EP1194967A1 - Pile a combustible htm ou batterie de piles a combustible htm a rin age de l'electrolyte reduit, et procede de demarrage - Google Patents

Pile a combustible htm ou batterie de piles a combustible htm a rin age de l'electrolyte reduit, et procede de demarrage

Info

Publication number
EP1194967A1
EP1194967A1 EP00929221A EP00929221A EP1194967A1 EP 1194967 A1 EP1194967 A1 EP 1194967A1 EP 00929221 A EP00929221 A EP 00929221A EP 00929221 A EP00929221 A EP 00929221A EP 1194967 A1 EP1194967 A1 EP 1194967A1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
fuel cell
cell
htm fuel
reservoir
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.)
Withdrawn
Application number
EP00929221A
Other languages
German (de)
English (en)
Inventor
Ulrich Gebhardt
Manfred Waidhas
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.)
Siemens AG
Original Assignee
Siemens 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 Siemens AG filed Critical Siemens AG
Publication of EP1194967A1 publication Critical patent/EP1194967A1/fr
Withdrawn legal-status Critical Current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
    • H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
    • H01M8/04283—Supply means of electrolyte to or in matrix-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
    • H01M8/04—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
    • 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
    • H01M8/04298—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
    • H01M8/24—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
    • H01M8/2425—High-temperature cells with solid 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
    • H01M8/2459—Comprising electrode layers with interposed electrolyte compartment with possible electrolyte supply or circulation
    • 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 an HTM fuel cell with reduced electrolyte flushing.
  • a new type of construction is proposed, with the aid of which the spilled electrolyte is collected and the HTM fuel cell is returned.
  • the invention deals with a method for starting an HTM fuel cell, in which, with the aid of the novel construction, the electrolyte which has been flushed out is returned to the cell during normal operation.
  • the polymer electrolyte membrane fuel cell which as the electrolyte has a base polymer on which [-S0 3 H] groups are attached.
  • the electrolytic conduction takes place via hydrated protons.
  • this membrane needs liquid water, ie operating temperatures below 100 ° C under normal pressure, in order to ensure proton conductivity. This leads to the problem that the inflowing process gases have to be humidified at temperatures above approx. 65 ° C.
  • membrane containing the [-SOjH] groups another membrane (this can also be an ion exchange membrane) and / or a matrix with free and / or physical and / or chemically bound
  • Phosphoric acid is used as the electrolyte of a fuel cell.
  • This fuel cell will be high temperature membrane Called fuel cell (HTM fuel cell).
  • HTM fuel cell high temperature membrane Called fuel cell
  • an HTM fuel cell tion with free phosphoric acid occurs, however at least one problem in the washing out of the electrolyte at temperatures below 100 ° C, so when starting the fuel cell system.
  • the electrolyte loss caused by the rinsing can lead to a loss of performance or even a functional failure of the cell.
  • the rinsed electrolyte leaves the cell with the process gas flow, for example. In order to maintain the functionality of the cell, electrolyte must be added.
  • PAFC Phosphoric Acid Fuel Cell
  • the object of the invention is therefore to provide a fuel cell which operates at operating temperatures above 100 ° C. and which functions without additional electrolyte.
  • the subject matter of the invention is an HTM fuel cell and an HTM fuel cell battery which comprises an electrolyte with an electrode coating on both sides, adjoining in each case a gas diffusion layer and a pole plate, a reservoir being provided, with which the electrolyte which is flushed out of the cell is temporary is storable and available for the cell again.
  • the invention also relates to a method for starting an HTM fuel cell, in which the spooled-out electrical trolyte is collected and the cell is returned.
  • a high-temperature membrane (HTM) fuel cell refers to a fuel cell that contains a conventional electrolyte membrane and / or that contains a membrane as a matrix for physical and / or chemical absorption of the electrolyte as a core piece and whose operating temperature is higher than that of conventional PEM -Fuel cell is, that is higher than 80 ° C, preferably higher than 100 ° C. The maximum operating temperature is around 220 ° C.
  • the HTM fuel cell has an electrolyte that has good conductivity in a non-water environment at the above-mentioned temperatures.
  • Each container is referred to as a reservoir, stored in the electrolyte and from which, under certain circumstances, product water and / or process exhaust gas can also evaporate.
