WO2007090284A1 - Intégration d'électrode passive dans une pile à combustible - Google Patents

Intégration d'électrode passive dans une pile à combustible Download PDF

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Publication number
WO2007090284A1
WO2007090284A1 PCT/CA2007/000189 CA2007000189W WO2007090284A1 WO 2007090284 A1 WO2007090284 A1 WO 2007090284A1 CA 2007000189 W CA2007000189 W CA 2007000189W WO 2007090284 A1 WO2007090284 A1 WO 2007090284A1
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WO
WIPO (PCT)
Prior art keywords
reactant
fuel cell
cell module
electrode
reservoir
Prior art date
Application number
PCT/CA2007/000189
Other languages
English (en)
Inventor
Nathaniel Joos
Stephen Joseph Burany
Original Assignee
Hydrogenics Corporation
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
Application filed by Hydrogenics Corporation filed Critical Hydrogenics Corporation
Priority to EP07710606A priority Critical patent/EP1987556A1/fr
Priority to CA2634157A priority patent/CA2634157C/fr
Publication of WO2007090284A1 publication Critical patent/WO2007090284A1/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
    • H01M8/04—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
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • 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
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04208—Cartridges, cryogenic media or cryogenic reservoirs
    • 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
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
    • 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
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
    • 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2457—Grouping of fuel cells, e.g. stacking of fuel cells with both reactants being gaseous or vaporised
    • 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 invention relates to fuel cells, and, in particular to reducing the rate of wear and degradation experienced by some components of a fuel cell during shutdown and restarting periods.
  • a fuel cell converts chemical energy stored in a fuel into a useful form of energy, such as for example, electricity.
  • a fuel cell is a Proton Exchange Membrane (PEM) fuel cell that is operable to produce electricity.
  • PEM Proton Exchange Membrane
  • a typical PEM fuel cell includes an electrolyte membrane arranged between an anode electrode and a cathode electrode. Hydrogen fuel is supplied to the anode electrode and an oxidant is supplied to the cathode electrode. Within the PEM fuel cell the hydrogen fuel and the oxidant are employed as reactants in a set of complementary electrochemical reactions that yield electricity, heat and water.
  • small amounts of hydrogen fuel and oxidant remaining inside a PEM fuel cell, after respective supplies of these reactants are closed off, are known to combust during shutdown and restarting processes.
  • Combustion within a PEM fuel cell causes the deterioration of various components including the electrolyte membrane and catalyst layers deposited on the electrodes.
  • the cumulative deterioration of various components significantly reduces the efficiency of the PEM fuel cell and may lead to failure of the PEM fuel cell.
  • Another undesired reaction that may occur is the electrochemical corrosion of at least one catalyst layer within a PEM fuel cell. This further deteriorates the performance of a PEM fuel cell.
  • One aspect of a fuel cell module described in the specification includes a first reactant holding tank, which is pressurized by a pump during normal operation of the fuel cell module so that a pre-determined mass of first reactant is present in the holding tank.
  • the first reactant supply is closed to the fuel cell module and the first reactant from the holding tank is provided instead to a first reactant inlet of the fuel cell module.
  • This system is useful when the first reactant supply pressure is low (e.g. a low pressure fuel cell module construction is used) and the use of a non-pressurized holding tank would necessitate a very large volume holding tank. Since the pressure in the first reactant holding tank is built up in this embodiment of the invention, the volume of the holding tank can be small but the provided mass of first reactant from the holding tank will still be sufficient to perform a blanketing shutdown as described above.
  • a fuel cell module described in the specification relates to a fuel cell stack including at least one fuel cell, each fuel cell including an anode electrode, a cathode electrode and an electrolyte medium arranged between the anode electrode and the cathode electrode.
  • each fuel cell including an anode electrode, a cathode electrode and an electrolyte medium arranged between the anode electrode and the cathode electrode.
  • the anode electrode is provided with a first reactant
  • the cathode electrode is provided with a first mixture containing a second reactant and a non-reactive agent.
  • the fuel cell module further comprises a parasitic load that is connectable across the anode and the cathode electrodes.
  • the fuel cell module further comprises a first reactant supply, fluidly connectable to the anode electrode, for supplying the first reactant to the anode electrode.
  • the fuel cell module further comprises a side stream, optionally connected in parallel to, and fluidly connectable to the first reactant supply and the anode electrode.
  • the fuel cell module further comprises a reactant reservoir, fluidly connectable to the side stream, for storing an amount of the first reactant suitable for a shutdown process of the fuel cell module. When the fuel cell module is shutdown, the stored amount of the first reactant is drawn from the reactant reservoir and electrochemically reacts with an amount of the second reactant remaining in the fuel cell module, to electrochemically consume all of the amounts of the first and second reactants, thereby leaving a second mixture that substantially comprises the non-reactive agent.
  • the fuel cell module further comprises a pressure -A-
  • generating device fluidly connectable to the side stream and positioned upstream of the reactant reservoir, for pressurizing and delivering the first reactant from the first reactant supply to the reactant reservoir.
  • a fuel cell module described in the specification relates to a fuel cell including a first electrode, a second electrode and an electrolyte medium arranged between the first and second electrodes.
  • the first electrode is provided with a first reactant and the second electrode is provided with a first mixture containing a second reactant and a non-reactive agent.
  • the fuel cell module further comprises a parasitic load that is connectable across the first and second electrodes.
  • the fuel cell module further comprises a first reactant supply, fluidly connectable to the anode electrode, for supplying first reactant to the anode electrode.
  • the fuel cell module further comprises a side stream, optionally connected in parallel to, and fluidly connectable to the first reactant supply and the anode electrode.
  • the fuel cell module further comprises a reactant reservoir, fluidly connectable to the side stream, for storing an amount of the first reactant suitable for a shutdown process of the fuel cell module.
