WO2003012905A2 - Pile a combustible methanol directe portable et procede d'utilisation correspondant - Google Patents

Pile a combustible methanol directe portable et procede d'utilisation correspondant Download PDF

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Publication number
WO2003012905A2
WO2003012905A2 PCT/DE2002/002754 DE0202754W WO03012905A2 WO 2003012905 A2 WO2003012905 A2 WO 2003012905A2 DE 0202754 W DE0202754 W DE 0202754W WO 03012905 A2 WO03012905 A2 WO 03012905A2
Authority
WO
WIPO (PCT)
Prior art keywords
methanol
portable
fuel cell
anode
dmfc
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/DE2002/002754
Other languages
German (de)
English (en)
Other versions
WO2003012905A3 (fr
Inventor
Manfred Baldauf
Klaus Dennerlein
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
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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, Siemens Corp filed Critical Siemens AG
Priority to AU2002321011A priority Critical patent/AU2002321011A1/en
Publication of WO2003012905A2 publication Critical patent/WO2003012905A2/fr
Anticipated expiration legal-status Critical
Publication of WO2003012905A3 publication Critical patent/WO2003012905A3/fr
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
    • H01M8/24—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • 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
    • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to a portable direct methanol fuel cell, with at least one fuel line unit from a polymer electrode forming a membrane electrode assembly with anode and cathode and an anode compartment on one hand and a cathode compartment on the other hand and with a storage container for a methanol / water mixture.
  • the invention also relates to an operating method of such a portable direct methanol fuel cell.
  • a methanol / water mixture is pumped through the anode compartment of the cell.
  • Concepts to solve the problem of the need-based methanol metering for small DMFC cells are not known from the prior art.
  • the object of the invention is therefore to keep the methanol loss in a miniature DMFC, especially after switch-off operations, negligible and to implement a simple methanol supply.
  • An associated operating procedure should also be specified.
  • the problem of dead volume in the anode space is solved with the invention.
  • the draining of the tank can be prevented by separating the tank from the cell, but not the loss of the fuel that is already present in the anode compartment.
  • the invention basically deviates from the previous version of the DMFC.
  • the methanol solution is pumped into the fuel cell (FC), for example.
  • the cell contains a distribution structure for the liquid anolyte.
  • An alternative, particularly in the small power range, is to provide a large anode space which also serves as a fuel reservoir.
  • the volume requirement for the methanol supply is greatly reduced, although an efficient supply of fuel is still guaranteed. This is done using the physical principle of capillary action instead of pumps. This considerably simplifies the periphery, but at the same time avoids dead volumes filled with methanol.
  • the extent of the methanol supply can be influenced by the pore structure and the chemical nature of the filler material.
  • FIG. 1 shows a PEM fuel cell according to the prior art and the Figures 2 to 4 alternative embodiments of DMFC s according to the invention.
  • a portable fuel cell for generating electrical energy according to the principle of the direct methanol fuel cell, or DMFC for short consists of at least one fuel cell unit and an associated container for the fuel.
  • the individual embodiments relate to the constructive coupling of the anode space to the storage container for the liquid fuel.
  • the methanol / water mixture realizes the fuel and the electrolyte, which is fed to the anode of the DMFC. It is also referred to as the anolyte and the anode compartment as the anolyte compartment.
  • PEM polymer electrolyte membrane
  • the arrangement is each completed by a bipolar plate 16 or 16 ', with sealing elements 17 being provided on the side.
  • FIG. 1 a storage container for the fuel is shown. This is indicated as 1 by way of example in FIGS. 2 to 4. There is a connection 2 between the storage container 1 and the anode compartment, which will be discussed further below.
  • a common feature of the individual examples is to design the anode compartment in such a way that existing distribution structures, such as channels or anolyte reservoirs, can be completely eliminated and replaced by structures or materials with a pronounced capillary action. Structures with pores ⁇ 1 ⁇ m, such as wicks, fabrics, tiles or the like, are suitable for this.
  • the electrode is directly coupled to the latter structures. If the electricity is to be transported in the axial direction, e.g. in a complete fuel cell stack, then the porous structures must be electrically conductive at the same time. Sufficient methanol transport for operation is ensured by capillary forces.
  • the anode space 14 behind the electrode 12 consists only of a carbon fleece 24, which is closed on the back with a smooth bipolar plate 16.
  • the methanol is supplied laterally or through the back through the bipolar plate 16.
  • the carbon fleece 24 is connected to a methanol tank 1 via a wick.
  • This connection which expediently as a thin ne capillary 2 can be formed, at the same time mechanically, for example by a shut-off valve, separable from the cell 10.
  • a shut-off valve separable from the cell 10.
  • Connected to the anode compartment 14 is a device which is not shown in detail in the figures, via which the CO 2 produced during the reaction can escape. It can be a valve, gas permeable membrane, etc.
  • the construction is the same as in example 1, but the carbon fleece is omitted here according to FIG. 3, so that the electrode 14 together with the current collector is in direct contact with the bipolar plate 16.
  • the capillary and storage effect of the appropriately designed electrode 14 is used to supply methanol and to distribute it over the entire surface.
  • the electrode 14 can be adjusted here specifically by additional additives according to their properties with regard to capillary action, etc.
  • Embodiment 3 The construction is carried out as in Example 1 or 2, but without a device for releasing C0 2 on the anode side or as a device which releases C0 2 only at a defined excess pressure.
  • the pressure difference from the tank 1 prevents the volumes between the shut-off valve of the tank and the electrolyte membrane 11 from running full of anolyte. Only the capillary spaces 14, 16 of the feed and the electrode 12 remain filled.
  • a C0 2 ventilation may be located on the tank side.
  • Example 1 or Example 2 is assumed. Operation takes place in such a way that after the battery is switched off, the cell is briefly continued to operate with the C0 valve closed, so that — as described with reference to Example 3 — methanol located in the anode space 14 is pressed back into the tank 1.
  • Example 5
  • the anode space 14 consists of a conductive, biporous material 44 with a proportion of small pores and a proportion of large pores.
  • the porous structure is coupled to the tank 1, namely laterally or at the rear, so that the small pores ensure the methanol transport from the tank 1 to the anode 12 due to their capillary action.
  • the C0 2 formed on the anode 12 can escape from the electrode through the large pores, but cannot penetrate into the small pores.
  • the CO 2 can be separated from the methanol and carried away from the cell 10. If, for example, an overpressure is built up in the coarse-porous structure via a valve, the subsequent transport of methanol from the tank is prevented. As in Example 4, this can be used as a shutdown procedure.