  • the container is so closely coupled to the HTM fuel cell stack that it can reach its temperature.
  • the material of the reservoir is to be selected accordingly so that it is resistant to the electrolyte and yet easy to heat.
  • a device for pressure compensation is contained in the reservoir.
  • the reservoir is made of stretchable and / or elastic material with variable absorption, so that the inflowing electrolyte significantly influences the volume of the reservoir (according to the principle of a balloon and / or an accordion bellows).
  • the electrolyte is phosphoric acid, sulfuric acid, sulfuric acid, etc., ie all compounds that physically and / or chemically attach to a membrane or an inert matrix within the HTM fuel cell (hereinafter referred to as electrical lyttrager or carrier) are bound and which cause the electrolytic conduction of the protons within the HTM fuel cell.
  • the electrolyte preferably phosphoric acid and / or a more complete on ⁇ eigendissoziierende Broensted acid used.
  • the electrolyte which has been rinsed out is collected and automatically returned to the cell after the equilibrium has been established.
  • a water-permeable barrier layer is located within the HTM fuel cell.
  • This barrier layer can be arranged between the electrode and the gas diffusion layer or the gas conducting layer and the gas space which is delimited by the pole plate.
  • the reservoir is connected directly to the HTM fuel cell (FIGS. 1 and 2), so that when the electrolyte is started with the product water, the reservoir is printed and when the cell is in operation, in particular with one Operating temperature of over 100 ° C, the product water evaporates and the resulting capillary negative pressure sucks the electrolyte back into the cell.
  • the electrolyte is simply removed from the stack with the process gas stream.
  • a collecting reservoir is provided only in the cell stack derivation of the process gas line. The electrolyte is stored in this collecting reservoir and / or cleaned of the process exhaust gas and / or the product water before it is sucked back through the additional line into the HTM fuel cell stack to the individual cells of the stack (e.g. via capillary effect).
  • the electrolyte is also washed out of the cell with the process exhaust gas and m to which Stack adjacent, Sam elreservoir headed where he gegebe ⁇ appropriate, nigt from the process gas and / or the product water gerei ⁇ is.
  • the process gas line is preferably used instead of an additional line to recirculate the electrolyte. The process gas line is switched over so that the process gas flows in the opposite direction and thus transports the electrolyte m the cell again (FIG. 4). In this case it is
  • the process gas pressure on one side of the electrolyte may exclusively cathode-side application of the electrolyte at the start and / or be favored when switching off, so that, for example bet ⁇ ebenen air in the HTM fuel cell, an additional to ⁇ Air supply line, for example from the compressor and / or from the air filter to the reservoir, is sufficient so that the cathode air flow can be switched in opposite directions for a short time (cf. FIG. 4).
  • the liquid barrier layer is known from DE 19844983.6 and can e.g. comprise a fine-pored carbon airgel and / or a xerogel.
  • FIG. 1 shows the configuration with a liquid barrier layer, one (FIG. 1 a) with the liquid barrier layer adjacent to the pole plate and the second (FIG. 1 b) with the liquid barrier layer between the electrode and the gas diffusion layer.
  • Figure 2 also shows embodiments with Flusstechniks ⁇ barrier layer, however, there are capillaries in Elek ⁇ trolyttrager integrated, which again zurucksaugen the electrolyte fast ⁇ ler the cell.
  • FIG. 3 shows an embodiment in which a collecting reservoir for the HTM fuel lines of a stack is provided
  • FIG. 4 finally shows a diagram of an HTM fuel cell, is present at a collection reservoir / reservoir in which a construction by which, after he ⁇ patentedtem start, the process gas stream may be switched in opposite directions, so that the electrolyte on the process gas flow again the HTM Fuel cell is transported back.
  • the electrolyte carrier 1 with electrolyte, e.g. a NafionQ membrane with free phosphoric acid.
  • the cell is delimited by the two pole plates 5 which open the reservoir 2 upwards.
  • the electrolyte carrier 1 also extends to the reservoir 2, so that when the cell overflows the electrolyte together with product water m the reservoir 2 is rinsed.
  • the figure shows the reservoir 2 half full.
  • the HTM fuel cell also contains two gas diffusion layers 3 with catalyst coating, such as Carbon mesh or other current collectors.
  • the two HTM fuel cells from FIG. 1 differ with regard to the arrangement of the liquid barrier layer 4 within the cell.