  • a reactant reservoir fluidly connectable to the side stream, for storing an amount of the first reactant suitable for a shutdown process of the fuel cell module.
  • the stored amount of the first reactant is drawn from the reactant reservoir and electrochemically reacts with an amount of the second reactant remaining in the fuel cell module, to electrochemically consume all of the amounts of the first and second reactants, thereby leaving a second mixture that substantially comprises the non-reactive agent.
  • the fuel cell module further comprises a pressure generating device, fluidly connectable to the side stream and positioned upstream of the reactant reservoir, for pressurizing and delivering the first reactant from the first reactant supply to the reactant reservoir.
  • a fuel cell including a first electrode, a second electrode and an electrolyte membrane arranged between the first and second electrodes.
  • the process comprises the step of providing the first electrode with a first reactant and the second electrode with a first mixture containing a second reactant and a non-reactive agent.
  • the operation process further comprises the step of pressurizing a portion of the first reactant and storing the first reactant in a reactant reservoir.
  • the process further comprises the step of stopping an inflow of the first reactant into the first electrode.
  • the shutdown process further comprises the step of cutting-off power to supporting balance of plant elements.
  • the shutdown process further comprises the step of drawing current through a parasitic load connectable across the first and second electrodes.
  • the shutdown process further comprises the step of permitting the stored first reactant to flow to the first electrode for the electrochemical consumption of a remaining amount of a second reactant.
  • the first reactant electrochemically reacts with the remaining amount of the second reactant, thereby leaving a second mixture that substantially comprises the non-reactive agent.
  • Figure 1 is a simplified schematic diagram of a fuel cell module
  • Figure 2 is a schematic diagram illustrating a first arrangement of a fuel cell module according to aspects of an embodiment of the invention
  • Figure 3 is a chart illustrating the composition of gases present in cathode electrodes of the fuel cell module shown in Figure 2 during sequential stages of a shutdown process
  • Figure 4 is a schematic diagram illustrating a second arrangement of a fuel cell module according to aspects of another embodiment of the invention.
  • Figure 5 is a schematic diagram illustrating a third arrangement of a fuel cell module according to aspects of another embodiment of the invention.
  • Figure 6 is a schematic diagram illustrating a fourth arrangement of a fuel cell module according to aspects of another embodiment of the invention.
  • Figures 7a, 7b and 7c are schematic diagrams illustrating fourth, fifth and sixth arrangements of a fuel cell module according to aspects of another embodiment of the invention.
  • Figure 8 is a schematic diagram illustrating a seventh arrangement of a fuel cell module according to another embodiment of the present invention.
  • a fuel cell module is typically made up of a number of fuel cells connected in series to form a fuel cell stack.
  • the fuel cell module also includes a suitable combination of associated structural elements, mechanical systems, hardware, firmware and software that is employed to support the function and operation of the fuel cell module.
  • Such items include, without limitation, piping, sensors, regulators, current collectors, seals and insulators.
  • FIG. 1 shown is a simplified schematic diagram of a Proton Exchange Membrane (PEM) fuel cell module, simply referred to as fuel cell module 100 hereinafter, that is described herein to illustrate some general considerations relating to the operation of fuel cell modules. It is to be understood that the present invention is applicable to various configurations of fuel cell modules that each include one or more fuel cells.
  • PEM Proton Exchange Membrane
  • PEM Proton Exchange Membrane
  • Other types of fuel cells include, without limitation, Alkaline Fuel Cells (AFC), Direct Methanol
  • DMFC Fuel Cells
  • MCFC Molten Carbonate Fuel Cells
  • PAFC Phosphoric Acid Fuel Cells
  • SOFC Solid Oxide Fuel Cells
  • the invention is generally applicable to any fuel cell that uses a gaseous fuel.
  • the invention is applicable to fuel cells fueled from a reformer, which generates a gaseous stream including hydrogen and other components.
  • the fuel cell module 100 includes an anode electrode 21 and a cathode electrode 41.
  • the anode electrode 21 includes a gas input port 22 and a gas output port 24.
  • the cathode electrode 41 includes a gas input port 42 and a gas output port 44.
  • An electrolyte membrane 30 is arranged between the anode electrode 21 and the cathode electrode 41.
  • the fuel cell module 100 also includes a first catalyst layer 23 between the anode electrode 21 and the electrolyte membrane 30, and a second catalyst layer 43 between the cathode electrode 41 and the electrolyte membrane 30.
  • the first and second catalyst layers 23, 43 are deposited on the anode and cathode electrodes 21 ,41 , respectively.
  • a load 115 is coupled between the anode electrode 21 and the cathode electrode 41.
  • hydrogen fuel is introduced into the anode electrode 21 via the gas input port 22 under some predetermined conditions.
  • the predetermined conditions include, without limitation, factors such as flow rate, temperature, pressure, relative humidity and a mixture of the hydrogen with other gases.
  • the hydrogen reacts electrochemically according to reaction (1), given below, in the presence of the electrolyte membrane 30 and the first catalyst layer 23.
  • the chemical products of reaction (1) are hydrogen ions (i.e. cations) and electrons.
  • the hydrogen ions pass through the electrolyte membrane 30 to the cathode electrode 41 while the electrons are drawn through the load 115.
  • Excess hydrogen (sometimes in combination with other gases and/or fluids) is drawn out through the gas output port 24.
  • an oxidant such as oxygen in the air
  • an oxidant is introduced into the cathode electrode 41 via the gas input port 42 under some predetermined conditions.
  • the predetermined conditions include, without limitation, factors such as flow rate, temperature, pressure, relative humidity and a mixture of the oxidant with other gases.
  • the excess gases, including un-reacted oxidant and the generated water are drawn out of the cathode electrode 41 through the gas output port 44.
