WO2001022516A1 - Brennstoffzelle mit internem reformer und verfahren zu deren betrieb - Google Patents
Brennstoffzelle mit internem reformer und verfahren zu deren betrieb Download PDFInfo
- Publication number
- WO2001022516A1 WO2001022516A1 PCT/DE2000/003167 DE0003167W WO0122516A1 WO 2001022516 A1 WO2001022516 A1 WO 2001022516A1 DE 0003167 W DE0003167 W DE 0003167W WO 0122516 A1 WO0122516 A1 WO 0122516A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fuel cell
- reformer
- catalyst layer
- membrane
- temperature
- Prior art date
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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
- H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
-
- 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
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
-
- 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 fuel cell with an internal reformer containing a reformer chamber and with a membrane electrode assembly containing an anode chamber and an anodic electrode coating.
- the invention also relates to a method for operating such a fuel cell.
- DMFC Direct Methanol Fuel Cell
- a disadvantage of this DMFC is that a methanol / water mixture is used as fuel, which results in a lower power density of the cell than would be the case when pure hydrogen was used as fuel.
- the object of the invention is to improve the power density from the prior art of the known fuel cell and to specify a suitable operating method for this.
- the object is achieved by the features of patent claim 1.
- a suitable method for operating such a fuel cell is the subject of claim 6. Further developments are specified in the respective dependent claims.
- the invention relates to a fuel cell with a membrane-electrode unit and an internal reformer, in which a second catalyst layer for the reforming reaction is provided in the anode chamber following the anodic electrode coating of the membrane-electrode unit.
- the reforming reaction takes place on the second catalyst layer, the hydrogen / hydrogen being obtained from the methanol / water fuel.
- the second catalyst layer is arranged within the anode reaction chamber, this is referred to as a cell with an internal reformer.
- the fuel cell is operated once as a direct methanol fuel cell with a methanol / water mixture as fuel. If the operating pressure and / or the operating temperature are sufficient, the reforming reaction can take place within the fuel cell and the fuel cell works with hydrogen as fuel.
- the fuel cell there is a separator between the two catalyst layers, the gas and / or gas separator, which is located after the active catalyst layer for the anodic oxidation, ie the anodic electrode coating of the membrane electrode unit of the fuel cell is permeable to liquids and conducts heat and electrical current.
- FIG. 1 represents a schematic representation of an embodiment.
- the figure represents an exploded view, see above that layers that directly adjoin each other are shown as separate blocks for the sake of clarity.
- membrane electrode assembly MEA
- the MEA is in each case connected to a current collector 6, 7, which connects directly to the bipolar plates (not shown) which comprise each cell.
- the current collectors 6.7 are used for current tapping and, under certain circumstances, also as gas and / or liquid distributors, depending on the structure.
- the material of the current collector should be porous, have good electronic conductivity, and have a low contact resistance.
- carbon paper can be used here, e.g. was treated with a hydrophobic polymer.
- the bipolar plates which are not shown in the figure and which close off the fuel cell unit and provide for the transport of process gas, electricity and heat and for cooling, can be made of different materials, for example of metal and / or coal.
- the electrolyte 1 is a membrane which preferably has good proton conductivity, does not necessarily require water for proton conduction and which is temperature-stable at least up to the upper operating temperatures of 250.degree. Such a membrane is known from the aforementioned DE 196 32 285 AI.
- the electrolyte membrane 1 can be provided with an additional textile fabric layer for stiffening or a textile insert Saving from Iononmer.
- the mechanical strength of the electrolyte membrane 1 can be increased to such an extent that it compensates for part of the pressure on the anode side and so the pressure on the cathode side does not necessarily have to be the same as the pressure on the anode.
- a textile insert of 20 to 70% of the volume not only saves the cost of the electrolyte membrane 1, but also drastically increases the compressive strength. This can also significantly reduce the thickness of the membrane.
- Adjacent to the electrolyte 1 is the active catalyst layer 2 for the anodic oxidation, which is separated from the reformer catalyst layer 5 by the separator 4.
- This separator like the current collectors 6 and 7, can be a thin carbon paper because the requirements for both components are similar.
- the separator 4 is comparatively thinner than the current collectors 6 and 7.
