WO2009120976A1 - Systèmes de pile à combustible utilisant la récupération passive d’eau liquide - Google Patents

Systèmes de pile à combustible utilisant la récupération passive d’eau liquide Download PDF

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Publication number
WO2009120976A1
WO2009120976A1 PCT/US2009/038591 US2009038591W WO2009120976A1 WO 2009120976 A1 WO2009120976 A1 WO 2009120976A1 US 2009038591 W US2009038591 W US 2009038591W WO 2009120976 A1 WO2009120976 A1 WO 2009120976A1
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WIPO (PCT)
Prior art keywords
fuel cell
layer
cathode
pem
cell system
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Ceased
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PCT/US2009/038591
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English (en)
Inventor
Alex Mossman
Brian Wells
Russell Barton
Henry Voss
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PolyFuel Inc
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PolyFuel Inc
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Publication date
Application filed by PolyFuel Inc filed Critical PolyFuel Inc
Publication of WO2009120976A1 publication Critical patent/WO2009120976A1/fr
Anticipated expiration legal-status Critical
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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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/861—Porous electrodes with a gradient in the porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • H01M8/04149—Humidifying by diffusion, e.g. making use of membranes
    • 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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
    • 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
    • H01M8/1065—Polymeric electrolyte materials characterised by the form, e.g. perforated or wave-shaped
    • 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
    • H01M8/1076—Micromachining techniques, e.g. masking, etching steps or photolithography
    • 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
    • H01M8/1079—Inducing porosity into non porous precursors membranes, e.g. leaching, pore stretching
    • 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
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • 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
    • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • 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 cathode further comprises one or more second layers selected from the group consisting of a gas diffusion barrier (GDB) layer, a gas diffusion layer (GDL) and a liquid water distribution (LWD) layer.
  • GDB gas diffusion barrier
  • GDL gas diffusion layer
  • LWD liquid water distribution
  • the GDB layer has hydrophobic pores, is optionally electrically conductive, allows the diffusion of oxygen gas and resists the flow of water vapor across said layer.
  • the GDL is optionally electrically conductive and allows the flow of gases across said layer.
  • the LWD layer is electrically conductive and allows the flow of liquid water through or across said layer.
  • Figure IB depicts an MEA cross section showing a laser drilled hole. Exit diameter of hole is 2 microns. Cross section was prepared using epoxy back-fill under vacuum with subsequent polishing; a portion of the hole shows it partially filled with epoxy.
  • Figure 3 schematically depicts the various layers that can be used alone or in combination to form a cathode useful in the passive recovery of water.
  • Such fuel cell systems provide a commercially viable fuel cell which is sufficiently powerful to power mobile computing devices, small enough to be volumetrically competitive with an extended run lithium ion battery, light enough to provide higher gravimetric energy density than lithium ion batteries, and instantly rechargeable with the supply of a fresh fuel cartridge.
  • the system also enables not only system simplification, but control of important system parameters and high energy conversion efficiency through reduction in the parasitic power demands of the system components.
  • the primary purpose of the invention is to provide fuel cells with simplified fuel cell systems. This is achieved by passive water recovery of a portion of the liquid water formed at, or transported to, the cathode of a fuel cell. This allows for the elimination of the cathode liquid water recirculation loop and optionally, the cathode heat exchange assembly. In the later case, this results in an air cooled fuel cell whereby the active cooling of the fuel cell is via the cathode air stream.
  • Passive water recovery means water recovery from the cathode side of a fuel cell that does not involve additional components external to the fuel cell itself to effect collection of water from the cathode exhaust stream (i.e., condensers, water traps, water pumps or other mechanisms for directing such water from the cathode oxidant exhaust back to the anode fuel stream).
