easily ejected from the print head, while limiting the cycle times, with the same uniformity characteristics as in the first example.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Sustainable Energy (AREA)
• Life Sciences & Earth Sciences (AREA)
• Sustainable Development (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Fuel Cell (AREA)
• Laminated Bodies (AREA)

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Cited By (1)

Citations (6)

• 2006
  • 2006-07-28 FR FR0606944A patent/FR2904477B1/fr not_active Expired - Fee Related
• 2007
  • 2007-07-23 WO PCT/FR2007/001261 patent/WO2008012423A2/fr active Application Filing
  • 2007-07-27 TW TW096127633A patent/TW200818584A/zh unknown

Patent Citations (6)

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