- a current collector such as carbon paper, which conducts the current from the cell to the bipolar or pole plate, is advantageously located after the reformer catalyst layer.
- the fuel cell described is operated at a temperature of 100 ° C. to 250 ° C., preferably 130 ° C. to 220 ° C. and in particular 200 ° C. and / or an operating pressure of 3 to 7 bar, in particular 5 bar.
- the fuel cell is operated with liquid fuel when starting up.
- the reforming reaction begins and the cell is no longer operated with a methanol / water mixture but with reformer gas as fuel.
- the cell is operated as a direct methanol cell at low pressure, even when gaseous fuel is present, while a reformer / hydrogen operation of the cell takes place at high operating pressure and high operating temperature.
- the methanol / water mixture which is used as fuel for operation as a direct methanol fuel cell, is preferably composed of a proportion of methanol of 0.5 mol / 1 to 20 mol / 1 and a proportion of water of 55 mol / 1 to 20 mol / 1 together.
- the "anodic electrode coating of the membrane electrode assembly” or the "active catalyst layer for the anodic oxidation", from which protons, i.e. hydrogen ions and electrons, are obtained from the hydrogen, preferably comprises a support, on the surface of which the catalyst, e.g. Platinum or a platinum / ruthenium alloy is applied.
- the carrier is preferably electronically conductive, e.g. a coal powder or soot.
- the distribution of the metallic catalyst which is very expensive because it is a noble metal, follows a distribution gradient in the active catalyst layer, so that at the point where the catalytic activity is most required, for example on Contact of the active catalyst layer to the membrane, the concentration of catalyst is highest and where the conversion rate and thus the need for catalyst is lower, for example on the side of the active catalyst layer facing away from the membrane, the concentration of catalyst is also lower is.
- the ratio of catalyst to support can be described via the distribution gradient, but also the ratio of metal I to metal II.
- the more expensive metal at the border to the membrane can be present in a ratio of 1: 1, as is the case for catalytic activity is cheapest, and only 9: 1 on the side facing away from the membrane.
- the concentration of the catalyst in the anodic electrode coating of the MEA is accordingly referred to as variable.
- the active catalyst layer of the anode consists only of the metallic catalyst, which is expensive, but the power loss due to transport is kept within limits.
- the reformer catalyst layer comprises different metals, for example a catalyst mixture with copper and zinc based on corundum (A1 2 0 3 ) has proven successful.
- the reformer catalyst layer has a mass between 3 to 50 mg / cm 2 , preferably between 7 to 30 mg / cm 2 and particularly preferably between 10 to 15 mg / cm 2 .
- the reformer catalyst layer is gas and / or liquid permeable.
- the fuel is reformed, which means that essentially the methanol / water mixture is converted to hydrogen and carbon monoxide.
- the carbon monoxide is converted to carbon dioxide, which is not a catalyst poison and is a relatively neutral and accepted exhaust gas.
- the anodic current transport through the cell is critical because, instead of a catalyst layer, the cell has two catalyst layers through which the current produced at the anode / membrane interface should be conducted to the bipolar plate with as little loss as possible. It is therefore advantageous if the catalyst for the reforming reaction is carried on an electronically highly conductive carrier, e.g. Soot and / or carbon powder is applied because the catalyst for the reforming reaction is neither a good current nor a good heat conductor.
- an electronically highly conductive carrier e.g. Soot and / or carbon powder
- the membrane-electrode unit (MEA) used here advantageously comprises a membrane with an electrode coating on both sides and, depending on the design, a current collector such as carbon paper, which may have been rendered hydrophobic.
- the electrode coating comprises an active catalyst layer, which may have the catalyst on an electronically conductive support.
- the fuel cell described therefore works once as a direct methanol fuel cell and then as a hydrogen-operated PEM fuel cell.
- the function of a high-temperature fuel cell i.e. an HT-PEM fuel cell.
- each fuel cell unit contains an internal reformer layer, on which the reforming reaction takes place at a sufficiently high pressure and / or temperature, the methanol / water fuel being converted to hydrogen.
- the arrangement of the reformer catalyst layer within the cell ensures that the heat of the anode is used for the reforming and conversely the anode is cooled via the endothermic reforming reaction.