  • the oxidant reacts electrochemically according to reaction (2), given below, in the presence of the electrolyte membrane 30 and the second catalyst layer 43.
  • reaction (2) The chemical product of reaction (2) is water.
  • the electrons and the ionized hydrogen atoms, produced by reaction (1) in the anode electrode 21, are electrochemically consumed in reaction (2) in the cathode electrode 41.
  • the electrochemical reactions (1) and (2) are complementary to one another and show that for each oxygen molecule (O 2 ) that is electrochemically consumed two hydrogen molecules (H 2 ) are electrochemically consumed.
  • a fuel cell module e.g. the fuel cell module 100 illustrated in Figure 1
  • hydrogen fuel and oxidant to drive electrochemical reactions (1) and (2)
  • electrochemical reactions (1) and (2) are wasteful and is unnecessary in many situations, such as, for example, where there is a fluctuating or intermittent load.
  • shutting down a fuel cell module initiates one or more undesired reactions that degrade some components of the fuel cell module.
  • a modification to a fuel cell module that reduces the rate of wear and degradation experienced by some components of the fuel cell module during shutdown and re-starting periods.
  • the modification is further adapted to passively reduce the rate of wear and degradation, whereas in other embodiments active mechanisms are employed to support passive reduction in the rate of wear and degradation.
  • the rate of wear and degradation is reduced by reducing the amount of combustion of the remaining reactants while increasing the electrochemical consumption of those reactants during a shutdown process.
  • the fuel cell module 300 includes a fuel cell stack 200 that is made up of one of more PEM fuel cells.
  • Each PEM fuel cell (not shown) includes an electrolyte membrane arranged between an anode electrode and a cathode electrode as schematically illustrated in Figure 1.
  • the fuel cell stack 200 has a cathode inlet port 202, a cathode outlet port 203, an anode inlet port 204 and an anode outlet port 205.
  • the cathode inlet and outlet ports 202,203 are fluidly connected to each of the respective cathode electrodes included in the fuel cell stack 200.
  • the anode inlet and outlet ports 204,205 are fluidly connected to each of the respective anode electrodes included in the fuel cell stack 200.
  • the fuel cell stack 200 also includes electrical connections
  • a relatively small parasitic load 17 is optionally connected across the electrical connections 18a, b of the fuel cell stack 200.
  • the small parasitic load 17 helps to limit the voltage response during a shutdown process, which is described in more detail below.
  • the value of the parasitic load 17 is preferably chosen to be relatively small compared to an actual load (e.g. the electric motor) that the fuel cell module 300 supplies power too, so that the amount of power dissipated by the parasitic load 17 during normal operation is relatively small compared to the amount of power dissipated through the actual load.
  • the parasitic load 17 is chosen such that it dissipates less than 0.03% the amount of power dissipated by the actual load during normal operation.
  • the small parasitic load 17 is permanently coupled across the electrical connections 18a,b; and thus, power is dissipated by the small parasitic load 17 during normal operation.
  • the small parasitic load 17 is arranged so that it is coupled across the electrical connections 18a,b of the fuel cell stack 200 immediately before or after the fuel cell module 300 is shutdown and is decoupled from the fuel cell stack 200 during normal operation.
  • the parasitic load 17 is made-up of internal impedances within the fuel cell stack 200.
  • the membrane(s) included in the fuel cell stack 200 provide enough of an internal resistance to serve as an adequate parasitic resistance during a shutdown process for limiting the voltage response of the fuel cell stack 200.
  • the fuel cell module 300 includes input valves 10 and 12 that are controllable to cut-off the inflow of reactant gases to the cathode inlet port 202 and the anode inlet port 204, respectively.
  • output valves 11 and 13 are provided to controllably cut-off the outflow of exhaust gases from the cathode outlet port 203 and the anode outlet port 205, respectively.
  • the input valve 10 is connected in series between the cathode inlet port 202 and a blower 60.
  • the blower 60 is any device (e.g., a motorized fan, a compressor, etc.) suitable to force air into the cathode inlet port 202 when the valve 10 is open.
  • the blower 60 also serves to passively deter, but not necessarily stop, the free flow of air into the cathode inlet port
  • the input valve 12 is connected in series between a fuel supply port 107 and the anode inlet port 204.
  • the fuel supply port 107 is further connectable to a hydrogen fuel supply vessel (not shown) or some other hydrogen fuel delivery system (not shown).
  • a fuel reservoir 19 and a flow control device 14 are connected respectively in series between the input valve 12 and the anode inlet port 204.
  • the output valve 11 is connected in series between the cathode outlet port 203 and a first exhaust port 108.
  • the output valve 13 is connected in series between the anode outlet port 205 and a second exhaust port 109.
  • the exhaust ports 108 and 109 are each optionally connectable to other devices, such as for example, an exhaust system including an electrolyzer for re-cycling exhaust gases or liquids from the fuel cell module 300.
  • a check valve 15 is connected between an air supply port 106 to the ambient environment (not illustrated) and the cathode inlet port 202, such that the check valve 15 is in parallel with the input valve 10.
  • the check valve 15 is a pressure sensitive mechanism that opens when the pressure at the cathode inlet port 202 drops below the air pressure of the ambient environment by a pre-set amount, known as a cracking pressure.
  • the cracking pressure is specifically set to correspond to a predetermined pressure differential between the air pressure in the ambient environment and the pressure inside of the cathode inlet port 202.
  • the predetermined pressure differential corresponds to a total volume of a mixture of gases in the cathode electrodes in the fuel cell stack 200 and, in particular, to an amount of oxygen in the cathode electrodes relative to other gases, such as for example nitrogen from the air. This is described in further detail below with reference to Figure 3.
  • the hydrogen reservoir 19 is provided to store a fixed amount of hydrogen that is employed during a shutdown process of the fuel cell module 300 that is described in further detail below with reference to Figure 3.