Landscapes

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

Abstract

Selon l'état antérieur de la technique, une pile à combustible méthanol directe comporte au moins une unité de pile à combustible composée d'une unité d'électrode à membrane, et un réservoir de méthanol. Selon l'invention, la chambre d'anode comporte ou est remplacée par des structures et/ou des matériaux à effet capillaire éliminant tout volume mort. Le procédé d'utilisation selon l'invention consiste à prolonger brièvement l'exploitation de l'unité de pile à combustible avec soupape à CO2 fermée, après coupure de la batterie de piles à combustible, de manière que le mélange méthanol/eau se trouvant dans la chambre d'anode est repoussé dans le réservoir.
PCT/DE2002/002754 2001-07-27 2002-07-26 Pile a combustible methanol directe portable et procede d'utilisation correspondant Ceased WO2003012905A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002321011A AU2002321011A1 (en) 2001-07-27 2002-07-26 Portable direct methanol fuel cell and corresponding operating method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10136755.4 2001-07-27
DE10136755A DE10136755A1 (de) 2001-07-27 2001-07-27 Portable Direkt-Methanol-Brennstoffzelle und zugehöriges Betriebsverfahren

Publications (2)

Publication Number Publication Date
WO2003012905A2 true WO2003012905A2 (fr) 2003-02-13
WO2003012905A3 WO2003012905A3 (fr) 2004-07-08

Family

ID=7693374

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2002/002754 Ceased WO2003012905A2 (fr) 2001-07-27 2002-07-26 Pile a combustible methanol directe portable et procede d'utilisation correspondant

Country Status (3)

Country Link
AU (1) AU2002321011A1 (fr)
DE (1) DE10136755A1 (fr)
WO (1) WO2003012905A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005011036A1 (fr) * 2003-07-29 2005-02-03 Statoil Asa Donnees de remplissage pour bloc electronique muni d'une pile a combustible
WO2003012906A3 (fr) * 2001-07-27 2005-02-10 Siemens Ag Pile a combustible methanol directe portable
CN109755606A (zh) * 2019-01-21 2019-05-14 西安交通大学 一种均匀流场板燃料电池及其工作方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006002926A1 (de) 2006-01-20 2007-08-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Direktoxidationsbrennstoffzelle und Verfahren zu deren Betreiben
DE102006030236A1 (de) * 2006-06-30 2008-01-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Direktoxidationsbrennstoffzelle für den konvektionsfreien Transport des Brennstoffs und Verfahren zum Betreiben der Brennstoffzelle

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5364711A (en) * 1992-04-01 1994-11-15 Kabushiki Kaisha Toshiba Fuel cell
US6054228A (en) * 1996-06-06 2000-04-25 Lynntech, Inc. Fuel cell system for low pressure operation
US6326097B1 (en) * 1998-12-10 2001-12-04 Manhattan Scientifics, Inc. Micro-fuel cell power devices
EP1293007A4 (fr) * 2000-06-13 2006-12-20 California Inst Of Techn Pile a combustible de taille reduite pour applications portables

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003012906A3 (fr) * 2001-07-27 2005-02-10 Siemens Ag Pile a combustible methanol directe portable
WO2005011036A1 (fr) * 2003-07-29 2005-02-03 Statoil Asa Donnees de remplissage pour bloc electronique muni d'une pile a combustible
CN109755606A (zh) * 2019-01-21 2019-05-14 西安交通大学 一种均匀流场板燃料电池及其工作方法
CN109755606B (zh) * 2019-01-21 2021-08-10 西安交通大学 一种均匀流场板燃料电池及其工作方法

Also Published As

Publication number Publication date
AU2002321011A1 (en) 2003-02-17
DE10136755A1 (de) 2003-02-20
WO2003012905A3 (fr) 2004-07-08

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