WO1997001194A1 - Systeme de cellules electrochimiques a electrolyte solide - Google Patents

Systeme de cellules electrochimiques a electrolyte solide Download PDF

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Publication number
WO1997001194A1
WO1997001194A1 PCT/DE1996/001123 DE9601123W WO9701194A1 WO 1997001194 A1 WO1997001194 A1 WO 1997001194A1 DE 9601123 W DE9601123 W DE 9601123W WO 9701194 A1 WO9701194 A1 WO 9701194A1
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WO
WIPO (PCT)
Prior art keywords
solid electrolyte
cell system
conductive
electrolyte cell
gas
Prior art date
Application number
PCT/DE1996/001123
Other languages
German (de)
English (en)
Inventor
Konstantin Ledjeff
Roland Nolte
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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
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Publication of WO1997001194A1 publication Critical patent/WO1997001194A1/fr

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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
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/241—Grouping of fuel cells, e.g. stacking of fuel cells with solid or matrix-supported electrolytes
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • 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 an electrochemical solid electrolyte cell system in which a first porous, electrically conductive electrode layer, a proton-conducting membrane layer and a second porous, electronically conductive electrode layer are applied to a surface of a gas-permeable support body by means of layer technology.
  • Electrochemical cells are known, for example, in the form of the fuel cell or the electrolysis cell.
  • Fuel cells for example, convert chemical energy directly into electrical energy with high efficiencies (50-60%). They simply consist of two electrodes and an electrolyte in between. The chemical energy carriers are continuously introduced to the electrodes and converted electrochemically.
  • Hydrogen-oxygen fuel cell called, where one electrode is supplied with hydrogen and the other electrode with oxygen. The following electrochemical reactions then take place voluntarily on the catalytically active electrodes.
  • a voltage can then be tapped at the two electrodes, which typically ranges between 0.5 and 1 V, depending on the electrical load.
  • the membranes which are typically coated on both sides with electrochemically active catalyst material are.
  • the membrane areas usually move between 1 and 1500 cm 2 , the membrane thickness between 30 and 200 ⁇ m.
  • Gas-permeable and electronically conductive current distributors press on the two catalyst-coated surfaces of the membrane, which ensure good electronic transverse conductivity and a homogeneous gas supply to the membrane.
  • the current distributors are separate structures with a thickness of, for example, 200-500 ⁇ m. This is followed on both sides by the electronically conductive bipolar plates, from which the voltage can be tapped and which contain internal channels for the gas supply to the respective electrode. They have thicknesses in the range of a few millimeters to centimeters.
  • a seal is provided between the membrane side and the bipolar plate to ensure the gas tightness of the cell stack.
  • This entire arrangement is to be pressed together, for example, by screwing in order to achieve electrical contacting of the membrane on the one hand and gas-tightness on the other.
  • a fuel cell arrangement is described in DE 39 07 485 AI.
  • This is a so-called SOFC (Solid Oxide Fuel Cell) arrangement.
  • SOFC Solid Oxide Fuel Cell
  • the electrolytes are ion-conducting oxide ceramics and the guiding mechanism takes place almost exclusively via oxygen ions.
  • the carrier material also used according to DE 39 07 485 is a porous ceramic material, such as, for example, magnesium aluminum spinel (MgAl 2 0 4 ) or zirconium oxide.
  • MgAl 2 0 4 magnesium aluminum spinel
  • zirconium oxide zirconium oxide
  • ceramic materials also have the disadvantage that they are very brittle. Once a shape has been specified, it can no longer be changed and only rigid structures can be maintained. A subsequent change in shape or geometry or an adaptation to different site modifications is no longer possible.
  • DE 43 29 819 A1 also describes a so-called strip membrane, which as an electrochemical cell with at least one core region forming the strip membrane, on each of which polymeric solid electrolytes are applied as an electrode layer on both sides and in which several individual cells are connected in series are trained.
  • a strip membrane can then be used in fuel cells.
  • the low strength must be taken into account here and a corresponding housing receptacle must be carried out.
  • the object of the present invention was therefore to propose a new electrochemical solid electrolyte cell system with which a miniaturization of a cell stack in the area and / or in the thickness of the components should be possible.
  • the object is achieved in relation to the cell system by the characterizing features of claim 1, according to the method by the characterizing features of claim 21 and according to use by the characterizing features of claims 24 and 25.
