Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0081—After-treatment of organic or inorganic membranes
  • B01D67/0093—Chemical modification
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/52—Polyethers
  • B01D71/522—Aromatic polyethers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
  • B01D71/68—Polysulfones; Polyethersulfones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
  • B01D71/80—Block polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
  • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
  • C08G75/23—Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/20—Manufacture of shaped structures of ion-exchange resins
  • C08J5/22—Films, membranes or diaphragms
  • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
  • C08J5/2218—Synthetic macromolecular compounds
  • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0289—Means for holding the electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—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
  • H01M8/1041—Polymer electrolyte composites, mixtures or blends
  • H01M8/1046—Mixtures of at least one polymer and at least one additive
  • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2323/00—Details relating to membrane preparation
  • B01D2323/30—Cross-linking
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
  • C08J2381/06—Polysulfones; Polyethersulfones
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0082—Organic polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0088—Composites
  • H01M2300/0091—Composites in the form of mixtures
• • 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 devices for the production of membranes.
• the invention provides methods "for producing membrane electrode assemblies, and membranes were prepared by these methods.
• the membranes and membrane electrode units according to the invention can be used to generate energy by electrochemical or photochemical means, in particular in membrane fuel cells (H 2 - or direct methanol fuel cells) at temperatures from -20 to + 180 ° C. In one embodiment, working temperatures up to 250 ° C are possible.
• the membranes and membrane electrode units according to the invention can be used in membrane processes. Especially in galvanic cells, in secondary batteries, in electrolysis cells, in membrane separation processes such as gas separation, pervaporation, perstraction, reverse osmosis, electrodialysis, diffusion dialysis and in the separation of alkene-alkane mixtures or in the separation of mixtures in which one component contains silver ions Forms complexes.
• PEM polymer electrolyte membrane fuel cells
• a polymer electrolyte membrane fuel cell has a layer structure, with each layer having to fulfill its specific tasks. Some of these tasks are opposite. For example, the membrane must have a very high ion conductivity, but should have no or only very low electron conductivity and be completely gas-tight. In the gas diffusion layer, it is exactly the other way around. A very high gas permeability with high electron conductivity is desirable. Since the different tasks that each individual layer has to be performed only with different materials, the problem of the incompatibility of these materials often arises.
• the structure of the layer structure is not starting from a membrane instead, so from inside to outside * but from outside (cathode or anode) on the inner (membrane) to outside (anode or cathode).
• the method according to the invention is characterized by a porous basic structure or a porous substrate (sub) on which one or more thin layers (ski) or layers, which in a particular embodiment contain catalytically active substances, are applied. This layer is followed by the selective separating layer (Membrane), optionally thin layers (Sch2) and finally a porous substrate (Sub2).
• the invention enables the production of units which are characterized by the following layer structure (Fig. 2): porous substrate - selective separation layer - porous substrate 2 starting from a porous substrate 1.
• the layers are built up successively from a porous electrode layer, followed by a largely dense ion-conducting electrolyte layer, which in turn is covered by a porous electrode layer.
• the individual layers are made from dispersions and / or solutions with special functional properties. Manufacturing techniques include spraying, rolling, printing (e.g. screen printing, letterpress printing, gravure printing, pad printing, inkjet printing, stencil printing), doctor blade, CVD, lithographic, laminating, decal and plasma processes.
• a special embodiment is the production of graded layers with flowing transitions, in particular of the functional properties.
• a unit can be used as a fuel cell, in particular as a polymer electrolyte membrane fuel cell.
• the layer-by-layer construction from one electrode to the other enables very thin layers due to the methods used.
• the individual units can be miniaturized and arranged side by side on the same substrate.
• the substrate preferably a flat structure, can in itself have different properties over the surface.
• the units formed via the layer structure can be connected in series and / or in parallel. The interconnection already occurs during the manufacturing process. With the methods presented, it is also possible to connect the electrodes through the membrane.
• the resulting fuel cell elements can be connected both horizontally and vertically.
• the resulting units can be of different sizes. Large and small units can be produced side by side on the same substrate surface. This can be used to selectively connect individual cells to a desired total voltage.
• An essential advantage of the invention is that the entire production of the layer structures, in particular of the galvanic element, can take place in a single production line, in a special process with only one production method. The production is therefore considerably easier, time-saving and less expensive.
