US20040234829A1 - Ambient pressure fuel cell system employing partial air humidification - Google Patents

Ambient pressure fuel cell system employing partial air humidification Download PDF

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Publication number
US20040234829A1
US20040234829A1 US10/792,403 US79240304A US2004234829A1 US 20040234829 A1 US20040234829 A1 US 20040234829A1 US 79240304 A US79240304 A US 79240304A US 2004234829 A1 US2004234829 A1 US 2004234829A1
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United States
Prior art keywords
stack
fuel cell
cell system
air
fuel
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Abandoned
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US10/792,403
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English (en)
Inventor
Richard Sederquist
Brian Wells
Alexander Mossman
Craig Louie
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mercedes Benz Group AG
Ford Motor Co
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Ballard Power Systems Inc
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Priority to US10/792,403 priority Critical patent/US20040234829A1/en
Assigned to BALLARD POWER SYSTEMS INC. reassignment BALLARD POWER SYSTEMS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WELLS, BRIAN W., SEDERQUIST, RICHARD A., MOSSMAN, ALEXANDER, LOUIE, CRAIG R.
Publication of US20040234829A1 publication Critical patent/US20040234829A1/en
Priority to US12/110,767 priority patent/US8304123B2/en
Assigned to FORD MOTOR COMPANY, DAIMLER AG reassignment FORD MOTOR COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BALLARD POWER SYSTEMS INC.
Abandoned legal-status Critical Current