  • the subclaims show advantageous configurations.
  • a flat, gas-permeable, non-conductive, flexible support body is used, on the surface of which the cell is then applied using layering technology.
  • the cell applied using layering technology is only one-sided, i.e. arranged only on one surface, so that in connection with the gas-permeable support body it is possible to lead a first partner involved in the fireplace insert reaction on the side opposite the cell area through the gas-permeable support body to the cell and the second Lead reactants directly to the surface of the cell.
  • this structure makes it possible to arrange and electrically connect a plurality of cell regions on a support body.
  • an arrangement can be implemented that is known from the prior art Technology known stack design corresponds.
  • At least up to 1,000,000 cell areas can be arranged in this way analogous to the integrated circuits.
  • a cell area is understood to mean an insulated structure of a cell, each consisting of a first porous, flexible, electrically conductive electrode layer, a proton-conducting membrane layer and a second porous, flexible, electronically conductive electrode layer.
  • These individual cell areas can each be applied by means of appropriate layer technology (e.g. mask technology) and interconnected by means of suitable electrical contacts.
  • layer technology used according to the invention thus opens up numerous possibilities for connecting the individual cell areas in series. For example, several of the cell areas described above, preferably 2-10,000, can be connected in series, so that a one-dimensional cell arrangement is created. With the cell system according to the invention, however, any arrangement of cells connected in series is also possible.
  • Such two-dimensional arrangements can be designed in such a way that several cell rows are arranged one behind the other in any shape on the supporting body, or else that several individual cell rows, preferably 2 to 10,000, are formed, which are then connected in parallel with one another (redundant arrangement ).
  • the basis of the cell system according to the invention is thus the gas-permeable, flat, non-conductive, flexible supporting body.
  • This support body serves as a mechanical basic structure for all subsequent layers to be applied.
  • the fuel supply for the one electrode also takes place through this support body.
  • a plurality of cells can also be applied next to one another on the support body, the support body need not be conductive, since otherwise the individual cells would be short-circuited via the support body.
  • the support body used in accordance with the invention has a thickness of 10 ⁇ m to 10 mm and an area of 1 mm 2 to Im 2 . The dimensioning of the support body depends on the application, ie whether one or more cells are applied to the surface.
  • the support body is preferably a non-conductive, gas-permeable, flat membrane.
  • the materials for the support body are typically polymeric supports made of, for example, polysulfone. Such porous membranes can have symmetrical, ie the same membrane structure over the entire membrane cross-section, or asymmetrical, ie changes in the membrane structure over the membrane cross-section. Composite membranes are also possible.
  • An overview of materials for the supporting body that can be used according to the invention can be found, for example, in "Membranes", Prof. Dr. Eberhard Staude, from Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, 1978, vol. 16, pages 515 to 535.
  • the PEMFC (polymer electrolyte membrane fuel cell) fuel lines designed according to the invention typically work in a temperature range between 80 and 100 ° C. and the ion conduit does not use the oxygen ions but proto Conductive membranes, which usually consist of proton-conducting polymer material. Since the solid electrolyte cell system designed according to the invention consists of polymer materials, they are suitable for use in PEMFC fuel lines and, in particular, are designed to be very light and flexible, which enables corresponding flexible structures. Porous, gas-permeable films can be produced inexpensively with the polymer materials, it being possible to use the phase inversion method known in membrane technology.
  • a polymer solution is immersed in a cell bath and the solution is separated into a polymer-rich and a polymer-poor phase. After the membrane has been dried, a gas-permeable, porous structure can be obtained. All other layers of the cell system according to the invention (ion-conducting plastic film or conductive structures) can then be applied to the porous polymer support thus obtained, which is also flexible. A completely flexible layer structure is achieved.
  • the cell system thus produced then takes the form of a flexible film which can be used in a wide variety of forms. For example
  • Winding modules are produced, the above-described film structure of the cell system according to the invention being overlaid with a second non-functional, non-conductive, thin, flexible plastic film and wound up accordingly.
  • Gas spaces should be formed between the latter plastic film and the "fuel cell film", so that the fuel cell film with hydrogen on one side and with on the other side Oxygen or air can be brought into contact, so that a functional fuel cell with a high output voltage that can be achieved by the possibility of series connection is formed.
  • the cell system is designed as a winding module
  • the use of the plastic starting materials means that the edges on the two end faces of the winding module can be sealed by simply gluing or welding the plastics with a suitable closure (cover).