  • the hydrogen reservoir 19 is a vessel that is appropriately sized to store enough hydrogen fuel to substantially electrochemically consume the oxygen remaining in the fuel cell module 300 when the valves 10, 11 , 12 and 13 are closed and the forced inflow of air from the blower 60 is terminated.
  • the hydrogen reservoir 19 is made-up of a predetermined length of hose or tubing (possibly coiled) for storing enough hydrogen for the same purpose.
  • the hydrogen reservoir 19 is smaller than required but the amount of hydrogen fuel in the hydrogen reservoir 19 is replenished as required during a shutdown process so that enough hydrogen fuel is provided to substantially electrochemically consume the remaining oxygen.
  • the amount of hydrogen (or reactant of interest) remaining in a fuel cell stack after shutdown is to be taken into consideration when sizing a hydrogen (reactant) reservoir.
  • the flow control device 14 is provided to regulate the supply of hydrogen fuel delivered to the anode inlet port 204 by, for example, setting the pressure of the hydrogen fuel delivered to the anode inlet port 204.
  • the flow control device 14 is specifically a forward pressure regulator that is dome loaded using air pressure in combination with a bias spring.
  • the forward pressure regulator sets the pressure at the anode inlet port 204 relative to the pressure at the cathode inlet port 202 by some amount.
  • the pressure at the anode inlet port 204 is regulated to be higher than the pressure at the cathode inlet port 202 by a predetermined fixed amount.
  • a flow control device requires a power supply for operation, whereas in other embodiments a flow control device is a passive element, such as for example, a passive forward pressure regulator.
  • the fuel cell module 300 optionally includes a hydrogen recirculation pump 16 connecting the anode outlet port 205 to the anode inlet port 204.
  • the hydrogen recirculation pump 16 is operable to re-circulate some portion of the unused hydrogen expelled through the anode outlet port 205 back to the anode inlet port 204.
  • valves 10, 11 , 12 and 13 include, without limitation, normally closed valves, normally open valves and latching valves. Those skilled in the art would appreciate that various other types of valves may be suitably employed. [0051] In some embodiments some of the valves 10, 11, 12 and 13 are normally closed valves. A normally closed valve is opened, thus permitting free flow of gases (or liquids), only when a control signal (or some electromotive force) is continuously supplied to the particular valve. That is, when power is not supplied to a particular normally closed valve, the valve remains closed, thus preventing the free flow of gases (or liquids) through the valve.
  • some of the valves 10, 11, 12 and 13 are normally open valves.
  • a normally open valve is closed, thus stopping the free flow of gases (or liquids), only when a control signal (or some electromotive force) is continuously supplied to the particular valve. That is, when power is not supplied to a particular normally open valve, the valve remains open, thus allowing the free flow of gases (or liquids) through the valve.
  • some of the valves 10, 11, 12 and 13 are latching valves.
  • a latching valve requires a control signal pulse to switch between "open” and “closed” positions. In the absence of a control signal pulse (or another electromotive pulse) a latching valve remains in the position it is in without change.
  • valves 10, 11, 12 and 13 are open permitting the free flow of gases (and liquids) to/from the respective ports 202, 203, 204 and 205. Moreover, power is supplied to the blower 60, the flow control device
  • Oxidant for the cathode electrodes in the fuel cell stack 200 is obtained from air, which, again, is made up of approximately 20% oxygen.
  • the blower 60 forces air into the cathode inlet port 202 via the open input valve 10. Once inside the cathode electrodes some of the oxygen from the air is employed in the electrochemical reaction (2) described above.
  • Hydrogen fuel travels through the fuel supply port 107 into the anode inlet port 204 via the hydrogen reservoir 19 and the flow control device 14.
  • the hydrogen recirculation pump 16 also contributes to the hydrogen fuel supply delivered to the anode inlet port 204, as it operates to force some portion of the unused hydrogen, that is expelled from the anode outlet port
  • the check valve 15 remains closed during normal operation since the pressure in the cathode inlet port 203 is equal to or greater than the air pressure of the ambient environment.
  • the fuel cell module 300 illustrated in Figure 2 is not a conventional fuel cell module, as the components of the fuel cell module 300 are configured to passively reduce the overall amount of combustion of hydrogen and oxygen within the fuel cell stack 200 during a shutdown process. This is accomplished by passively inducing an increase in the electrochemical consumption of hydrogen and oxygen that is left inside the fuel cell module 300 relative to what would normally occur during a shutdown process in a conventional fuel cell module.
  • the hydrogen reservoir 19 serves as a source for a sufficient amount of additional hydrogen fuel for the fuel cell stack 200 after the input valve 12 has been closed.
  • the additional hydrogen fuel drawn from the hydrogen reservoir 19, in combination with other parts of the fuel cell module 300 induces the electrochemical consumption of the oxygen remaining inside the fuel cell stack 200.
  • the source of the oxygen is air (which is approximately 80% nitrogen)
  • the electrodes within the fuel cell stack 200 are passively blanketed with nitrogen. A high concentration of nitrogen reduces the amount of combustion that occurs subsequently within the fuel cell stack 200.
  • the passive blanketing process is a function of the change in pressures within the fuel cell module 300 and specifically within the fuel cell stack 200. The blanketing process that occurs during a shutdown process is described in detail below with reference to Figure 3 and continued reference to Figure 2.
  • Figure 3 shows a chart illustrating an approximate and simplified breakdown of the mixture of gases present in the cathode electrodes of the fuel cell stack 200 shown in Figure 2 during sequential stages of a shutdown period.
  • Figure 3 is provided only as an aid for the visualization of a substantially continuous and fluid process and it is in no way intended to limit the scope of the invention as claimed in the following section.
