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WO2009049779A1 - Procédé de fonctionnement d'un système de pile à combustible - Google Patents

Procédé de fonctionnement d'un système de pile à combustible Download PDF

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Publication number
WO2009049779A1
WO2009049779A1 PCT/EP2008/008403 EP2008008403W WO2009049779A1 WO 2009049779 A1 WO2009049779 A1 WO 2009049779A1 EP 2008008403 W EP2008008403 W EP 2008008403W WO 2009049779 A1 WO2009049779 A1 WO 2009049779A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel
anode
fuel cell
phase
cell system
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2008/008403
Other languages
German (de)
English (en)
Inventor
Jörg STRAUHS
Markus Walter
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
Original Assignee
Daimler AG
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 Daimler AG filed Critical Daimler AG
Publication of WO2009049779A1 publication Critical patent/WO2009049779A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • H01M8/04089—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
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • H01M8/04302—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during start-up
    • 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
    • H01M8/04225—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 start-up
    • 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
    • H01M8/04231—Purging 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
    • H01M8/04223—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
    • H01M8/04268—Heating of fuel cells during the start-up of the fuel cells
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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 a method for operating a fuel cell system, which is started after a shutdown and in which in the start-up phase, a fuel is passed through the at least partially filled with air anode chamber of the fuel cell system.
  • An anode gas mixture emerging from the anode probe during the start-up phase is conducted at least partially back into the anode chamber in a recirculation circuit of the fuel cell system.
  • the anode flow field exhaust gas recycle loop is triggered when this anode flow field gas is 100% air.
  • the start-up phase is a
  • Anode exhaust vent valve is at least partially opened with a fan turned on to begin recirculating the anode flow field exhaust gases through the recycle circuit.
  • a fuel flow valve disposed in a supply line between a hydrogen source and the anode is set in an unchangeable opening state during the start-up phase so that only a continuous, continuous stream of hydrogen-containing fuel can flow from the hydrogen source to the anode.
  • in the Recirculation of the hydrogen and the anode exhaust gases necessarily pass through a plurality of burners.
  • a method for operating a fuel cell system is further known in which in a start phase to avoid undersupply of a fuel cell with fuel, the amount of fuel to be supplied in the fuel cell system, taking into account a content of stored in the fuel cell Fuel is added. It is thus determined when starting the still existing in the anode amount of fuel and depending on then a still missing residual amount constantly supplied, so that there is a total amount of fuel by the sum of the still present in the fuel cell amount of fuel and the remaining amount supplied.
  • the problem of occurring hydrogen oxygen gradient formation in the anode can only be avoided to a limited extent.
  • a hydrogen mass flow conducted into the anode displaces the oxygen still present there.
  • the resulting hydrogen-oxygen gradient is the main reason for the premature aging of fuel cells.
  • the catalyst of the fuel cell is damaged by excessive hydrogen oxygen gradients along a channel within a fuel cell.
  • a switched-off fuel cell is restarted.
  • a fuel is passed through the at least partially filled with air anode space of the fuel cell system.
  • an anode gas mixture emerging from the anode chamber is mixed in one
  • the fuel supplied from a fuel reservoir to the anode chamber is varied at least temporarily in its quantity during the start-up phase. This means that during the start-up phase, at least temporarily, there is no continuous supply of the fuel quantity from the fuel storage to the anode space, but that this supply is changed quantitatively at least once during a feed operation.
  • the varying metering of the supplied fuel allows a very precise and optimized at the current times tuned addition of the amount of fuel. It particularly efficiently prevents the avoidance of too high a fuel-oxidant gradient along a channel within the fuel cell.
  • the fuel supplied from the fuel reservoir to the anode chamber is at least temporarily increased in its quantity during the start-up phase.
  • the fuel supplied from the fuel reservoir to the anode chamber is varied in its quantity during the start-up phase, at least temporarily, continuously and continuously.
  • a fan is preferably arranged, which in the start-up phase for returning the anode gas mixture in the Anode space is at least temporarily operated in a specific return mode.