  • the closures are made of a stable, non-conductive, gas-impermeable material.
  • the cell system designed according to the invention in addition to being used as a winding module, a wide variety of structures and shapes can be formed, so that it is possible to provide fuel cells in a relatively small space, which, if desired, can deliver a high output voltage .
  • the surface of the support body usually has an area of 1 cm 2 to 1000 cm 2 .
  • the electrode layers deposited on the support body described above by means of layer technology typically have a thickness of 10 nm to 100 ⁇ m.
  • the materials for this are all, in and of themselves, already known from the prior art. knew electrode materials in question.
  • Electrodes are electronically conductive and catalytically active.
  • suitable catalysts are necessary for the course of the electrochemical partial reactions in order to avoid high transition voltages.
  • platinum is typically used as the electrode material catalyst.
  • Other examples of electrode materials are platinized carbon or iridium. Additives such as Hydrophobie ⁇ be included.
  • the membrane layer which is likewise deposited on the first electrode layer by means of layer technology, it is important that it is proton-conductive in order to ensure the ionic charge transport between the two electrodes.
  • polymers have sulfonic acid, carboxylic acid or
  • Phosphonic acid groups contain the property of proton conductivity in the presence of water. Examples are sulfonated polysulfones or sulfonated polyether sulfones. Another possibility is the organic-inorganic polymer class of the ormolytes
  • ORGANIC MOdified ceramics elektroLYTES such as, for example, aminosile, poly (benzylsulfonic acid) siloxanes or sulfonamidosile, all of which are produced via sol-gel processes.
  • Aminosils are obtained from a solution of aminated organotrisiloxane, an acid HX and water. Materials of the general formula SiO 3/2 , R- (HX) X , 0 ⁇ x ⁇ 0.5 are obtained via a sol-gel process.
  • An example of an aminosil is Si0 3/2 (CH 2 ) 3 NH (CH 2 ) 2 NH 2 - (HCF 3 S0 3 ) 02 .
  • Inorganic compounds can also have proton conductivity, especially at higher temperatures.
  • Examples are modified alkaline earth metal ceramates or zirconates such as
  • the invention further provides that, in addition to the electrical contact, an insulating layer, ie non-conductive areas, which can also be applied by means of layer technology, is arranged between the contact and the membrane. These non-conductive areas, ie insulating layers, must not be ionically or electronically conductive. Metal oxides such as aluminum oxide or non-conductive polymers such as polysulfones are therefore typically used as materials.
  • Methods of layering technology such as sputtering, CVD processes, plasma-assisted CVD processes, plasma polymerization, sol-gel technology, electroplating or coating from solution or from suspensions with powders.
  • Metal layers can be applied by sputtering processes, metal oxides are also accessible by reactive sputtering.
  • CVD processes e.g. the decomposition of organometallic starting compounds is made possible by metal oxide layers, with plasma-assisted CVD coatings being suitable for temperature-sensitive substrates.
  • thin platinum layers are accessible through the decomposition of TrCyclopentadienyltrimethylplinin in the plasma.
  • Organic layers are also accessible, for example, by plasma polymerization of ethylene or other organics.
  • carboxylate groups in the plasma polymerization enables the production of proton-conducting plasma polymers.
  • Ormolytes as proton conductors are produced, for example, by means of the sol-gel process, other sulfonated polymers can be applied as a solution.
  • sulfonated polysulfones generally dissolve well in dimethyl sulfoxide and can thus be applied in a viscous form.
  • Suitable masks during the deposition process or covering with photoresists enable the application of geometrically defined areas, as are necessary for the integrated fuel line system.
  • the integrated fuel cell is self-supporting, simple encapsulation in plastic housings is possible. After applying all layers The layered fuel cell system is welded or cast into the corresponding plastic housing on the supporting body.
  • Fig. 1 shows the cross section through the schematic
  • FIG. 2 shows the structure analogous to FIG. 1, but with an insulating layer that only partially projects into the membrane in cross section;
  • FIG. 7a shows a further embodiment relating to the installation of the cell system in a housing, but here with an integrated gas supply
  • Fig. 9 the integration of water cooling in a housing
  • FIG. 10 shows a structure according to the invention in the form of a winding module in cross section
  • FIG. 11 shows a further exemplary embodiment using additional gas-impermeable, non-conductive foils and
  • FIG 12 shows an arrangement in which that in FIG shown embodiment is wound on a body.