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- 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)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00967564A EP1224705B1 (de) | 1999-09-23 | 2000-09-12 | Brennstoffzelle mit internem reformer und verfahren zu deren betrieb |
AT00967564T ATE245854T1 (de) | 1999-09-23 | 2000-09-12 | Brennstoffzelle mit internem reformer und verfahren zu deren betrieb |
JP2001525788A JP2003510767A (ja) | 1999-09-23 | 2000-09-12 | 内部改質器を有する燃料電池及びその作動方法 |
DE50003031T DE50003031D1 (de) | 1999-09-23 | 2000-09-12 | Brennstoffzelle mit internem reformer und verfahren zu deren betrieb |
CA002385622A CA2385622A1 (en) | 1999-09-23 | 2000-09-12 | Fuel cell with internal reformer and method for its operation |
US10/105,548 US20020132145A1 (en) | 1999-09-23 | 2002-03-25 | Fuel cell with internal reformer and method for its operation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19945667.4 | 1999-09-23 | ||
DE19945667A DE19945667C2 (de) | 1999-09-23 | 1999-09-23 | Brennstoffzelle, Verfahren zu deren Betrieb und zugehörige Verwendung |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/105,548 Continuation US20020132145A1 (en) | 1999-09-23 | 2002-03-25 | Fuel cell with internal reformer and method for its operation |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001022516A1 true WO2001022516A1 (de) | 2001-03-29 |
Family
ID=7923072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/DE2000/003167 WO2001022516A1 (de) | 1999-09-23 | 2000-09-12 | Brennstoffzelle mit internem reformer und verfahren zu deren betrieb |
Country Status (7)
Country | Link |
---|---|
US (1) | US20020132145A1 (de) |
EP (1) | EP1224705B1 (de) |
JP (1) | JP2003510767A (de) |
AT (1) | ATE245854T1 (de) |
CA (1) | CA2385622A1 (de) |
DE (2) | DE19945667C2 (de) |
WO (1) | WO2001022516A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001048854A2 (de) * | 1999-12-23 | 2001-07-05 | Siemens Aktiengesellschaft | Membran-elektroden-einheit für eine brennstoffzelle und herstellungsverfahren dazu |
EP1172876A2 (de) * | 2000-07-11 | 2002-01-16 | XCELLSIS GmbH | Brennstoffzelle mit einer internen Reformierungseinheit |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4171978B2 (ja) * | 2002-05-27 | 2008-10-29 | ソニー株式会社 | 燃料改質器及びその製造方法、並びに電気化学デバイス用電極及び電気化学デバイス |
DE10317976B4 (de) * | 2003-04-17 | 2013-05-29 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Festelektrolyt-Brennstoffzelle und Verfahren zu ihrer Herstellung sowie Verwendung der Festelektrolyt-Brennstoffzelle als Elektrolyseur |
WO2006014403A2 (en) * | 2004-06-30 | 2006-02-09 | Georgia Tech Research Corporation | Microstructures and methods of fabrication thereof |
WO2007048612A2 (en) * | 2005-10-27 | 2007-05-03 | Ird Fuel Cells A/S | Membrane electrode assemblies for dmfc having catalyst concentration gradient |
DE102008061771A1 (de) | 2008-12-11 | 2010-06-24 | Volker Harbusch | Brennstoffzelleneinheit für gasförmige Brennstoffe |
DE102010049794A1 (de) * | 2010-05-25 | 2011-12-01 | Diehl Aerospace Gmbh | Verfahren zur Erzeugung von Energie und die Verwendung eines Stoffgemisches zur Erzeugung von Energie |
DE102014100702B4 (de) | 2014-01-22 | 2017-06-29 | Siqens Gmbh | Brennstoffzellensystem zur thermisch gekoppelten Reformierung mit Reformataufbereitung und Verfahren dazu |
US11011763B2 (en) | 2016-10-24 | 2021-05-18 | Precison Combustion, Inc. | Solid oxide fuel cell with internal reformer |
CN106410244A (zh) * | 2016-11-02 | 2017-02-15 | 上海钧希新能源科技有限公司 | 一种分段式甲醇重整制氢燃料电池系统 |