  • the recycling process of the anode gas mixture is carried out very specific and adapted to the current situation.
  • the situation-dependent adjustment of the concentrations of the fuel on the one hand and of the oxidant on the other hand can be further refined.
  • a speed of the fan is set in the return mode of the fan, which is greater than the set in the set after the startup normal operation of the fuel cell system speed.
  • a maximum speed of the fan is set in the return mode.
  • the fan is thus operated at least temporarily in the start-up phase at full load. It is preferably provided that in the return mode, the speed of the fan is set substantially constant for the entire duration substantially. However, it can also be provided that the rotational speed in the return mode during the start-up of the
  • Fuel cell system is varied at least once.
  • the most effective mode of operation can be selected and carried out depending on the situation.
  • the anode gas mixture guided in the recirculation circuit is at least temporarily removed from the recirculation circuit during the start-up phase proportionately via a discharge device coupled to the recirculation circuit. This procedure achieves a further improvement with regard to the concentration of the fuel and the oxidant currently required or to be set during a start-up phase.
  • the duration of the discharge via the discharge device and / or the amount of the anode gas mixture to be discharged via the discharge device is dependent on the fuel concentration and / or the
  • Oxidant concentration determined in the anode compartment Thereby, the vote with regard to the supplied amount of the anode gas mixture can be made very fine and accurate.
  • the anode gas mixture discharged via the discharge device from the recirculation circuit is supplied to the cathode compartment of the fuel cell system. It can be provided that this supply takes place at the entrance of the cathode space or else at the exit of the cathode space.
  • anode gas mixture discharged via the discharge device from the recirculation circuit is fed into the environment or an exhaust air path leading away from the cathode compartment.
  • the steady increase in the hydrogen concentration during a sufficiently high recirculation rate and the resulting mixing of the anode gas mixture can cause harmful high fuel-Oxidationsmittelgradienten be prevented.
  • the fuel is hydrogen and the oxidant is oxygen, a harmful high hydrogen-oxygen gradient can thus be avoided.
  • the start-up or start-up of the fuel cell system is therefore characterized in particular by the fact that there is no abrupt continuous supply of hydrogen at the moment, but rather a gradual increase in the addition of hydrogen from the fuel reservoir during the start-up phase, at least temporarily.
  • a high recirculation rate of the anode volume should be ensured, as a result of which, in particular, the recycling of the anode gas mixture takes place at least proportionally in the anode chamber. If the oxidant concentration in the anode compartment is then reduced and close to zero percent, the start-up phase is completed.
  • the targeted opening of the recirculation circuit via the discharge device, the starting process can be additionally accelerated.
  • FIG. 1 shows a schematic representation of subcomponents of a fuel cell system, with which the method according to the invention is carried out;
  • Fig. 2 is a diagram in which the rotational speed of the fan arranged in the recirculation circuit is shown as a function of time;
  • FIG. 3 is a diagram showing the concentration of the fuel and the oxidizing agent as a function of time.
  • FIG. 1 shows a schematic illustration of a fuel cell system 1, which merely shows the components which are sufficient for the understanding of the invention.
  • the fuel cell system 1 comprises at least one fuel cell 2.
  • a fuel cell stack with a plurality of fuel cells 2 is preferably provided.
  • the fuel cell 2 comprises an anode chamber 4 and one of them separated by a membrane 5 cathode compartment 3.
  • the fuel cell 2 is formed as a PEM fuel cell.
  • the fuel cell system 1 is provided as a mobile system and arranged in a vehicle.
  • the fuel cell system 1 comprises a fuel storage 6, which is connected via a supply line 7 with the anode compartment 4.
  • a fuel storage 6 as the fuel, hydrogen or a hydrogen-containing gas is contained or may be generated therein.
  • an element 8 for changing the flow cross-section of the supply line 7 is arranged.
  • the element 8 is a valve, which is referred to below as the valve 8.
  • the fuel cell system 1 comprises a recirculation device 9.
  • This has a recirculation line 10 which extends from the exit of the anode compartment 4 to a junction 11.
  • the recirculation line 10 thus opens into the supply line 7 between the valve 8 and the inlet of the anode compartment 4.
  • a fan 12 connected to the recirculation line 10 is arranged in the device 9 and is driven by a motor 13.