  • FIG. 1 shows, in cross section, the structure of a cell system according to the invention using the example of a fuel cell.
  • FIG. 1 In the embodiment according to FIG. 1, four individual cells (cells 1-4) are connected in series one after the other.
  • the cell 1 is formed by the cell area 3 and a part of the supporting body which is assigned to this area 3.
  • the basis of the cell system according to the invention is the gas-permeable, flexible support body 1.
  • the gas-permeable support body 1 is shown in FIG. 1, as in the following figures, only for better clarity in the form of a perforated support body.
  • the invention includes all variants of a support body, provided that they are gas-permeable.
  • the support body can accordingly itself be made of porous material or be made of non-porous material and have corresponding openings for the gas inflow.
  • a support body which is otherwise made from a closed material, but which has corresponding openings for the gas flow.
  • the dimensions of the supporting body ie the thickness and the surface, are selected depending on the conditions of use and the desired output voltages.
  • the thickness is in the range from 10 ⁇ m to 10 mm, the surface in the range from 1 mm 2 to 1 m 2 .
  • a likewise flexible insulating technique is then applied to the gas-permeable, flexible support body 1 in a first step on its surface 2 at certain intervals using layer technology. rende layer 15 of non-conductive material applied. This non-conductive material serves to isolate the cell regions 3 that then arise.
  • the thickness of the insulation 15 is in the range from 10 nm to 1 mm.
  • the gas-permeable support body 1 is coated with electronically conductive, flexible material for producing the first electrode layer 7.
  • the electronic partial reactions for example, hydrogen oxide oxidation, then take place on this electrode layer 7.
  • This layer (first electrode) must not be tight, but, like the supporting body 1, must have a certain porosity.
  • small, electronically conductive areas which represent the electrical contact 12 are then applied directly next to the insulating layer 15 and on the first electrode layer 7.
  • a flexible proton-conducting layer is applied in the depressions now formed between the insulating layer 15 and the conductive contact 12. This proton-conducting layer then forms the membrane layer 8.
  • the membrane layer 8 is in contact with the conductive material of the electrode layer 7 on the underside.
  • a coating is then again carried out with an electronically conductive flexible material for producing the second electrode layer 11, on which the other partial electrochemical reaction takes place (second electrode).
  • second electrode an electronically conductive flexible material for producing the second electrode layer 11, on which the other partial electrochemical reaction takes place
  • the oxygen reduction then takes place here.
  • This layer must be such that a three-phase contact between the supplied gas, second electrode 11 and
  • Membrane layer 8 is possible, i.e. it must not be a dense layer. Furthermore, the layer 11 must be applied in such a way that an electronically conductive connection between the lower electrode 7 of one cell and the upper electrode 11 of the following cell is achieved with the aid of the electrical contact 12. An internal electrical series connection of the individual cells 1 to 4 is thus realized and the sum of all cell voltages can be tapped at the first upper electrode with the connection 20 and the last lower electrode with the connection 21.
  • FIG. 2 now shows a further embodiment of a cell system according to the invention.
  • the structure corresponds essentially to the structure according to FIG. 1, however, according to FIG. 2, the connection is realized differently by means of the electrical contact.
  • the connection according to FIG. 2 is carried out here by an electrical contact 13, which is designed in such a way that it directly connects the upper electrode layer 7 to the lower electrode layer 7.
  • the electrical contact 13 is consistently formed from a dense material.
  • the dense material was only arranged in the area of the proton-conducting membrane layer.
  • the insulating layer 16 is not designed here in such a way that it extends over the entire thickness of the membrane layer 9, but only partially.
  • FIG. 3 now shows an embodiment in which the insulating layers are entirely dispensed with.
  • the membrane layer 10 is formed in such a way that it is guided down to the supporting body 1 in the area of the electrical contact 14. This also makes it possible to implement a series connection of the cell region 5.
  • FIG. 4 now shows the cell structure according to the invention according to FIG. 1 in a top view.
  • the cells 1 to 4 arranged one behind the other can be seen, the individual voltages of which, according to the series connection according to FIG. 4, add up to a total voltage which can be tapped off at the connections 20 and 21.
  • This arrangement of the individual cells is an arrangement in one direction.
  • 5 now shows an embodiment in which the individual cells are arranged so that they expand in two directions, which is easily possible with the aid of the layer technique.