  • Fluid connection via pipes, tubes, manifolds, channels, or other mechanisms which have sufficiently low liquid water flow resistance can be used to direct the recovered water to the desired location without substantial loss of water to other locations.
  • Non-passive recovery of water typically requires some form of power to direct the collected water to a desired location where the water is either used in an electrochemical reaction or rejected to the environment or collected for future use. It further typically represents an additional heat load on the system, to condense water from the vapor state and direct such water to a desired location.
  • liquid water pressure created by the build-up of liquid water at the liquid barrier layer is often insufficient to motivate liquid water to permeate through conventional PEM membranes having thicknesses between 50 and 175 microns (as measured in the dry state). However, the pressure may be sufficient to cause water transport across thinner membranes.
  • the liquid barrier layer can be used with per-fluorinated membranes such as Nafion, manufactured by E.I. du Pont de Nemours and Company, either alone or in combination with the formation of passages across the Nafion membranes.
  • the gas diffusion barrier layer (GDB) layer is preferably interposed between the liquid barrier layer and the cathode gas diffusion layer although it may be interposed between the gas diffusion layer and the oxidant air flow passages.
  • the gas barrier layer has low gas permeability and may also be hydrophobic. The purpose of this layer is to restrict to a certain degree the diffusion rate of water vapor through it from the cathode catalyst layer to the oxidant air stream but also to enable sufficient diffusion of the reactant species oxygen from the oxidant air stream through this layer, through the liquid water barrier layer, through the liquid water distribution layer (if present) to the cathode catalyst layer to support and maintain the electrochemical reaction.
  • LWB and GDB layers in making a cathode.
  • the properties of the separate layers can be combined in a single layer.
  • a LWB/GDB ink can be layered on a plastic coupon to produce a single layer with properties of the LWD and GDB layers.
  • the LWD/GDB ink can be layered directly on a GDL.
  • Example 1 sets forth the preferred method of forming such a layer by repeated application of the LWB/GDB ink on a gas diffusion layer.
  • MEA Embodiments [0070] The following are MEA embodiments that can be used in the fuel cell system using either a standard PEM or a water permeable PEM.
  • the PEM membrane can be used to transport water directly from the cathode to the anode.
  • Typical PEM membranes have insufficient permeability to enable sufficient liquid water transport.
  • Special PEM membranes are fabricated, ones that are especially thin or ones that have high water permeation properties, can be used to provide a water transport path from cathode to anode. But such membranes present challenges because they would also enable the permeation of fuel from anode to cathode. It is preferred to have a PEM with a combination of low and high water permeability properties and more preferred to have the high permeability properties over a minority of the surface area of the PEM. It is further preferred to use the PEM with low and high water permeation properties in combination with a cathode electrode structure which includes a liquid water barrier layer and a gas barrier layer.
  • [ooo5] i and j are independently integers equal to or greater than 1 ;
  • At least one Of Ar 2 comprises an ion-conducting group; [ooi3] T, U, V and W are independently a bond, -O-, -S-, -C(O)-, -S(O) 2 -,
  • [ooi5] i and j are independently integers equal to or greater than 1 ;
  • At least one OfAr 2 comprises an ion-conducting group
  • a, b, c, and d are mole fractions wherein the sum of a, b, c and d is 1, a is at least 0.3 and at least one of b, c and d are greater than 0; and
  • Polymer membranes may be fabricated by solution casting of the ion-conductive copolymer.
  • the polymer membrane may be fabricated by solution casting the ion-conducting polymer the blend of the acid and basic polymer.
  • a number of cells can be combined to achieve appropriate voltage and power output.
  • Such applications include electrical power sources for residential, industrial, commercial power systems and for use in locomotive power such as in automobiles.
  • Other uses to which the invention finds particular use includes the use of fuel cells in portable electronic devices such as cell phones and other telecommunication devices, video and audio consumer electronics equipment, computer laptops, computer notebooks, personal digital assistants and other computing devices, GPS devices and the like.
  • the fuel cells may be stacked to increase voltage and current capacity for use in high power applications such as industrial and residential sewer services or used to provide locomotion to vehicles.
  • Such fuel cell structures include those disclosed in U.S. Patent Nos.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Fuel Cell (AREA)
  • Composite Materials (AREA)