• the elements can be constructed in a modular manner and that any performance can be achieved by interconnecting individual elements.
• the production of fuel cell units with higher voltage or higher current densities is considerably simplified by the production method according to the invention, since the individual cells can be connected in series or in parallel in the plane during production.
• the performance of the galvanic element can thus be adapted to the respective application in a simple manner. '.
• Another advantage of the invention is the production of graded layers. Through them, the functional properties can be better adapted and coordinated.
• the invention allows the production of galvanic elements with flexible shapes and considerable space savings.
• a particular advantage of the invention is that the galvanic elements can be operated with a simple structure under simple operating conditions, in particular environmental conditions, and without pressure losses.
• An embodiment in this sense is, for example, a fuel cell unit consisting of one or more cells with a structure according to FIG. 4, the cathodes of which are located on the carrier substrate and the anodes of which are above the electrolyte layers.
• Such a fuel cell unit can be operated in a simple manner without additional components at ambient pressure and ambient temperature if the unit is installed in a housing in such a way that a fuel chamber is located directly above the anode and the cathode is supplied with air by the carrier substrate in a self-breathing manner.
• hydrogen, methanol or ethanol can be used as fuel.
• the flat interconnected cells are wound, for example in FIGS. 4, 5 or 7. It is important to ensure that the porous structure on its underside is completely sealed.
• the carrier substrate should preferably meet the following requirements: an open porosity that allows the passage of a gas or a fuel to a minimum that is necessary for the application.
• the porosity should be in the range from 20 to 80% by volume, 50 to 75% being particularly preferred.
• the fuel supply or the gas supply can be adjusted via the porosity.
• the porous structure With a cylindrical arrangement of the porous substrate with a central supply channel, a porosity below 60 vol.% Is sufficient, depending on the cell structure, the porous structure can have electronic conductivity or no conductivity, the smoothest possible surface, chemical stability, in particular with respect to acids and organic solvents, and thermal resistance of -40 ° C to 300 ° C, preferably up to 200 ° C, high mechanical stability, in particular with a bending stiffness of greater than 35 MPa and a modulus of elasticity of greater than 9000 MPa.
• the functional properties of the layers can be specifically adapted by adding suitable substances to the dispersions or solutions.
• suitable substances include in particular pore formers for increasing the porosity, hydrophobic or hydrophilic additives for varying the wetting behavior (e.g. Teflon and / or sulfonated and / or nitrogen-containing polymers), substances for increasing the electrical conductivity, in particular carbon black, graphite and or electrically conductive polymers such as Polyaniline and / or polythiophene and derivatives of the polymers or additives to increase the ionic conductivity (eg sulfonated polymers). It is also possible to add supported or unsupported catalysts, in particular platinum-containing metals. Carbon black and graphite are particularly preferred as carrier substances.
• a further embodiment includes the addition of a combination of different polymers both to the carrier substrate and to the solutions and / or dispersions which are used to build up the layers applied to the carrier substrate.
• polymers both to the carrier substrate and to the solutions and / or dispersions which are used to build up the layers applied to the carrier substrate.
• DE 10208679.6 This application was not published at the time of the present application.
• These are new polymeric materials, processes for their production and crosslinking processes for membrane polymers and polymers which are already partially disclosed therein and which are contained in catalyst inks.
• the use for the electrode display of the polymers, polymer building blocks, main chains and functional groups shown there is expressly referred to here.
• the materials described in the application DE 10208679.6 can be used both for inks and for membranes.
• Polymers with the functional groups are particularly preferred which are described in the application DE 10208679.6 with the abbreviations (2A) to (2R), (3A) to (3J) and the definition of the radical R 1 there and the crosslinking bridges (4A) to (4C) are listed.
• the following are examples of compositions for dispersions and manufacturing conditions for manufacturing fuel cell units.
• Nafion® can all soluble or dispergierbDC polymers containing one or more after-treatments according to at least one proton-functional group having an IEC greater than 0.7, are preferred and Polyarylmaterialien 'polymers of the invention of the parent application, the protic and in aprotic
• Solvents such as DMSO, NMP, THF, water and DMAc, with DMSO being preferred again, are soluble.