  • 5 shows this using the example of 16 individual cells, 4 cells (cell range 1-4) being arranged in each axis direction. All cells are mounted on the supporting body 1 and connected in series according to the principle described in FIG. 1, so that 16 times the output voltage is available compared to an individual cell. The voltage can then be tapped at the connections 20 and 21.
  • the support body regions which are not covered by the cell arrangement are coated with a non-conductive substance 40 in such a way that no gas penetration occurs from the bottom to the top.
  • the sequence and type of electrical connection in a cell arrangement in two directions is shown as an example in FIG. 5.
  • FIGS. 6 to 9 now show, by way of example, how the fuel cell according to the invention can be introduced into a plastic housing 17, 18, 19 simply by encapsulation.
  • 6 a shows an example in the side view
  • FIG. 6 b in the front view.
  • the integrated fuel cell 22 is welded or cast in a gas-tight manner into a non-conductive plastic housing 17, openings 23, 24 being provided on both sides of the cell for the fuel supply. hen are.
  • the electrical connections 25, 26 of the cell are also encapsulated and are led to the outside as a metal contact.
  • FIGS. 7a and 7b show a further variant, for an advantageous gas supply of several integrated fuel cell systems.
  • the integrated fuel cell 22 is welded / poured in a gas-tight manner into a non-conductive plastic housing 18, but channels 27-30 running through the entire cell for fuel supply and removal are present.
  • a hydrogen-supply channel 27 which is connected to one side of the integrated fuel cell 22, and an oxygen-supply channel 30, which is connected to the other side of the integrated fuel cell.
  • Any inert gases can be discharged through the discharge channels 28 and 29 for each side of the integrated fuel cell.
  • the electrical connections of the cell 25, 26 are also encapsulated and are led to the outside as metal contacts. In this arrangement, a large number of these encapsulated cells can be arranged one behind the other via seals, the channels meaning a central fuel supply for all cells.
  • the encapsulation technique also enables the installation of several integrated fuel cell systems in a plastic housing 19, as shown in FIG. 8.
  • cooling of the cells becomes necessary, this can be done, for example, by applying heat sinks.
  • Metallic heat sinks for example made of aluminum, can be glued onto the cell.
  • Water cooling is also possible (FIG. 9), in which case, in addition to the fuel supply channels 27-30, a channel for the water supply 31 and a channel for the water discharge 32 are integrated in the housing 33.
  • the front and back of the housing contain corresponding large-area depressions 34, the actual cooling structures then being formed when several modules are assembled, for example by gluing, welding or by means of seals and pressure.
  • depressions 34 described above are to be integrated as cavities in the housing.
  • the gas-permeable support body, through which the fuel gas flows serving as a heat exchanger, which means that the coolant channels run through this support body.
  • the plastic housings 17, 18, 19 and 33 are preferably made of a flexible material.
  • the housing walls and the fuel cells 22 are kept at a distance, so that the gas supply to the fuel cell 22 can take place without interference.
  • spacers made of non-conductive material, not shown there, can be used.
  • FIG. 10 shows a cross section of the construction diagram of a fuel cell winding module based on the described flexible fuel cell film, which is particularly advantageous and can be used in a small space.
  • the structure initially consists of the fuel cell film, which in the variant shown here consists of the porous support body 40, the electrodes 41 on both sides, the polymeric solid electrolyte 42, the electronically conductive regions 43 and the insulation regions 44.
  • This fuel cell film is wound up together with a non-conductive and gas-impermeable film 45, so that two gas spaces - 46 and 47 - which are separate from one another are created.
  • chemical Energyträ ⁇ ger be supplied for the fuel cell foil, in the case of H 2/0 2 or H 2 / air fuel cell ⁇ ind this spiel ⁇ weise examples in the gas space 46 and in the gas space 47 Wasser ⁇ toff air.
  • the electrodes 41 applied on both sides of the polymer electrolyte regions thus receive the energy carriers required for the oxidation and reduction processes of the fuel cell.
  • spacers 48 can practically be produced by polymer networks which are co-wound in the module and generate free volume for a glass flow.
  • no spacers are used, but rather that small channels are provided in the separating film 45 on both sides are located, through which gas can flow to the electrodes.
  • the spacers 48 can, however, also be used for cooling, and coolant can be passed through a tubular or tubular design.