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    • 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
    • H01M8/04029—Heat exchange using liquids
    • 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
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—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
    • H01M8/04141—Humidifying by water containing exhaust gases
    • 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
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the reactants
    • 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
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0432—Temperature; Ambient temperature
    • 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
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to fuel cell systems operating at or near ambient pressure.
  • the present invention relates to fuel cell systems operating at or near ambient pressure with partial air humidification, and methods of operating such systems.
  • Fuel cells are known in the art. Fuel cells electrochemically react a fuel stream comprising hydrogen and an oxidant stream comprising oxygen to generate an electric current. Fuel cell electric power plants have been employed in transportation, portable and stationary applications.
  • reactants can be humidified by flowing the reactant stream and liquid water on opposite sides of a water permeable membrane.
  • Product water from the fuel cell can be condensed from the reactant exhaust streams and then used for humidification.
  • Water vapor or atomized water droplets may be injected into the reactant streams, as well.
  • the oxidant stream may also be heated and humidified by flowing it and the oxidant exhaust stream on opposite sides of a water permeable membrane in a combined heat and humidity exchange apparatus. Examples of the latter apparatus are described in U.S. Pat. No. 6,007,931 and commonly assigned U.S. Pat. No. 6,416,895 B1.
  • An alternative approach employs wicking or similar passive means to provide water to the membrane.
  • PEM fuel cell power plants developed by UTC Fuel Cells, LLC, for example, employ this approach.
  • Porous water transport plates adjacent porous anode and/or cathode support layers facilitate water transport to the anode and/or cathode surfaces.
  • These power plants can be operated at near-ambient pressures, which can reduce the cost and power loss associated with an air compressor.
  • U.S. Pat. No. 6,451,470 B1 and CA 2,342,825 A1 disclose gas diffusion layers having a gas permeability gradient perpendicular to the membrane that inhibits the diffusion of water from the membrane (a “gas diffusion barrier”, or GDB). This permits fuel cell operation without external humidification of the reactants.
  • GDB structure also allows air-cooling of the fuel cell by supplying air to the cathode flow fields at relatively high stoichiometries.
  • the '825 application discloses adopting air ratios, i.e., stoichiometries, of 8-70.
  • the '470 patent discloses that the maximum operating temperature of fuel cells employing a GDB is about 75° C. if air is supplied at ambient pressure. According to the '470 patent, at higher temperatures, a GDB having a sufficiently low effective diffusion coefficient for water would no longer ensure sufficient diffusion for reactant gases, in particular oxygen; although increasing air pressure permits increased operating temperatures (col. 3, lines 29-42). Indeed, the system disclosed in the '470 patent demonstrated a drastic drop in performance above a power density of 503 mA/cm 2 at near-ambient air pressure (col. 7, lines 50-60). Published results of stacks employing UTC Fuel Cell porous bipolar plates disclose optimized performance at 65° C. (see, D. J. Wheeler et al., J New Mat. Electrochem. Systems 4, 233-238 (2001)).
  • a fuel cell system and methods of its operation are provided. Fuel cell power plants and vehicles incorporating the present fuel cell system are also provided.
  • the present fuel cell system comprises: a fuel cell stack; a fuel system for supplying fuel to the stack; a blower for supplying air to the stack at near-ambient pressure; a humidification device in fluid communication with an air stream supplied to the stack and a cathode exhaust stream exiting the stack for transferring water vapor from the cathode exhaust stream to the air stream; and a coolant loop for circulating a liquid coolant through the stack.
  • the fuel cells in the stack incorporate a cathode gas diffusion barrier layer.
  • the present fuel cell system comprises: a fuel cell stack with fuel cells having a cathode gas diffusion barrier means; a fuel system for supplying a fuel to the stack; supply means for supplying air to the stack at near-ambient pressure; humidification means for transferring water vapor from the cathode exhaust stream with the air supplied to the stack; and, a coolant loop for circulating a liquid coolant through the stack.
  • the present fuel cell system may be part of a power plant for use in vehicles; as part of a cogeneration system for stationary applications; or as part of a generator for portable power, back-up power or UPS applications.
  • the present method comprises: supplying a stoichiometric excess of air to the stack at near-ambient pressure; supplying a cathode exhaust stream to a humidification device; maintaining the relative humidity of the air stream below a stack inlet saturation point; maintaining the relative humidity of the cathode exhaust stream below a stack inlet saturation point; and, operating the stack at a temperature greater than about 75° C.
  • FIGS. 1 and 2 are schematic representations of embodiments of the present fuel cell system.
  • blowers refers to blowers, fans and similar means for supplying a gas stream to a fuel cell stack at or near ambient pressure.
  • the present fuel cell system can maintain adequate water balance in the fuel cells of a fuel cell stack operating at high current densities and temperatures, without requiring liquid water removal or a pressurized air supply.
  • the present fuel cell system may be incorporated into a fuel cell power plant.
  • the fuel cell power plant may be used in various applications, such as an engine for a fuel cell-powered vehicle.
  • FIG. 1 is a schematic representation of an embodiment of the present fuel cell system.