• a variant for the production of electrode-electrolyte-electrode units is the spraying process (airbrush).
• the cathode or anode layer is applied to the carrier substrate.
• the respective dispersion according to the above recipe is sprayed onto the carrier substrate.
• the carrier substrate has a temperature of 20 to 180 ° C, 110 ° C is preferred.
• the electrode-substrate unit is then annealed at a temperature of 130 ° C. to 160 ° C. for at least 20 minutes.
• the electrolyte is also applied using the spray method. If a Naf ⁇ on-DMSO dispersion is used as the electrolyte starting substance, heating the unit to approx. 140 ° C is advantageous.
• the drying of the electrolyte layer can be accelerated with a hot air jet.
• Aftertreatment in a vacuum drying cabinet follows, depending on the electrolyte dispersion used, between 130 ° C and 190 ° C, 10 min to 5 h.
• the unit After cooling to room temperature, the unit is at 30 to 100 ° C, 30 min. to 3 h, preferably 1.5 h are back-protonated in 0.3 M - 3 M H2S04, i.e. converted to the acid form.
• the unit is 30 min. up to 5 h at 80-150 ° C thoroughly cleaned in Millipore H20.
• the corresponding second electrode is again sprayed onto the electrolyte film at approximately 20 to 180 ° C. and annealed at 130 ° C.
• the graphite paper TGP-H-120 from Toray can be used as a carrier substrate for individual cells. It is advantageous if the paper is teflon-coated (approx. 15% to 30% PTFE content).
• electrically non-conductive substrates are used. Possible materials include stretched, filled foils, porous ceramics, membranes, filters, felts, fabrics, nonwovens, in particular made of temperature-resistant plastics and with low surface roughness.
• films are used as porous materials which contain layered and / or framework silicates and are stretched.
• FIGs 1, 1 (A), 1 (B) and 1 (C) the cross section of a fuel cell with an electrode structure is shown schematically, as can be produced using the conventional method, coating a membrane with catalyst-containing inks or using a printing method.
• the fuel cell unit contains gas or liquid reactants, ie the supply of a fuel and the supply of an oxidizing agent. The reactants diffuse through porous gas diffusion layers and reach the porous electrodes, which form the anode and cathode and on which the electrochemical reactions take place.
• the anode is separated from the cathode by a polymer membrane that is ion-conductive.
• Fig. 1 (A) is an enlarged view of the porous Kathode- gasdif divesionselektrdde which is gefrägert Gasdif Schosion GmbH-on one side and with the - communicating ⁇ elektfpjytiscjien polymer membrane.
• the reactants diffuse through the ⁇ D ⁇ ffusionssff ⁇ fktur be evenly distributed and then react in the porösen- ⁇ "electrode.
• Figure 1 (B) and 1 (C) shows a further increase of the electrode.
• Catalytically active particles either non-supported catalysts or carbon-supported catalysts (Metal particles distributed on the support) determine the porous structure.
• Additional hydrophilic or hydrophobic particles can be present in order to change the water wettability of the electrode or to determine the pore size.
• ionomer parts are impregnated into the electrode by impregnation or inserted by other methods to perform the various functions of an efficient electrode.
• An increase in the ionic conductivity of the electrode and, associated therewith, an enlargement of the reaction zone of the catalytically active particles is achieved.
• the electronic conductivity is achieved by d he introduction of the ionomer portions, in particular perfluorinated sulfonic acids, is reduced. With an empirical optimization of the content, however, a compromise can be found between electronic and ionic conductivity, which maximizes the reaction zone.
• the ionomer components serve to improve the adhesion of the electrode to the membrane, which is particularly true for chemically similar materials. This is caused by the flow behavior of the fluorinated polymers, which is favorable for the adhesion.
• novel and inexpensive polymer membranes such as acid-base blends based on aryl polymers
• the described electrode concept leads to the formation of poorly adhering layers.
• the electrode structure and in particular the interface to the membrane can be improved by the invention described here.
• an ionomer in the protonated form one or preferably more ionomers in a precursor form are brought into a dispersion or in solution.
• the electrolyte membrane or the diffusion layer is coated with this dispersion and / or solution as an electrode ink by means of suitable processes.