  • the end faces, which are not recognizable in the illustration, are particularly advantageous
  • Winding modules are sealed gas-tight with cover-shaped closures, which consist of a non-conductive material.
  • FIG. 11 shows a further, universal and inexpensive possibility for designing the invention.
  • First 3 foils are needed and placed one on top of the other.
  • Such a combination has a gas-impermeable film on both the top and bottom and is therefore gas-tight on both sides. So it does not have to be completely wound in itself as in Figure 10, but can be wound on any curves or body.
  • the two gas spaces required are located between foils 50 and 51 and between foils 51 and 52 and, as already described, can be produced by inserting porous foils or meshes between foils 50 and 51 on the one hand and foils 51 and 52 on the other hand .
  • the arrangement shown in FIG. 11 is then wound up, for example onto a body 53, as shown in FIG.
  • the gas can be supplied in different ways: On the one hand, the sides A and D (FIG. 11) can be sealed gas-tight between the foils 50, 51 and 52 by gluing, welding or by inserting strips of sealing material between the foil ends. In addition, the space between film 50 and 51 is sealed on side B and the space between film 51 and 52 is sealed on side C. After winding, the gas is supplied on the sides of the roll, for example hydrogen on one side (wound side) B), and oxygen is fed on the other side of the roll (wound side C).
  • the sides B, C and D can each be sealed gas-tight between the foils 50, 51 and 52 by gluing, welding or by inserting strips of sealing material. The gas is then supplied and removed, for example, for hydrogen on side A between foils 50 and 51 and for oxygen between foils 51 and 52.
  • the gas guiding structures can ensure optimal feeding of the gas to the electrodes.
  • the gas guiding structures can be channels, for example, which are integrated in the impermeable foils 50 and 52.
  • Suitable materials for the films are preferably materials which can be produced as a flexible film and which can withstand the conditions in the fuel cell, ie which are resistant to oxygen, hydrogen and hydrolysis. Examples are films made of polysulfones or perfluorinated materials can be used.

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  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
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  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne un système de cellules électrochimiques à électrolyte solide comprend un substrat plat (1) non conducteur et perméable aux gaz. Au moins une zone de cellules électrochimiques (3) constituée d'une première couche poreuse (7) électroconductrice d'électrode, d'une couche (8) formant une membrane conductrice de protons et d'une deuxième couche poreuse (11) d'électrode conductrice d'électrons superposées est appliquée selon la technique des couches minces sur une surface (2) du substrat (1).
PCT/DE1996/001123 1995-06-21 1996-06-21 Systeme de cellules electrochimiques a electrolyte solide WO1997001194A1 (fr)

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DE19522506.6 1995-06-21
DE19522506 1995-06-21

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WO1998016963A1 (fr) * 1996-10-16 1998-04-23 W.L. Gore & Associates, Inc. Ensemble tubulaire polymere pile a combustible a electrolyte et procede de fabrication
DE19739019A1 (de) * 1997-09-06 1999-03-11 Forschungszentrum Juelich Gmbh Gewickelte Brennstoffzelle
WO1999052159A2 (fr) * 1998-04-04 1999-10-14 Forschungszentrum Jülich GmbH Production d'une cellule electrochimique dotee d'un traitement au plasma
DE19904203A1 (de) * 1999-02-03 2000-08-10 Forschungszentrum Juelich Gmbh Brennstoffzelle nebst Herstellung in Batterieform
FR2819107A1 (fr) * 2000-12-29 2002-07-05 Commissariat Energie Atomique Procede de fabrication d'un assemblage d'elements de base pour un etage de pile a combustible