DE102021204452A1 (de) | 2021-05-04 | 2022-11-10 | Siemens Mobility GmbH | Mitteltemperatur-Brennstoffzelle mit interner Reformierung und Schienenfahrzeug |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1553361A (de) * | 1967-02-01 | 1969-01-10 | ||
US5795668A (en) * | 1994-11-10 | 1998-08-18 | E. I. Du Pont De Nemours And Company | Fuel cell incorporating a reinforced membrane |
JPH1116588A (ja) * | 1997-06-25 | 1999-01-22 | Japan Storage Battery Co Ltd | 固体高分子電解質を備えた直接型メタノ−ル燃料電池およびその製造方法 |
WO1999008336A2 (de) * | 1997-08-11 | 1999-02-18 | Forschungszentrum Jülich GmbH | Brennstoffzelle zur direkten verstromung von methanol |
WO2000030200A1 (en) * | 1998-11-12 | 2000-05-25 | Ballard Power Systems Inc. | Fuel cell system with improved starting capability |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5077148A (en) * | 1989-05-03 | 1991-12-31 | Institute Of Gas Technology | Fully internal manifolded and internal reformed fuel cell stack |
US6162556A (en) * | 1995-12-04 | 2000-12-19 | Siemens Aktiengesellschaft | Method for operating a high-temperature fuel cell installation, and a high-temperature fuel cell installation |
-
1999
- 1999-09-23 DE DE19945667A patent/DE19945667C2/de not_active Expired - Fee Related
-
2000
- 2000-09-12 DE DE50003031T patent/DE50003031D1/de not_active Expired - Fee Related
- 2000-09-12 AT AT00967564T patent/ATE245854T1/de not_active IP Right Cessation
- 2000-09-12 JP JP2001525788A patent/JP2003510767A/ja not_active Withdrawn
- 2000-09-12 CA CA002385622A patent/CA2385622A1/en not_active Abandoned
- 2000-09-12 EP EP00967564A patent/EP1224705B1/de not_active Expired - Lifetime
- 2000-09-12 WO PCT/DE2000/003167 patent/WO2001022516A1/de active IP Right Grant
-
2002
- 2002-03-25 US US10/105,548 patent/US20020132145A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1553361A (de) * | 1967-02-01 | 1969-01-10 | ||
US5795668A (en) * | 1994-11-10 | 1998-08-18 | E. I. Du Pont De Nemours And Company | Fuel cell incorporating a reinforced membrane |
JPH1116588A (ja) * | 1997-06-25 | 1999-01-22 | Japan Storage Battery Co Ltd | 固体高分子電解質を備えた直接型メタノ−ル燃料電池およびその製造方法 |
WO1999008336A2 (de) * | 1997-08-11 | 1999-02-18 | Forschungszentrum Jülich GmbH | Brennstoffzelle zur direkten verstromung von methanol |
WO2000030200A1 (en) * | 1998-11-12 | 2000-05-25 | Ballard Power Systems Inc. | Fuel cell system with improved starting capability |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 04 30 April 1999 (1999-04-30) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001048854A2 (de) * | 1999-12-23 | 2001-07-05 | Siemens Aktiengesellschaft | Membran-elektroden-einheit für eine brennstoffzelle und herstellungsverfahren dazu |
WO2001048854A3 (de) * | 1999-12-23 | 2002-03-28 | Siemens Ag | Membran-elektroden-einheit für eine brennstoffzelle und herstellungsverfahren dazu |
EP1172876A2 (de) * | 2000-07-11 | 2002-01-16 | XCELLSIS GmbH | Brennstoffzelle mit einer internen Reformierungseinheit |
EP1172876A3 (de) * | 2000-07-11 | 2004-06-16 | Ballard Power Systems AG | Brennstoffzelle mit einer internen Reformierungseinheit |
Also Published As
Publication number | Publication date |
---|---|
DE19945667A1 (de) | 2001-04-05 |
DE50003031D1 (de) | 2003-08-28 |
EP1224705A1 (de) | 2002-07-24 |
CA2385622A1 (en) | 2001-03-29 |
ATE245854T1 (de) | 2003-08-15 |
JP2003510767A (ja) | 2003-03-18 |
US20020132145A1 (en) | 2002-09-19 |
DE19945667C2 (de) | 2003-06-26 |
EP1224705B1 (de) | 2003-07-23 |
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