  • reactant gases hydrogen fuel and oxygen carried in the air
  • valves 10, 11, 12 and 13 are closed and the power supplied to the blower 60, the flow control device 14 and the hydrogen recirculation pump 16 is cut-off. Closing the output valves 11 and 13 reduces the amount of gases that leak into the cathode and anode electrodes, respectively, via the corresponding outlets 203 and 205, when the fuel cell module 300 is shut down.
  • the role of the parasitic load 17, whether it is connected permanently or not, is to limit the voltage of the fuel cell stack 200 (i.e. the stack voltage) when the fuel cell module 300 is shutdown and/or de-coupled from the actual load. If the parasitic load 17 is not connected permanently, the parasitic load 17 is coupled across the electrical connections 18a,b immediately before or after a shutdown process is initiated. Preventing the output voltage of the fuel cell stack 200 from reaching a very high level helps to limit an electrochemical corrosion mechanism that can be triggered by a high stack voltage. The presence of the parasitic load 17 further induces the electrochemical consumption of the hydrogen and oxygen remaining within the fuel cell module 300 when a shutdown process is initiated.
  • the parasitic load 17 passively induces the electrochemical consumption of the remaining reactant gases by providing a path for current and voltage to be discharged from the fuel cell stack 200. As the concentration of the reactant gases is reduced on either one or both of the anode or cathode electrodes, the electrochemical potential of the constituent fuel cells (measured as voltage) of the fuel cell stack 200 decreases. If the parasitic load 17 is a simple resistor, as the fuel cell voltage decreases, the corresponding current flowing through the resistor also decreases.
  • the cathode electrodes within the fuel cell stack 200 contain a mixture of gases that roughly corresponds to the composition of air
  • each cathode electrode in the fuel cell stack 200 contains a mixture of gases that are approximately 80% nitrogen and 20% oxygen
  • each cathode electrode is approximately the same as the air pressure in the ambient environment (e.g. about 1 atm).
  • the oxygen in the cathode electrodes of the fuel cell stack 200 is primarily electrochemically consumed according to electrochemical reactions (1) and (2).
  • the required hydrogen fuel used to sustain the electrochemical reactions (1) and (2) is supplied from the hydrogen reservoir 19.
  • the volume of the gas mixture in the cathode electrodes drops significantly causing a corresponding drop in internal pressure within the cathode electrodes. Illustrated at 3-2 of Figure 3 is an example of the breakdown of a mixture of gases within the cathode electrodes after the oxygen has been substantially consumed. Nitrogen makes up approximately 98% of the gases present in the cathode electrodes and the pressure within the cathode electrodes is approximately 0.8 atm.
  • the total amount of nitrogen present in the cathode electrodes is about 96% and the pressure is about the same as the air pressure of the ambient environment (e.g. 1 atm).
  • This process is repeated, with the oxygen present in the cathode electrode (being approximately 4% of the cathode electrode volume) being electrochemically consumed with hydrogen provided from the hydrogen reservoir 19.
  • the void created in the cathode electrodes by the oxygen consumption would be filled with air from the ambient environment (once again composed of approximately 80% nitrogen and 20% oxygen). Consequently, the cathode electrodes of the fuel cell stack 200 are blanketed with predominantly nitrogen gas by this substantially continuous process.
  • the arrangement of the fuel cell module 300 illustrated in Figure 2 also induces passive nitrogen blanketing of the anode electrodes in the fuel cell stack 200.
  • the hydrogen fuel from the hydrogen reservoir 19 is consumed, the volume of the gas mixture present in the anode electrodes drops, which, subsequently results in a corresponding pressure drop within the anode electrodes.
  • the pressure drop within the anode electrodes induces a pressure gradient to be established across the respective membranes from the cathode to the anode side of each membrane in the fuel cell stack 200. This pressure gradient will passively draw nitrogen across the membranes from the respective cathode electrodes to the anode electrodes, thus, causing the anode electrodes to be blanketed with nitrogen as well.
  • FIG. 4 shown is a schematic diagram illustrating a fuel cell module 302 according to aspects of another embodiment of the invention.
  • a fuel cell module includes a suitable combination of supporting elements and that the fuel cell module 302 is illustrated showing only those elements necessary to describe aspects of an embodiment of the invention.
  • the fuel cell module 302 illustrated in Figure 4 is similar to the fuel cell module 300 illustrated in Figure 2. Accordingly, elements common to both fuel cell modules 300 and 302 share common reference indicia. The differences between the two fuel cell modules 300 and 302 are that the fuel cell module 302 does not include input valve 10, output valve 11 , check valve 15 and air supply port 106.
  • the blower 60, illustrated in Figure 4 is coupled to the cathode inlet port 202 without a valve (e.g. input valve 10) arranged there between.
  • the blower 60 is any device (e.g., a motorized fan, a compressor, etc.) that serves to force air into the cathode inlet port 202.
  • the blower 60 also serves to passively deter, but not necessarily stop, the free flow of air into the cathode inlet port 202 when power is cut-off from the blower 60.
  • the fuel cell module 302 operates in a substantially identical manner to fuel cell module 300 described above.
  • the operation of the fuel cell module 302 is similar to the operation of the fuel cell module 300; however, as already noted, there is no check valve to deter and permit free air flow into the cathode inlet port 202. Instead, the flow of air into the cathode inlet port 202 is slowed down enough by the path through the blower 60 that the oxygen remaining in the cathode electrodes of the fuel cell stack 200 (when the fuel cell module 300 is shutdown) is substantially electrochemically consumed before additional air flows into the cathode electrodes to replace the lost volume of the consumed oxygen.
  • the breakdown of the mixture of gases in the cathode electrodes is similar to what is shown at 3-2 before additional air is passively drawn into the cathode electrodes by the relative drop in pressure. Once additional air makes its way through the blower 60 into the cathode electrodes of the fuel cell stack 200 the breakdown in the mixture of gases in the cathode electrodes is similar to what is shown in 3-3 (and, equivalently 3-4).