  • hydrogen is supplied via valve 10 to the anodes 12 of the PEM fuel cells in stack 14 and air is supplied via variable-speed blower 16 to the cathodes 18 .
  • the hydrogen and oxygen in the air are electrochemically reacted to generate electrical power.
  • Liquid coolant is circulated via pump 20 through the stack coolant circuit 22 and radiator 24 , maintaining stack 14 within a suitable operating temperature range.
  • the cathodes of stack 14 incorporate a gas diffusion barrier (GDB) to assist in maintaining adequate humidification of the fuel cell membrane.
  • GDB is a gas diffusion layer that comprises a region spaced apart from the membrane that has a lower water vapor permeability than a region adjacent to the membrane, and which inhibits the diffusion of water vapor away from the membrane.
  • Suitable materials for use as GDB include expanded graphite sheet materials having transverse fluid channels that have larger openings on the surface in contact with the membrane than the openings in contact with the fuel cell plate, such as described in U.S. Pat. No. 6,521,369B1.
  • porous electrode material that is (partially) filled or coated with solid or liquid materials that decrease the permeability of water vapor, such as described in U.S. Pat. No. 6,451,470 B1 may be utilized.
  • the barrier layer may comprise substantially impermeable materials with mechanical openings therein (like expanded graphite sheet, for example), filled or partially filled materials or microporous materials.
  • the selection and design of the GDB is not essential to the present fuel cell system, and persons skilled in the art can readily select a suitable GDB for a given application.
  • the GDB should be capable of maintaining adequate humidification of the fuel cell membranes at the selected temperature under partial power conditions.
  • Air is supplied to stack 14 at or near ambient pressure.
  • the pressure drop associated with the stack air supply is about 0.3-0.5 psid (20-35 mbar).
  • the air stoichiometry may be about 1.2-3.0.
  • Inlet air is drawn through filter 26 , which removes particulates and may also remove other contaminants, such as carbon dioxide and/or hydrocarbons, for example.
  • the filtered air enters ventilation box 28 where it is partially preheated by stack 14 . Allowing stack 14 to preheat the inlet air, which is rejected as higher temperature cathode exhaust, reduces the overall heat rejection requirements of the fuel cell system by this amount of sensible heating.
  • any hydrogen leakage from stack 14 is collected in ventilation box 28 , mixed with the inlet air and consumed in cathodes 18 .
  • the ventilation box is not essential to the present fuel cell system, and it is omitted in other embodiments.
  • the preheated air is directed to the “dry” side of gas-exchange humidifier 30 , where it is further heated and partially humidified by the flow of cathode exhaust entering the “wet” side of humidifier 30 .
  • Damper 32 may be opened to allow at least a portion of the cathode exhaust to be recycled to stack 14 , if desired.
  • cathode recycle could be used during partial power operation and/or to reduce the load on humidifier 30 .
  • Suitable gas-exchange humidifiers may incorporate semipermeable membranes, such as ion exchange or paper membranes, for example.
  • semipermeable membranes such as ion exchange or paper membranes
  • An example of a suitable gas-exchange humidifier is disclosed in US 2001/0046616 A1, commonly assigned to the present applicants. The selection of gas-exchange humidifier, however, is not essential to the present fuel cell system, and persons skilled in the art can readily select a suitable humidifier for a given application.
  • blower 16 may be located upstream of humidifier 30 , if desired, having air drawn through the dry side results in a slightly higher pressure on the wet side. Any leak in the membrane would cause the cathode exhaust to mix with the air. This is equivalent to partial cathode recycle and is an acceptable failure mode for humidifier 30 . This may allow for cost-savings in designing or selecting a humidifier due to less restrictive sealing requirements, for example.
  • FIG. 2 is a schematic representation of another embodiment of the present fuel cell system.
  • the system of FIG. 2 employs air blower 36 and cathode recycle blower 38 for independent control of the air and cathode exhaust recycle flow rates.
  • an enthalpy wheel 40 is employed to partially humidify the air stream supplied to stack 14 .
  • Enthalpy wheels are known in the art; the enthalpy wheel available from Emprise Corporation (Marietta, Ga.), incorporating a cordierite ceramic honeycomb material, for example, may be suitable.
  • the particular enthalpy wheel is not essential to the present fuel cell system, and persons skilled in the art can readily select a suitable such device for a given application.
  • air and fuel may be supplied to the stack and the fuel cells operated at low load and low voltage to enhance internal heat generation.
  • the load may be increased such that the partial pressure of water vapor produced in the fuel cells is below the saturation pressure to ensure that the air/cathode exhaust in the stack remains undersaturated.
  • fuel and air may be catalytically combusted on the cathodes of the fuel cell in a controlled manner to heat the stack.
  • a catalytic heater may be incorporated into the coolant loop, if desired; fuel and air may be combusted in the heater to heat the coolant circulating in the stack.
  • bypass valve 34 may be activated so that coolant bypasses radiator 24 during start up.
  • air is also supplied to the stack at high air stoichiometries (e.g., ⁇ 200) at start-up.
  • higher temperature operation e.g., >75° C.
  • higher operating temperatures increase the heat rejection capacity of the cooling system.
  • heat rejection is a limiting factor in the maximum power output for the stack, as radiator frontal area and performance are difficult to increase.
  • increasing the heat rejection capacity of the cooling system enables fuel cell power plants with higher engine ratings for automotive applications.
  • Higher temperature operation also provides higher cogeneration temperatures for stationary applications and better temperature derate characteristics for intermittent use applications.