• Another embodiment is the combination of several precursor ionomers and inorganic particles in order to improve the wettability and the retention of the water in the electrode.
• the properties of the electrode are improved by a targeted aftertreatment, for example by hydrolysis or by an annealing step.
• the electrode thus produced advantageously fulfills the functions necessary for the application.
• ionic and / or covalent crosslinking of the ionomers takes place in the electrode, which results in an extensive ionic and / or covalent network leads in the electrode layer.
• An electrode manufactured in this way has advantageous properties both with regard to the expansion of the reaction zone and with regard to the adhesion to the membrane. This applies in particular to membranes that do not consist of perfluorinated “hydrocarbons.
• the use of multi-component ⁇ electrolyte materials allows the catalyst layer to be built up in layers, which means that the structure and properties of the catalyst layer can be used in a targeted manner, for example by building up in layers or by using processes that are suitable for multicolor printing will be described below.
• a water-insoluble sulfonated ionomer is dissolved in a dipolar aprotic solvent (suitable ⁇ solvents: N-methylpyrrolidinone NMP, N, N-dimethylacetamide DMAc, NN-dimethylformamide DMF, " N-methylacetamide, N-methylformamide, dimethyl sulfoxide " DMSO, sulfolane) / Microgel particles of the polymer are generated by the controlled addition of water. Catalyst and possibly pore former are added to the suspension formed and stirred until the suspension is as homogeneous as possible.
• a dipolar aprotic solvent suitable ⁇ solvents: N-methylpyrrolidinone NMP, N, N-dimethylacetamide DMAc, NN-dimethylformamide DMF, " N-methylacetamide, N-methylformamide, dimethyl sulfoxide " DMSO, sulfolane
• the membrane electrode assembly is diluted in aqueous acid, preferably mineral acid, particularly preferably phosphorus -, sulfuric, nitric, and hydrochloric acid, the ionic crosslinking sites of the acid-base blend are formed, resulting in a what Insolubility of the ionomer portion and leads to mechanical stabilization in the electrode layer.
• aqueous acid preferably mineral acid, particularly preferably phosphorus -, sulfuric, nitric, and hydrochloric acid
• heating the membrane electrode unit is also sufficient.
• the prerequisite is that the acid-base blend is blocked by bonds that are released by the application of heat or by the attack of heated warm water.
• Examples include polymeric sulfonic acids that have been deprotonated by cold urea.
• Heating can also take place in water or steam, the temperature range between 60 ° C. and 150 ° C. is particularly preferred when using water.
• After-treatment in acid can then be dispensed with. Temperatures above 100 ° C are achieved under pressure, for example in an autoclave.
• the heating process can also be carried out under microwave conditions by " microwave radiation " .
• the advantage of the above-mentioned method is that no anions from which the acid or the ink itself come into contact with the catalyst.
• the ink can only be made with water.
• the water-insoluble cation exchange ionomer is in the salt form S03M, P03M2 or
• a solution of a polymeric amine, polymer with nitrogen groups or imine e.g. polyethyleneimine
• a suitable solvent dipolar aprotic solvents such as N-methylpyrrolidinone NMP, N, N-dimethylacetamide DMAc, NN-dimethylformamide DMF
• the polymer Amine, polymer with nitrogen groups or imine may carry primary, secondary or tertiary amino groups or other N-basic groups (pyridine groups or other heteroaromatic or heterocyclic groups).
• Catalyst and possibly pore former are added to the solution formed and the suspension is homogenized as much as possible.
• the aim is to ensure that the water content is as high as possible when using solvent / water mixtures.
• the MEA is aftertreated in acid, preferably in dilute aqueous mineral acid.
• the ionic crosslinking sites of the acid-base blend are formed, which leads to a stabilization of the ionomer content in the electrode layer.
• aftertreatment can again be carried out in water, as when using water-soluble polymers.
• Alkene groups -RC CR2 (are crosslinked with peroxides or with siloxanes containing Si-H groups via hydrosilylation) and / or sulfinate groups -S02M (are crosslinked with di- or oligohalogen compounds, e.g. alpha, omega-dihaloalkanes) and / or Tertiary amino groups or pyridyl groups (are crosslinked with di- or oligohalogen compounds, e.g. alpha, omega-dihaloalkanes)
• Catalyst and possibly pore former are added to the solution formed and the suspension is homogenized as much as possible. The aim is to ensure that the water content is as high as possible when using solvent / water mixtures.