  • the partial restriction of the air flow through the blower 60 prevents the continuous, rapid replenishment of the electrochemically consumed oxygen on the cathode electrode which would prevent the formation of a predominately nitrogen rich gas composition on the cathode electrode.
  • a gradual depletion of oxygen concentration on the cathode electrode follows a similar process as described above with respect to Figure 2, with the exception that no large measurable vacuum is created in the cathode electrodes. Rather the electrochemical depletion of oxygen creates a volumetric void and a localized depleted oxygen concentration in the cathode electrodes that draws additional air to the electrode surface (through a combination of pressure and concentration differential driving forces).
  • there is no output valve e.g.
  • FIG. 5 shown is a schematic diagram illustrating a fuel cell module 304 according to aspects of another embodiment of the invention.
  • a fuel cell module includes a suitable combination of supporting elements and that the fuel cell module 304 is illustrated showing only those elements necessary to describe aspects of an embodiment of the invention.
  • the fuel cell module 304 illustrated in Figure 5 is similar to the fuel cell module 300 illustrated in Figure 2. Accordingly, elements common to both fuel cell modules 300 and 304 share common reference indicia. The differences between the two fuel cell modules 300 and 304 are that the fuel cell module 304 does not include output valve 11 , check valve 15 and air supply port 106.
  • the fuel cell module 304 operates in a substantially identical manner to fuel cell module 300, described above. [0086] During a shutdown process the operation of the fuel cell module
  • the 304 is similar to the operation of the fuel cell module 302 described above. Again, there is no check valve to deter and permit free air flow into the cathode inlet port 202. Moreover, the input valve 10 is arranged between the blower 60 and the cathode inlet port 202, so additional air cannot flow into the cathode electrodes of the fuel cell stack 200 via the blower 60 during a shutdown process since the input valve 10 is closed. Instead, the flow of air into the cathode electrodes comes through the cathode outlet port 203 via the first exhaust port 108.
  • the first exhaust port 108 it is desirable to size and/or shape the first exhaust port 108 such that the flow of air in the reverse direction is slowed down enough by the reverse path through the first exhaust port 108 so that the oxygen remaining in the cathode electrodes of the fuel cell stack 200 (when the fuel cell module 300 is shutdown) is substantially electrochemically consumed before additional air flows into the cathode electrodes to replace the lost volume of the consumed oxygen. That is, with further reference to Figure 3, the breakdown of the mixture of gases in the cathode electrodes is similar to what is shown at 3-2 before additional air is passively drawn into the cathode electrodes by the relative drop in pressure.
  • FIG. 6 shown is a schematic diagram illustrating a fuel cell module 306 according to aspects of another embodiment of the invention.
  • a fuel cell module includes a suitable combination of supporting elements and that the fuel cell module 306 is illustrated showing only those elements necessary to describe aspects of an embodiment of the invention.
  • the fuel cell module 306 illustrated in Figure 6 is similar to the fuel cell module 300 illustrated in Figure 2. Accordingly, elements common to both fuel cell modules 300 and 306 share common reference indicia. The differences between the two fuel cell modules 300 and 306 are that the fuel cell module 306 does not include input valve 10, check valve 15 and air supply port 106.
  • the blower 60 illustrated in Figure 6 is coupled to the cathode inlet port 202 without a valve (e.g. input valve 10) arranged there between.
  • the blower 60 is any device (e.g., a motorized fan, a compressor, etc.) that serves to force air into the cathode inlet port 202.
  • the blower 60 also serves to passively deter, but not necessarily stop, the free flow of air into the cathode inlet port 202 when power is cut-off from the blower 60.
  • the fuel cell module 306 operates in a substantially identical manner to fuel cell module 300, described above.
  • the operation of the fuel cell module 306 is similar to the operation of the fuel cell modules 300 and 302; however, as already noted, there is no check valve to deter and permit free air flow into the cathode inlet port 202. Instead, the flow of air into the cathode inlet port 202 is slowed down enough by the path through the blower 60 that the oxygen remaining in the cathode electrodes of the fuel cell stack 200 (when the fuel cell module 300 is shutdown) is substantially electrochemically consumed before additional air flows into the cathode electrodes to replace the lost volume of the consumed oxygen.
  • the breakdown of the mixture of gases in the cathode electrodes is similar to what is shown at 3-2 before additional air is passively drawn into the cathode electrodes by the relative drop in pressure. Once additional air makes its way through the blower 60 into the cathode electrodes of the fuel cell stack 200 the breakdown in the mixture of gases in the cathode electrodes is similar to what is shown in 3-3 (and, equivalently 3-4).
  • the fuel cell module 306 includes the output valve 11 , additional air is prevented from entering the cathode outlet port 203 during a shutdown process since the output valve 11 is closed during the shutdown process. Also, as described above with respect to Figure 2, as hydrogen is consumed, in the fuel cell module 306 (of Figure 6), the pressure in the anode electrodes drops causing nitrogen to be drawn across the respective membranes. [0094] Again, those skilled in the art will appreciate that the blanketing of the cathode and the anode electrodes occurs in concert in a continuous and fluid manner and it is thus difficult to illustrate this process in discrete steps. Thus, the description provided above is not intended to limit the scope of the invention to a specific sequence of discrete events or processes.
  • an optional second check valve (not illustrated) can be coupled between the anode inlet port 204 and the cathode inlet port 202.
  • the second check valve is configured to open when there is a pre-determined pressure differential between the pressure in the anode electrode(s) and the cathode electrode(s) during a shutdown process permitting flow from only the cathode electrodes(s) to the anode electrode(s); and, during normal operation the second check valve is configured to remain closed.