  • a further element 15 is arranged, which is designed to change the flow cross-section of the conduit 14.
  • the element 15 is designed as a valve, which is referred to below as a valve 15.
  • the line 14 and the valve 15 are associated with a discharge device for discharging the guided from the anode chamber 4 via the recirculation device 9 anode gas mixture.
  • the line 14 is guided to the cathode space 3 of the fuel cell 2.
  • the proportion of the anode gas mixture, which is guided by the recirculation line 10 via the discharge device 14, 15, is thus conducted into the cathode space 3.
  • the discharge device 14, 15 opens into the environment or into a discharge path leading away from the exit of the cathode space 3.
  • the fuel cell system 1 also has a control unit, not shown, which is designed to control the valve 8. It is preferably provided that this control unit is also designed to control the valve 15 and the motor 13 in order to adjust the speed of the fan 12 can.
  • the fuel cell system 1 comprises a sensor, not shown, in order to detect the fuel concentration and the oxidant concentration in the fuel cell 2 can.
  • Fuel cell system 1 explained in more detail. After that Fuel cell system 1 is in a disconnected state, it is started following and is then initially in a start-up phase. In the parked state, an oxygen concentration has accumulated in the anode chamber 4, so that in a subsequent abrupt supply of the fuel hydrogen, a high hydrogen oxygen gradient would arise, which can damage the fuel cell 2.
  • the hydrogen contained in the fuel storage 6 is supplied to the anode space 4 at least temporarily in a modified amount via the supply line 7.
  • the valve 8 is controlled via the control unit so that the mass flow flowing through the valve 8 is continuously increased as the starting phase progresses.
  • the valve 8 is continuously opened continuously as the starting phase progresses.
  • FIG. 3 shows the course of the oxygen concentration and the hydrogen concentration in the anode space 4.
  • the concentration of hydrogen is zero. As the time progresses, the concentration of hydrogen in the anode compartment 4 increases steadily from time t 2 .
  • valve 8 is continuously opened more and more and thus the from Fuel storage 6 to the anode compartment 4 flowing hydrogen mass flow steadily increases.
  • the blower 12 is started at the time t 0 .
  • the blower 12 is operated in a return mode in that the anode gas mixture located in the anode chamber 4 is returned to the input of the anode chamber 4 via the return line 10 of the recirculation circuit.
  • the full load operation is set in the embodiment in the return mode of the blower 12, wherein for this purpose the maximum speed Dl is set. Until a time t lf when the startup phase is completed and the oxygen concentration in the anode chamber 4 is substantially zero percent, this maximum speed Dl is maintained constant.
  • the blower 12 is controlled via the control unit so that the speed is reduced from the maximum speed Dl to a lower speed D2.
  • This rotational speed D2 characterizes the normal operation of the fan 12 in the operation of the fuel cell system 1 following the start-up phase.
  • a lower speed than the maximum speed Dl is set in the start-up phase.
  • the set in the start-up phase and thus in the return mode speed Dl of the blower 12 is greater than the set in normal operation speed D2.
  • the rotational speed Dl in the return mode of the blower 12 is not constant over the entire duration but is changed at least temporarily during the start-up phase.
  • the time between the times t 0 and t 2 is minimal, since immediately after starting the fuel cell system 1, a supply of hydrogen from the fuel reservoir 6 via the valve 8 to the anode chamber 4 takes place.
  • the starting process of the fuel cell system 1 is initiated by a recirculation of the volume in the anode chamber 4.
  • a comparatively high recirculation rate for normal operation is set by operating the blower 12 in the specific return mode.
  • the continuously increasing addition of the quantity of hydrogen from the fuel reservoir 6 then takes place. This also results in a correspondingly slower anode-side pressure build-up. An undesirable high hydrogen oxygen gradient formation in the anode compartment 4 can be prevented.
  • supplied amount of the anode gas mixture can be varied. This can be made possible on the one hand via the speed control of the blower 12 and additionally on the other hand via the discharge of a portion of the anode gas mixture via the line 14 and the valve 15.
  • the duration of the discharge and / or the amount of anode gas mixture to be discharged via line 14 and valve 15 is preferably dependent on the concentration of hydrogen measured by a suitable sensor and / or determined by the concentration of oxygen in the anode compartment 4. As a result, the starting behavior can be optimally tuned and beyond accelerated.
  • the supply of the fuel from the fuel storage 6 to the anode chamber 4 is started simultaneously with the return of the anode gas mixture via the recirculation device 9 to the anode chamber 4.