• crosslinking initiators e.g. peroxides
• crosslinking agents di- or oligohalogen compounds, hydrogen siloxanes etc.
• the crosslinkable groups in the ink react with each other and with the crosslinkable groups of the membrane.
• the MEA After application of the catalyst layer, the MEA is in dilute aqueous mineral acid and / or in water at a temperature between 0 and 150 ° C, preferably between 50 ° and After-treated at 90 ° C.
• the water-insoluble nonionic precursor of a cation exchange ionomer S02Y, POY2, COY (Y Hal (F, Cl, Br, I), OR, NR2, pyridinium, imidazolium) in a suitable solvent (ether solvent such as tetrahydrofuran, diethyl ether, dioxane, oxane, Glyme, diglyme, triglyme, dipolar aprotic solvents such as N-methylpyrrolidinone NMP, N, N-dimethylacetamide DMAc, N, N-dimethylformamide DMF, N-methylacetamide, N-methylformamide, dimethyl sulfoxide DMSO, sulfolane or mixtures of these solvents with one another or mixtures this solvent is dissolved with water or alcohols (methanol, ethanol, i-propanol, n-propanol, ethylene glycol, glycerin etc.) Catalyst and,
• x can be between 1 and 5
• Polyether sulfones such as PSU Udel®, PES Victrex®, PPhSU Radel R®, PEES Radel A®,
• Polyphenylenes such as poly-p-phenylene, poly-m-phenylene and poly-p-stat-m-phenylene,
• Polyphenylene ethers such as polyphenylene oxide PPO poly (2,6-dimethylphenylene ether) and
• Polyether ketones such as polyether ketone PEK Victrex®, polyether ether ketone PEEK Victrex®,
• the use of the ionomer materials described above opens up a wide variability in the transport properties for ions, water and reactants in the fuel cell.
• the coating of electrolyte membranes with a porous catalyst layer made of an aqueous or solvent-containing suspension has proven particularly promising.
• the finished catalyst layer consists of the following solid components
• water repellent e.g. PTFE
• pore formers e.g. (NH 4 ) 2 C0 3
• Printing process e.g. Screen printing, letterpress printing, gravure printing, pad printing, inkjet printing,
• Stencil printing - doctor blade process The use of multi-component electrolyte materials allows the catalyst layer to be built up in layers, which enables the structure and properties of the catalyst layer to be selected, e.g. through layered construction or through the use of processes that are suitable for multi-color printing.
• the porosity and conductivity of the layers can be influenced in a targeted manner by varying the total proportion of the ionically conductive phase and its presence in the electrode ink (solution, suspension).
• the release of inorganic nanoparticles can have a positive effect on the water balance in the catalyst layer.
• a method according to the invention is described below - polymers which are contained in an ink are covalently bound to a membrane. It is assumed that a membrane has sulfonyl chloride groups at least on its surface. In an aqueous sodium sulfite solution, these are partially reduced to sulfinate groups, preferably on the surface.
• the catalyst ink also contains at least one polymer which carries sulfinate groups. In short, i.e. less than 15 minutes before spraying the ink on the membrane, a di or oligo-halogen compound is added to the ink.
• the known covalent crosslinking of the molecules carrying sulfinate groups occurs both from the polymeric molecules in the ink and also between the polymeric molecules of the ink and the membrane polymers, which indeed have crosslinkable sulfinate groups on their surface.
• a variation of this process is to allow the sulfinate groups on the surface of the membrane to react with an excess of di- or oligo-halogen compounds on the surface of the membrane before contacting them with the catalyst ink, so that residues carrying terminal halogen groups are now on the membrane surface , If the ink is sprayed on, the sulfinate groups of the ink polymers will only be covalently cross-linked with the terminal cross-linkable halogen groups on the membrane surface (Fig. 9).
• the order can also be reversed.
• the membrane surface carries the sulfinate groups, while the ink polymers carry terminal crosslinkable halogen groups.
• This process involves polymers with terminal crosslinkable halogen groups and polymers.