  • the second check valve is used to ensure that nitrogen from the cathode electrodes is passed to the anode electrodes when a sufficient portion of the hydrogen fuel from the hydrogen reservoir 19 is consumed electrochemically, which will result in a corresponding pressure drop as described above. This is to supplement and/or replace the need for nitrogen diffusion across the respective membranes in the fuel cell stack 200, as a means for blanketing the anode electrode(s).
  • the flow control device 14 is provided to regulate the supply of hydrogen fuel delivered to the anode inlet port 204 by, for example, setting the pressure of the hydrogen fuel delivered to the anode inlet port 204.
  • the pressure of the hydrogen fuel is typically set in a range of between about 65 psi to about 85 psi. Accordingly, the hydrogen fuel supply (not shown) is capable of supplying the hydrogen fuel at these pressures.
  • low pressure hydrogen gas source first reactant
  • the use of a hydrogen reservoir as described earlier would result in a large volume reservoir relative to the fuel cell module. This may not be efficient or cost effective.
  • low pressure hydrogen supplies include, but are not limited to, metal hydride storage vessels and a hydrogen reformer coupled with a palladium membrane.
  • a fuel cell module (essentially as described above) having a fuel cell stack 200 and a first reactant holding tank 190, which is pressurized by a pressure generating device, such as, for example, a positive displacement pump 195 during normal operation of the fuel cell module so that a pre-determined amount of first reactant is present in the holding tank under a higher pressure than when the first reactant is fed to the fuel cell stack.
  • a pressure generating device such as, for example, a positive displacement pump 195 during normal operation of the fuel cell module so that a pre-determined amount of first reactant is present in the holding tank under a higher pressure than when the first reactant is fed to the fuel cell stack.
  • positive style displacement pumps include, but are not limited to, piston pumps, diaphragm pumps, and rotary screw pumps.
  • Other examples of pressure generating devices can include, but are not limited to, a blower, a motorized fan, and a compressor.
  • the pump 195 and the first reactant holding tank 190 are provided in a side stream, the ends of which are connected, in a parallel arrangement, to the line between the valve 12 and the anode inlet port 204. It will be understood that the other anode and cathode ports, as shown in the earlier figures, are still present in the fuel cell stack 200, but for simplicity are not shown in Figures 7a, b and c. Further, while the holding tank is shown with one connection to the side stream, it is possible that it could be provided with an inlet port connected to the pump 195 and a separate outlet port connected to a flow control device 14', detailed below, so as to form a series configuration.
  • the first reactant supply is closed to the fuel cell stack via input valve 12 (as described earlier).
  • the first reactant from the holding tank 190 is provided to the anode inlet port 204 of the fuel cell stack, via a flow control device 14', such as a forward pressure regulator (FPR), which in function corresponds to the earlier mentioned flow control device 14, to perform the blanketing shutdown process as described in conjunction with earlier embodiments.
  • a flow control device 14' such as a forward pressure regulator (FPR), which in function corresponds to the earlier mentioned flow control device 14, to perform the blanketing shutdown process as described in conjunction with earlier embodiments.
  • Further embodiments of the invention may include a pressure feedback sensor 192 to allow at least limited automated control of the pump 195 as shown in Figure 7b.
  • the pressure sensor 192 can be programmed with a preset pressure value.
  • the pressure sensor When the pressure in the holding tank 190 exceeds the preset value, the pressure sensor sends an electronic signal to shut off the power to the pump 195. When the pressure in the holding tank 190 falls below the preset value, the pressure sensor sends an electronic signal to turn back on the power to the pump 195.
  • the preset pressure value will be selected taking into account the volume of the holding tank and its maximum working pressure.
  • a solenoid valve 196 can be arranged between the pump 195 and the flow control device 14' to prevent hydrogen from leaking through the flow control device since this leakage could cause unnecessary start/stop cycles for the pump.
  • the pump 195 may be any device which can pressurize the first reactant in the first reactant holding tank 190.
  • the pump acts as a "solenoid valve" (i.e.
  • solenoid valve 196 to prevent reverse flow of the high pressure stored gas in the first reactant holding tank 190 into the low pressure system gas feed to the stack, or if the pump does not form a complete seal, an additional solenoid valve (not shown), similar to solenoid valve 196, may be added to prevent this reverse flow.
  • the low pressure system of the embodiment as shown in Figures 7a to 7c is useful when the first reactant supply pressure is low (typically 1 to 3 psi as opposed to high pressure supply of around 65 to 85 psi). Since the pressure in the first reactant holding tank is built up during normal operation, the volume of the holding tank can be small but the provided mass of first reactant from the holding tank will still be sufficient to perform a blanketing shutdown as described above. It should be noted that Figures 7a to 7c only show those features which are particularly relevant to the low pressure system. Further features of the fuel cell module are essentially identical to what has been shown for previous embodiments of the invention.
  • FIG 8 shows an alternative arrangement. Instead of the parallel arrangement shown in Figures 7a, b and c.
  • a first reactant holding tank 190' is shown at the end of a side branch having a single connection to the line supplying the first reactant to the anode inlet port 204.
  • the pump here designated 195', and optionally a valve indicated schematically at 196'.
  • the pump 195' is preferably a pump that when turned off or inoperative permits backflow through the pump. Then, in use, the pump in normally operated to establish and maintain a desired pressure in the first reactant holding tank 190'. At shutdown, the pump 195' is turned off, and the stored first reactant is permitted to flow back through the pump 195' to the anode of the fuel cell stack 200 as described above. [00108] If the pump 195' is a positive displacement pump that does not permit backflow when inoperative, then a bypass line around the pump and controlled by a valve can be provided (not shown).
  • the valve 196' can be provided as required. Thus, if the configuration is such that the pump 195' is only operated until a desired pressure is established in the holding tank 190' and then turned off, it may be necessary to have a valve 196' that is open during operation of the pump 195', and then closed to retain and hold the first reactant in the holding tank 190' until required.