GB2412005A (en) * 2004-03-08 2005-09-14 Antig Tech Co Ltd Flexible fuel cell
WO2007063257A1 (fr) * 2005-11-30 2007-06-07 Stmicroelectronics Sa Pile a combustible integree empilable
EP1394884A3 (fr) * 2002-08-28 2008-10-08 Toyota Jidosha Kabushiki Kaisha Membrane électrolytique pour pile à combustible fonctionnant sur une plage de temperature moyenne, pile à combustible l'utilisant et son procédé de fabrication
US8765469B2 (en) 2005-08-17 2014-07-01 Takara Bio Inc. Method of producing lymphocytes
US8927273B2 (en) 2003-08-22 2015-01-06 Takara Bio Inc. Process for producing cytotoxic lymphocytes
US8975070B2 (en) 2002-03-25 2015-03-10 Takara Bio Inc. Process for producing cytotoxic lymphocyte
CN108290119A (zh) * 2015-11-26 2018-07-17 富士胶片制造欧洲有限公司 膜堆叠及其制造方法
CN109193017A (zh) * 2018-08-27 2019-01-11 京东方科技集团股份有限公司 电池

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DE19914661C2 (de) * 1999-03-31 2002-11-14 Joerg Mueller Verfahren zur Herstellung einer intergriert verschalteten Polymer-Elektrolyt-Membran-Brennstoffzelle
DE19916239C2 (de) * 1999-04-10 2001-07-05 Piller Gmbh Brennstoffzelle
EP1232533A2 (fr) 1999-11-17 2002-08-21 Neah Power Systems, Inc. Piles a combustible ayant des substrats de silicium et/ou des structures de soutien derivees de sol-gel
US20020022170A1 (en) 2000-08-18 2002-02-21 Franklin Jerrold E. Integrated and modular BSP/MEA/manifold plates for fuel cells
EP1415361A2 (fr) * 2000-08-18 2004-05-06 Jerrold E. Franklin Plaques de collecteurs bsp/mea int gr s modulaires et contacts flexibles pour piles combustible
US6756145B2 (en) * 2000-11-27 2004-06-29 California Institute Of Technology Electrode and interconnect for miniature fuel cells using direct methanol feed
US20030096146A1 (en) * 2001-03-30 2003-05-22 Foster Ronald B. Planar substrate-based fuel cell Membrane Electrode Assembly and integrated circuitry
US6620542B2 (en) 2001-05-30 2003-09-16 Hewlett-Packard Development Company, L.P. Flex based fuel cell
CA2436018C (fr) * 2001-12-28 2008-11-25 Dai Nippon Insatsu Kabushiki Kaisha Pile a combustible a electrolyte polymerique et separateur pour pile a combustible a electrolyte polymerique
DE10201148A1 (de) * 2002-01-15 2003-07-31 H2 Interpower Brennstoffzellen Verfahren und Vorrichtung zum Aufbringen einer Anpresskraft auf die Flächenelektroden einer Brennstoffzelle/eines Hydrolyseurs
DE10205852A1 (de) * 2002-02-13 2003-08-21 Creavis Tech & Innovation Gmbh Elektrolytmembran mit Diffusionsbarriere, diese umfassende Membranelektrodeneinheiten, Verfahren zur Herstellung und spezielle Verwendungen
ITTO20020643A1 (it) * 2002-07-23 2004-01-23 Fiat Ricerche Pila a combustibile ad alcool diretto e relativo metodo di realizzazione
US20040142227A1 (en) * 2002-11-26 2004-07-22 Kyocera Corporation Fuel cell casing, fuel cell, and electronic apparatus
US7670707B2 (en) 2003-07-30 2010-03-02 Altergy Systems, Inc. Electrical contacts for fuel cells
US7521145B2 (en) * 2003-10-16 2009-04-21 Wistron Corp. Fuel cells for use in portable devices
JP4794178B2 (ja) 2004-05-10 2011-10-19 新光電気工業株式会社 固体電解質燃料電池
DE102004048526A1 (de) * 2004-08-12 2006-02-23 Bayerische Motoren Werke Ag Brennstoffzellen-System
FR2880994B1 (fr) 2005-01-17 2010-08-20 Pierre Forte Convertisseur electrochimique compact
US8153318B2 (en) 2006-11-08 2012-04-10 Alan Devoe Method of making a fuel cell device
US8293415B2 (en) 2006-05-11 2012-10-23 Alan Devoe Solid oxide fuel cell device and system
US20080182012A1 (en) * 2007-01-31 2008-07-31 Motorola, Inc. Micro fuel cell having macroporous metal current collectors
US8278013B2 (en) 2007-05-10 2012-10-02 Alan Devoe Fuel cell device and system
US8227128B2 (en) 2007-11-08 2012-07-24 Alan Devoe Fuel cell device and system
FR2958798B1 (fr) 2010-04-07 2015-04-03 Commissariat Energie Atomique Pile a combustible comportant une membrane a conduction ionique localisee et procede de fabrication.