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

Abstract

L'invention concerne un procédé de fonctionnement d'un système de pile à combustible (1) qui est mis en route après un arrêt et dans lequel, durant la phase de mise en route, un combustible est acheminé à travers l'espace anode (4) au moins partiellement rempli d'air d'une pile à combustible (2), et un mélange gazeux sortant de l'espace anode (4) dans un dispositif de recyclage (9) du système de pile à combustible (1) est au moins partiellement renvoyé dans l'espace anode (4), la quantité de combustible passant d'un réservoir de combustible (6) à l'espace anode (4) variant au moins temporellement dans la phase de mise en route.
PCT/EP2008/008403 2007-10-09 2008-10-04 Procédé de fonctionnement d'un système de pile à combustible Ceased WO2009049779A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007048317.3A DE102007048317B4 (de) 2007-10-09 2007-10-09 Verfahren zum Betreiben eines Brennstoffzellensystems
DE102007048317.3 2007-10-09

Publications (1)

Publication Number Publication Date
WO2009049779A1 true WO2009049779A1 (fr) 2009-04-23

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ID=40010716

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/008403 Ceased WO2009049779A1 (fr) 2007-10-09 2008-10-04 Procédé de fonctionnement d'un système de pile à combustible

Country Status (2)

Country Link
DE (1) DE102007048317B4 (fr)
WO (1) WO2009049779A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9716283B2 (en) 2013-01-29 2017-07-25 Honda Motor Co., Ltd. Method of starting fuel cell system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102019128422A1 (de) * 2019-10-22 2021-04-22 Audi Ag Verfahren zum Neustart einer Brennstoffzellenvorrichtung nach einem vorherigen Abstellen, Brennstoffzellenvorrichtung sowie Kraftfahrzeug

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1615283A1 (fr) * 2004-07-06 2006-01-11 Nissan Motor Co., Ltd. Système de pile à combustible
US20060093879A1 (en) * 2001-01-25 2006-05-04 Deliang Yang Procedure for starting up a fuel cell system having an anode exhaust recycle loop
WO2006134461A1 (fr) * 2005-06-13 2006-12-21 Nissan Motor Co., Ltd. Systeme de pile a combustible et procede de demarrage
CA2629627A1 (fr) * 2005-12-02 2007-06-02 Nissan Motor Co., Ltd. Systeme de pile a combustible et procede de reduction de la deterioration des electrodes au demarrage

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004037097A1 (de) 2004-07-30 2006-03-23 Daimlerchrysler Ag Verfahren zum Betreiben eines Brennstoffzellensystems

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060093879A1 (en) * 2001-01-25 2006-05-04 Deliang Yang Procedure for starting up a fuel cell system having an anode exhaust recycle loop
EP1615283A1 (fr) * 2004-07-06 2006-01-11 Nissan Motor Co., Ltd. Système de pile à combustible
WO2006134461A1 (fr) * 2005-06-13 2006-12-21 Nissan Motor Co., Ltd. Systeme de pile a combustible et procede de demarrage
CA2629627A1 (fr) * 2005-12-02 2007-06-02 Nissan Motor Co., Ltd. Systeme de pile a combustible et procede de reduction de la deterioration des electrodes au demarrage

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9716283B2 (en) 2013-01-29 2017-07-25 Honda Motor Co., Ltd. Method of starting fuel cell system

Also Published As

Publication number Publication date
DE102007048317A1 (de) 2009-04-16
DE102007048317B4 (de) 2025-04-03

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