Abstract

L’invention concerne un système  de pile à combustible comprenant (1) une alimentation en combustible; (2) une pile à combustible, et (3) un circuit anodique. La pile à combustible contient un ensemble d’électrodes membranaire (MEA) comprenant une membrane électrolytique polymère (PEM) comprenant un polymère conducteur d’ions. Dans un mode de réalisation, le PEM est un PEM perméable à l’eau avec des passages qui passent à travers le PEM depuis la surface de la cathode vers la surface de l’anode. Le PEM perméable à l’eau peut être utilisé en combinaison avec une cathode comprenant une couche écran contre l’eau liquide (LWB) et optionnellement d’autres couches qui fournissent une récupération passive de l’eau liquide à la cathode. Dans un autre mode de réalisation, le PEM n’est pas un PEM perméable à l’eau, mais est utilisé en combinaison avec la cathode susmentionnée pour fournir une récupération passive de l’eau. Une telle récupération passive de l’eau liquide peut simplifier les systèmes de pile à combustible par la réduction ou l’élimination des dispositifs de récupération d’eau liquide à la cathode et optionnellement des ensembles d’échange de chaleur à l’anode, permettant une pile à combustible simplifiée refroidie à l’air.
PCT/US2009/038591 2008-03-28 2009-03-27 Systèmes de pile à combustible utilisant la récupération passive d’eau liquide Ceased WO2009120976A1 (fr)

Applications Claiming Priority (2)

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US4053908P 2008-03-28 2008-03-28
US61/040,539 2008-03-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8945790B2 (en) 2013-03-15 2015-02-03 Ford Global Technologies, Llc Microporous layer structures and gas diffusion layer assemblies in proton exchange membrane fuel cells
US9461311B2 (en) 2013-03-15 2016-10-04 Ford Global Technologies, Llc Microporous layer for a fuel cell

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451470B1 (en) * 1997-03-06 2002-09-17 Magnet-Motor Gesellschaft Für Magnetmotorische Technik Mbh Gas diffusion electrode with reduced diffusing capacity for water and polymer electrolyte membrane fuel cells
WO2004093231A2 (fr) * 2003-04-15 2004-10-28 Mti Microfuel Cells Inc. Techniques passives de gestion de l'eau dans des piles a combustible a methanol direct
US20040241531A1 (en) * 2001-09-18 2004-12-02 Hubertus Biegert Membrane-electrode assembly for a self-humidifying fuel cell
US20050100780A1 (en) * 2003-11-06 2005-05-12 Matsushita Electric Industrial Co., Ltd. Fuel cell and fuel cell system
US20070269708A1 (en) * 2006-05-17 2007-11-22 In-Hyuk Son Fuel cell system having water recovering and circulating structure
WO2008079529A2 (fr) * 2006-11-07 2008-07-03 Polyfuel, Inc. Récupération passive de l'eau liquide produite par des piles à combustible

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6451470B1 (en) * 1997-03-06 2002-09-17 Magnet-Motor Gesellschaft Für Magnetmotorische Technik Mbh Gas diffusion electrode with reduced diffusing capacity for water and polymer electrolyte membrane fuel cells
US20040241531A1 (en) * 2001-09-18 2004-12-02 Hubertus Biegert Membrane-electrode assembly for a self-humidifying fuel cell
WO2004093231A2 (fr) * 2003-04-15 2004-10-28 Mti Microfuel Cells Inc. Techniques passives de gestion de l'eau dans des piles a combustible a methanol direct
US20050100780A1 (en) * 2003-11-06 2005-05-12 Matsushita Electric Industrial Co., Ltd. Fuel cell and fuel cell system
US20070269708A1 (en) * 2006-05-17 2007-11-22 In-Hyuk Son Fuel cell system having water recovering and circulating structure
WO2008079529A2 (fr) * 2006-11-07 2008-07-03 Polyfuel, Inc. Récupération passive de l'eau liquide produite par des piles à combustible

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8945790B2 (en) 2013-03-15 2015-02-03 Ford Global Technologies, Llc Microporous layer structures and gas diffusion layer assemblies in proton exchange membrane fuel cells
US9461311B2 (en) 2013-03-15 2016-10-04 Ford Global Technologies, Llc Microporous layer for a fuel cell

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