  • the present fuel cell system employs an undersaturated air supply. That is, the relative humidity of the air supplied to the present fuel cell system is kept below the inlet cell saturation point, and the relative humidity of the cathode exhaust is kept below the outlet cell saturation point.
  • an undersaturated air supply can also inhibit or substantially prevent liquid water from condensing and accumulating in the stack. This may provide several further advantages over similar fuel cell systems employing liquid water management. For example, liquid water management equipment, such as gas/water separators, drain traps, deionized or particulate water filters, or tanks for water fill or overflow, is not required. This may decrease the cost and complexity of the present fuel cell system.
  • coolant load through the coolant system.
  • Product water present in the stack is substantially or completely in the vapor phase; hence, the heat of condensation of liquid product water does not have to be rejected through the coolant.
  • Performance losses due to flooding of the fuel cells may also be reduced or eliminated.
  • freezability and cold start-up capability may be increased because freezing of liquid water in the stack is reduced or eliminated.
  • lower component corrosion and/or carrying of corrosion products in the stack by liquid water may result in longer stack lifetime and/or enable the use of lower-cost materials.
  • the present fuel cell system may be operated at lower temperatures at lower power outputs and higher temperatures at higher power outputs. At lower power output, less or no external humidification of the air stream may be required because of the ability of the cathode GDB to inhibit water vapor diffusion away from the membrane, as described above. At the same time, higher air stoichiometries may be employed to assist in maintaining undersaturated conditions in the cathode flow field.
  • the fan speed or output of the radiator in the present fuel cell system may be increased at high power output.
  • the associated small increase in parasitic power loss may be offset in significantly enhanced cooling system performance and a reduced maximum fuel cell operating temperature.
  • the speed of the blower in the air supply system is controlled to provide the desired amount of humidification to the air stream supplied to the stack at a given operating temperature. Controlling the speed of the blower allows for varying the dwell time of the incoming air in a gas-exchange humidifier or enthalpy wheel, for example. The longer the dwell time, the greater the heat and water vapor transfer rate from the cathode exhaust to the air stream. In other embodiments, the amount of cathode exhaust recycled into the incoming air stream is controlled with temperature to achieve the same result. In yet other embodiments, the speed of the blower is kept constant, and the amount of air supplied to the stack is controlled with temperature to provide the desired amount of humidification supplied to the stack. For example, controlled valves, dampers or diverters could be employed to vary the amount of air supplied to the stack from the blower. Combinations of the foregoing controls may also be used.
  • Hydrogen supply to stack 14 is dead-ended in the illustrated embodiments.
  • anodes 12 may be purged of accumulated inert gases that may build up over time.
  • anode purge gas may be introduced into ventilation box 28 , where it is diluted in the inlet air to below 4% and consumed at cathodes 18 .
  • Other means of disposing of the anode vent gas may be employed, if desired, including catalytically combusting it in a separate combustor or exhausting it to the environment.
  • a hydrogen recycle system is employed instead. The hydrogen supply need not be closed, though.
  • the fuel cell system includes a fuel processing system for reforming a fuel to produce hydrogen-rich reformate stream for the stack.
  • the anode exhaust can be combusted to produce heat energy for upstream or downstream processing steps, if desired.
  • the hydrogen source and configuration of the hydrogen supply system are not essential to the present fuel cell system; persons skilled in the art can readily design a suitable hydrogen supply system for a given application.
  • liquid coolant is not essential to the present fuel cell system. Suitable coolants include deionized water, ethylene glycol and mixtures thereof. Other suita 5 ble liquid coolants will be readily apparent to persons skilled in the art. While a radiator is described in the illustrated embodiments, other heat exchange apparatus may be substituted in the present fuel cell system, provided adequate cooling of the fuel cell stack can be achieved.
  • the present fuel cell system is not limited to these external air humidification devices. Other humidification devices that can recover water vapor from the cathode exhaust may also be employed. Similarly, while the illustrated embodiments employ a cathode recycle loop, the present fuel cell system does not require one.
  • the cathode exhaust is preferred for humidifying the incoming air stream, as this reduces or eliminates the requirement for water storage systems in the presen 6 t fuel cell system.
  • the air supply is may also be humidified by a separate water source, in addition to the cathode exhaust.
  • a fuel cell system employing cathode GDB in the stack cannot be operated at high temperatures with unhumidified air at high stoichiometries and near-ambient pressure without drying out the fuel cell membranes.
  • partial humidification of the air stream enables high temperature operation at near-ambient pressures while maintaining fuel cell performance.
  • liquid water removal is minimized or eliminated, thereby reducing parasitic losses due to pressurized operation and flooding.
  • the present fuel cell system also avoids problems associated with passive water management systems, as mentioned earlier.

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US12/110,767 US8304123B2 (en) 2003-03-03 2008-04-28 Ambient pressure fuel cell system employing partial air humidification

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US10/792,403 US20040234829A1 (en) 2003-03-03 2004-03-03 Ambient pressure fuel cell system employing partial air humidification

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EP1604417A2 (en) 2005-12-14
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US20080199743A1 (en) 2008-08-21
CN101369666A (zh) 2009-02-18

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