US9373875B2 (en) 2011-11-09 2016-06-21 Siemens Aktiengesellschaft Storage element for a solid electrolyte energy store
US8899995B2 (en) 2012-09-14 2014-12-02 Lenovo Enterprise Solutions (Singapore) Pte. Ltd. Modular battery
US10003062B2 (en) 2012-09-14 2018-06-19 Lenovo Enterprise Solutions (Singapore) Pte. Ltd. Modular battery cover
US9583792B2 (en) 2014-06-11 2017-02-28 Lenovo Enterprise Solutions (Singapore) Pte. Ltd. Dynamically configurable auto-healing battery
US9438048B2 (en) 2014-06-20 2016-09-06 Lenovo Enterprise Solutions (Singapore) Pte. Ltd. Modular battery cell architecture and control method
WO2016024035A1 (fr) * 2014-08-13 2016-02-18 Nokia Technologies Oy Appareil et procédé pour radiocommunication et stockage d'énergie
US9557387B2 (en) 2015-02-10 2017-01-31 Lenovo Enterprise Solutions (Singapore) Pte. Ltd. Testing individual cells within multi-cell battery applications
DE102021127547A1 (de) 2020-10-24 2022-04-28 Jakob Schillinger Elektrochemische Reaktorzelle

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998016963A1 (fr) * 1996-10-16 1998-04-23 W.L. Gore & Associates, Inc. Ensemble tubulaire polymere pile a combustible a electrolyte et procede de fabrication
DE19739019A1 (de) * 1997-09-06 1999-03-11 Forschungszentrum Juelich Gmbh Gewickelte Brennstoffzelle
DE19739019C2 (de) * 1997-09-06 2002-10-31 Forschungszentrum Juelich Gmbh Gewickelte Brennstoffzelle
WO1999052159A2 (fr) * 1998-04-04 1999-10-14 Forschungszentrum Jülich GmbH Production d'une cellule electrochimique dotee d'un traitement au plasma
WO1999052159A3 (fr) * 1998-04-04 2000-01-13 Forschungszentrum Juelich Gmbh Production d'une cellule electrochimique dotee d'un traitement au plasma
DE19904203A1 (de) * 1999-02-03 2000-08-10 Forschungszentrum Juelich Gmbh Brennstoffzelle nebst Herstellung in Batterieform
DE19904203C2 (de) * 1999-02-03 2001-05-10 Forschungszentrum Juelich Gmbh Brennstoffzelle nebst Herstellung in Batterieform
FR2819107A1 (fr) * 2000-12-29 2002-07-05 Commissariat Energie Atomique Procede de fabrication d'un assemblage d'elements de base pour un etage de pile a combustible
WO2002054522A1 (fr) * 2000-12-29 2002-07-11 Commissariat A L'energie Atomique Procede de fabrication d'un assemblage d'elements de base pour un etage de pile a combustible
US8975070B2 (en) 2002-03-25 2015-03-10 Takara Bio Inc. Process for producing cytotoxic lymphocyte
EP1394884A3 (fr) * 2002-08-28 2008-10-08 Toyota Jidosha Kabushiki Kaisha Membrane électrolytique pour pile à combustible fonctionnant sur une plage de temperature moyenne, pile à combustible l'utilisant et son procédé de fabrication
US7491462B2 (en) 2002-08-28 2009-02-17 Toyota Jidosha Kabushiki Kaisha Electrolyte membrane for fuel cell operable in medium temperature range, fuel cell using the same, and manufacturing methods therefor
US8927273B2 (en) 2003-08-22 2015-01-06 Takara Bio Inc. Process for producing cytotoxic lymphocytes
GB2412005A (en) * 2004-03-08 2005-09-14 Antig Tech Co Ltd Flexible fuel cell
US8765469B2 (en) 2005-08-17 2014-07-01 Takara Bio Inc. Method of producing lymphocytes
WO2007063257A1 (fr) * 2005-11-30 2007-06-07 Stmicroelectronics Sa Pile a combustible integree empilable
CN108290119A (zh) * 2015-11-26 2018-07-17 富士胶片制造欧洲有限公司 膜堆叠及其制造方法
CN109193017A (zh) * 2018-08-27 2019-01-11 京东方科技集团股份有限公司 电池
CN109193017B (zh) * 2018-08-27 2020-04-14 京东方科技集团股份有限公司 电池
US11283105B2 (en) 2018-08-27 2022-03-22 Boe Technology Group Co., Ltd. Battery having high battery capacity

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