• Covalent crosslinking of terminal sulfinate groups can also be used in the spray processes mentioned above for the selective build-up of selective or functional layers.
• the polymers bearing halogen groups or the polymers carrying sulfinate groups additionally have further functional groups on the same main polymer chain.
• Example of execution Polyether ether ketone sulfonic acid chloride is dissolved in NMP on a base, for example a glass plate is pulled out to a thin film. The solvent is evaporated in a drying cabinet. The film is separated from the glass plate and placed in an aqueous sodium sulfite solution. The sodium sulfite solution is a solution saturated in water at room temperature. The membrane is brought to a temperature of 60 ° C. with the solution. The sulfonic acid chloride groups are preferably reduced to sulfinate groups on the surface. Now you can continue in several ways.
• Route 1 The film with the surface sulfinate groups is mixed with a di- or oligo-halogen compound, for example diiodoalkane in excess in a solvent which does not dissolve the membrane (for example acetone).
• a di- or oligo-halogen compound for example diiodoalkane in excess in a solvent which does not dissolve the membrane (for example acetone).
• excess is meant that more than twice as much Hajogeriat me present in the alkylation reagent, as on sulfinate groups to be reacted - exist.
• the sulfinate groups react with the di-iodo-alkane to form polymer SO2-alkane-iodine.
• Water-soluble sulfonated polymers form water-insoluble complexes with polymeric amines. This is state of the art. It has now surprisingly been found that sulfonated polymers in water can be applied to a surface in a defined manner using a conventional inkjet printer. The limit is the dot resolution (dot / inch) of the print cartridge.
• Polymeric amines with a high content of nitrogen groups, the IEC of basic groups must be above 6, in particular polyvinylpyridine (P4VP) and polyethyleneimine can be dissolved in dilute hydrochloric acid, polyethyleneimine also only in water. The pH of the solution increases. This succeeds until neutrality.
• the hydrochloride of the polymeric amine here of P4VP
• P4VP polymeric amine
• any mixture of a polymeric acid and a polymeric base can be printed or applied to a surface.
• the basic and acidic polymers react to form water-insoluble, dense polyelectrolyte complexes.
• the ratio between the polymeric acid and the polymeric base can be set as required using the software. Gradients of acidic and basic polymers and the mixtures can be produced in any desired ratio. The resolution depends solely on the resolution of the print cartridge.
• this process can also be used to spray dispersions of catalyst inks containing carbon particles in combination with polymeric acids and polymeric bases. This makes it possible to produce micro fuel cells that can be connected through the membrane via printed electron-conductive structures, either in series or in parallel.
• Example of execution The print cartridge from a Deskjet (HP) is removed from the foam cushion ⁇ and ⁇ the corresponding aqueous solution of either the polymeric amine or the polymeric acid is filled in. The container is expediently not completely filled (half is sufficient).
• Graphite paper. ⁇ B ⁇ ⁇ SBB from the company " Toray, which has already been coated with a catalyst " by spraying " is now printed like normal paper. The process can be changed several times and repeated to create an acid-base blend the surface of the graphite paper.
• a multi-chamber color cartridge is filled with the solutions for the polymeric acid and the polymer base.
• the third chamber (HP inkjet cartridge) is filled with a solution containing platinum-hexa-chloride.
• the cartridge for the "black" color is used for a carbon dispersion which also contains additions of low-boiling alcohols as blowing agents in the inkjet process, 3-7% isopropanol being preferred. It can be used to spray carbon particles that are smaller than the nozzle openings of the inkjet cartridge.
• Fig. 4 The flat serial connection in side view, with four units as an example
• Fig. 5 Schematic of the flat serial connection in plan view, for example with four
• Fig. 6 a possible embodiment of a flat serial interconnection with additional external interconnection
• Fig. 7 schematically the simultaneous serial and parallel connection on one
• Fig. 8 schematically the interconnection of individual cells, whereby the porous substrate has a cylindrical shape
• Fig. 8b schematic connection of individual cells, whereby the porous substrate has a cylindrical shape and through the cylinder the fuel e.g. Hydrogen or methanol is supplied
• the fuel e.g. Hydrogen or methanol
• Fig. 8c schematic connection of individual cells, the porous substrate has a cylindrical shape and the oxygen or air is supplied through the cylinder

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