  • Adjacent m Figure la is at the pole plates 5 a Flusstechnikssperr GmbH 4, such as a microporous carbons ⁇ fabric structure that ensures that the cell is not the gas discharge channels 7 of the pole plates 5, via runs, but the reservoir. 2
  • this liquid barrier layer 4 is located directly adjacent to the electrolyte carrier, so that the electrolyte cannot even overflow into the gas diffusion layer 3.
  • FIG. 2 again shows two HTM fuel cells, which are identical except for the arrangement of the liquid barrier layer 4.
  • the electrolyte carrier e.g. the porous matrix or membrane, here capillaries and / or channels integrated, which are directed and facilitate and / or accelerate the return of the electrolyte from the reservoir 2.
  • the product water is released from the cell in gaseous form and a negative pressure is created in the cell, which supports the electrolyte, if necessary by, preferably directed , Capillaries and / or channels in the electrolyte carrier, the cell is sucked back out of the reservoir.
  • FIG. 3 shows an embodiment in which the liquid barrier layer of the cell can be omitted and the overflow of the electrolyte is collected by all cells of a stack 31 and the collection reservoir 32 is led through the line 33 m.
  • At least one process exhaust gas line 34 also leads through the collecting reservoir 32, so that the amount of electrolyte which has been removed from the cells with the process gas also ends up in the collecting reservoir 32.
  • FIG. 4 shows an embodiment in which the
  • Electrolyte no longer automatically flows back into the cell, but instead the cells are blown back by switching the process gas line after the start procedure.
  • a single cell is again shown (as in Figures 1 and 2), although the application is also obvious in a stack.
  • the HTM fuel cell has the electrolyte carrier 43 arranged in the center, which, as in all exemplary embodiments, can have directed capillaries.
  • the cell is delimited by the pole plates 5.
  • Arranged at a distance from the cell is the collecting reservoir 46, which is shown in the figure immediately below the cell for reasons of clarity.
  • the process gas 1 flows, e.g.
  • the process exhaust gas 1 enriched with electrolyte vapor and / or droplets then flows via line 41 m to the collecting reservoir 46, where conditions (pressure, temperature, etc.) prevail that cause at least the electrolyte to be separated from the process exhaust gas 1 there.
  • the collecting reservoir 46 is preferably constructed so that the
  • the process exhaust gas (1) line which leads out of the collecting reservoir 46, has a valve 49 which is closed after the starting process has ended, that is to say when the operating temperature of the cell is preferably greater than 100 ° C. Simultaneously with the closing of the valve 49, the valve 50 is opened.
  • the process gas 2 flows through the valve 50 is the same type as the process gas 1, for example air again, m the collecting reservoir 46, preferably through the liquid electrolyte, where the conditions are now set so that the process gas 2 is enriched with electrolyte.
  • the process gas 2 leaves the collecting reservoir 46 via the line 41 and flows the HTM fuel cell through the gas distribution channels 48, to which it releases the electrolyte to the cell.
  • the process gas 2 leaves the cell again through the process exhaust gas (2) line 42 and the valve 51. When starting, the valve 51 remains closed.
  • the present invention solves the problem of electrolyte loss from a liquid electrolyte of an HTM fuel cell.
  • the invention is primarily designed for starting an HTM fuel cell that has an operating temperature of greater than 100 ° C., however, the application is to similar problems (leakage and / or overflow) of these or other HTM fuel cells and outside the starting process obvious.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (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 une pile à combustible HTM à rinçage de l'électrolyte réduit et, en particulier, une nouvelle construction au moyen de laquelle l'électrolyte rincé est collecté (32) et recyclé dans la pile à combustible HTM (31). L'invention concerne en outre un procédé de démarrage d'une pile à combustible HTM, selon lequel, grâce à la nouvelle construction, l'électrolyte rincé est recyclé dans la pile en régime normal de fonctionnement.
EP00929221A 1999-03-29 2000-03-17 Pile a combustible htm ou batterie de piles a combustible htm a rin age de l'electrolyte reduit, et procede de demarrage Withdrawn EP1194967A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914247A DE19914247A1 (de) 1999-03-29 1999-03-29 HTM-Brennstoffzelle mit verminderter Elektrolytausspülung, HTM-Brennstoffzellenbatterie und Verfahren zum Starten einer HTM-Brennstoffzelle und/oder einer HTM-Brennstoffzellenbatterie
DE19914247 1999-03-29
PCT/DE2000/000829 WO2000059060A1 (fr) 1999-03-29 2000-03-17 Pile a combustible htm ou batterie de piles a combustible htm a rinçage de l'electrolyte reduit, et procede de demarrage