  • valve 196' can be any suitable type of valve, including any valve as detailed above.

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Abstract

Un certain nombre de facteurs entraînent la survenue de réactions indésirables qui accélèrent l'usure et la dégradation subie par des composants de pile à combustible pendant les opérations d'arrêt et les périodes de redémarrage. Afin d'atténuer les problèmes associés à ces facteurs, l'invention concerne un module de pile à combustible amélioré comprenant (i) un empilement de piles à combustible comprenant au moins une pile à combustible, chaque pile comprenant une électrode anode, une électrode cathode et un milieu électrolyte agencé entre l'anode et la cathode, en fonctionnement normal, l'électrode anode étant pourvue d'un premier réactif et l'électrode cathode étant pourvue d'un premier mélange contenant un second réactif et un agent non réactif, (11) une charge parasite qui peut être connectée à travers les électrodes anode et cathode, (111) un premier orifice d'alimentation de réactif qui peut être connecté à l'électrode anode destiné à alimenter le premier réactif à l'électrode anode, (iv) un flux latéral qui peut être fluidiquement connecté à la première alimentation de réactif et à l'électrode anode, (v) un réservoir de réactif, qui peut être fluidiquement connecté au flux latéral de façon à stocker une quantité du premier réactif souhaitable pour un processus d'arrêt du module de pile à combustible, en utilisation, lorsque le module de pile à combustible est arrêté, la quantité stockée du premier réactif est amenée du réservoir de réactif et elle réagit électrochimiquement avec le second réactif dans le module de pile à combustible de façon à consommer électrochimiquement le premier et le second réactif, laissant ainsi un second mélange qui comprend sensiblement l'agent non réactif, (vi) et un dispositif de génération de pression, qui peut être connecté fluidiquement au flux latéral et placé en amont du réservoir de réactif pour pressuriser et délivrer le premier réactif en provenance de la première alimentation de réactif au réservoir de réactif.
PCT/CA2007/000189 2006-02-08 2007-02-08 Intégration d'électrode passive dans une pile à combustible WO2007090284A1 (fr)

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EP07710606A EP1987556A1 (fr) 2006-02-08 2007-02-08 Intégration d'électrode passive dans une pile à combustible
CA2634157A CA2634157C (fr) 2006-02-08 2007-02-08 Integration d'electrode passive dans une pile a combustible

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US60/771,018 2006-02-08

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FR2941094A1 (fr) * 2009-02-27 2010-07-16 Michelin Soc Tech Dispositif pour augmenter le volume du circuit hydrogene d'une pile a combustible
WO2013149337A1 (fr) 2012-04-02 2013-10-10 Hydrogenics Corporation Procédé de démarrage de pile à combustible
WO2014001253A1 (fr) 2012-06-27 2014-01-03 Compagnie Generale Des Etablissements Michelin Système d'alimentation de pile à combustible
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WO2002005997A1 (fr) * 1999-04-19 2002-01-24 Filezall, Inc. Adaptateur de lime pour scie électrique
US20050026022A1 (en) * 2003-06-25 2005-02-03 Joos Nathaniel Ian Passive electrode blanketing in a fuel cell
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Cited By (19)

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Publication number Priority date Publication date Assignee Title
WO2009124737A1 (fr) * 2008-04-11 2009-10-15 Basf Se Procédé d’exploitation d’une pile à combustible
WO2010031601A1 (fr) * 2008-09-17 2010-03-25 Belenos Clean Power Holding Ag Procédé d'arrêt et de démarrage d'une pile a combustible
US9413020B2 (en) 2008-09-17 2016-08-09 Belenos Clean Power Holding Ag Method of shut-down and starting of a fuel cell
FR2941094A1 (fr) * 2009-02-27 2010-07-16 Michelin Soc Tech Dispositif pour augmenter le volume du circuit hydrogene d'une pile a combustible
US10741859B2 (en) 2012-04-02 2020-08-11 Hydrogenics Corporation Fuel cell start up method
WO2013149337A1 (fr) 2012-04-02 2013-10-10 Hydrogenics Corporation Procédé de démarrage de pile à combustible
US11804611B2 (en) 2012-04-02 2023-10-31 Hydrogenics Corporation Fuel cell start up method
EP2834868A4 (fr) * 2012-04-02 2016-01-06 Hydrogenics Corp Procédé de démarrage de pile à combustible
US11495807B2 (en) 2012-04-02 2022-11-08 Hydrogenics Corporation Fuel cell start up method
US11101477B2 (en) 2012-04-02 2021-08-24 Hydrogenics Corporation Fuel cell start up method
US10084196B2 (en) 2012-05-04 2018-09-25 Hydrogenics Corporation System and method for controlling fuel cell module
WO2014001253A1 (fr) 2012-06-27 2014-01-03 Compagnie Generale Des Etablissements Michelin Système d'alimentation de pile à combustible
CN103887538A (zh) * 2012-12-20 2014-06-25 中国科学院大连化学物理研究所 一种燃料电池系统停车控制方法
US10680258B2 (en) 2013-10-02 2020-06-09 Hydrogenics Corporation Fast starting fuel cell
US11309556B2 (en) 2013-10-02 2022-04-19 Hydrogenics Corporation Fast starting fuel cell
US10181610B2 (en) 2013-10-02 2019-01-15 Hydrogenics Corporation Fast starting fuel cell
US10930950B2 (en) 2016-12-21 2021-02-23 Hydrogenics Corporation Closed anode fuel cell startup method
US11362349B2 (en) 2016-12-21 2022-06-14 Hydrogenics Corporation Closed anode fuel cell startup method
US11411232B2 (en) 2016-12-21 2022-08-09 Hydrogenics Corporation Closed anode fuel cell startup method

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