Publications (1)

Publication Number Publication Date
EP1194967A1 true EP1194967A1 (fr) 2002-04-10

Family

ID=7902838

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00929221A Withdrawn EP1194967A1 (fr) 1999-03-29 2000-03-17 Pile a combustible htm ou batterie de piles a combustible htm a rin age de l'electrolyte reduit, et procede de demarrage

Country Status (7)

Country Link
US (1) US20020076584A1 (fr)
EP (1) EP1194967A1 (fr)
JP (1) JP2002540586A (fr)
CN (1) CN1347574A (fr)
CA (1) CA2369001A1 (fr)
DE (1) DE19914247A1 (fr)
WO (1) WO2000059060A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2001003218A1 (fr) * 1999-07-05 2001-01-11 Siemens Aktiengesellschaft Systeme de pile a combustible htm et procede permettant de faire fonctionner un tel systeme
DE19962684A1 (de) * 1999-12-23 2001-07-26 Siemens Ag Brennstoffzellenanlage als Antriebseinheit für ein Fahrzeug
DE10214565A1 (de) * 2002-03-31 2003-10-23 Siemens Ag Verfahren zur Verringerung der Degradation von HT-PEM-Brennstoffzellen und zugehörige Brennstoffzellenanlage
US20040202921A1 (en) * 2003-04-14 2004-10-14 Gencell Corporation Apparatus and method for addition of electrolyte to fuel cells
US7749637B2 (en) * 2005-09-19 2010-07-06 Gm Global Technology Operations, Inc. Water blocking layer and wicking reservoir for PEMFC
DE102006026080A1 (de) * 2006-06-03 2007-12-06 Sartorius Ag Brennstoffzellensystem und Verfahren zum Betreiben eines Brennstoffzellensystems mit flüssigem Energieträger
WO2010041332A1 (fr) * 2008-10-10 2010-04-15 トヨタ自動車株式会社 Pile à combustible
WO2011006623A1 (fr) * 2009-07-16 2011-01-20 Basf Se Procédé pour faire fonctionner une pile à combustible
DE112010003228A5 (de) * 2009-07-16 2013-06-06 Basf Se Verfahren zum Betrieb einer Brennstoffzelle und zugehörige Brennstoffzelle
DE102009028308A1 (de) 2009-08-06 2011-02-10 Volkswagen Ag Membran-Elektroden-Einheit sowie eine solche umfassende Brennstoffzelle
DE102014104310A1 (de) * 2014-03-27 2015-10-01 Siqens Gmbh Vorrichtung und Verfahren zur Lebensdauerverlängerung von HT-PEM Brennstoffzellen

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Also Published As

Publication number Publication date
CN1347574A (zh) 2002-05-01
WO2000059060A1 (fr) 2000-10-05
JP2002540586A (ja) 2002-11-26
CA2369001A1 (fr) 2000-10-05
DE19914247A1 (de) 2000-10-19
US20020076584A1 (en) 2002-06-20

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