EP1060532A1 - Liquid fuel cell system - Google Patents
Liquid fuel cell systemInfo
- Publication number
- EP1060532A1 EP1060532A1 EP99913181A EP99913181A EP1060532A1 EP 1060532 A1 EP1060532 A1 EP 1060532A1 EP 99913181 A EP99913181 A EP 99913181A EP 99913181 A EP99913181 A EP 99913181A EP 1060532 A1 EP1060532 A1 EP 1060532A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel cell
- anode
- cathode
- water
- 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.)
- Withdrawn
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
- H01M8/10—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
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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 system with a fuel cell which has an anode compartment and a cathode compartment which are separated from one another by a proton-conducting membrane.
- the anode space of the stack is part of an anode circuit, comprising a heat exchanger for cooling the coolant / fuel mixture containing carbon dioxide derived from the anode outlet, a circulation tank in which the cooled mixture is added to a newly supplied coolant / fuel mixture, one in the circulation tank Integrated gas separator for separating carbon dioxide, and a pump for supplying the coolant / fuel mixture from the circulation tank to the anode compartment via a corresponding supply line.
- the cathode exhaust gas comprising oxygen and water vapor from the known fuel cell system is passed through a water separator, the separated water being fed to the coolant / fuel mixture to be fed to the anode circuit and part of the remaining oxygen being fed into the oxidant feed for the cathode compartment.
- the object of the invention is to provide a fuel cell system with a proton-conducting membrane that is simplified in terms of its structure and has an improved overall efficiency.
- a fuel cell system with the features of claim 1 is proposed according to the invention.
- evaporative cooling takes place in the fuel cell when the water is absorbed by the hot air of the cathode space, and is used according to the invention to cool the anode circuit. This measure saves the cooler, which would otherwise have to be provided in the anode circuit.
- the fuel cell is advantageously operated in an equilibrium of the heat balance, ie the fuel cell is operated stationary at a temperature which depends on the one hand on the properties of the proton-conducting membrane and on the other hand can be set by the speed of the liquid pump.
- the temperature of stationary operation is between 90 and 110 ° C.
- the setting of a stationary operating temperature is of crucial importance for increasing the efficiency of the fuel cell or the stack formed from several fuel cells, since isothermal operation of the stack is now possible, i.e. temperature differences over the stack length, such as those in known systems of the order of magnitude of approx. 10 ° C are common, no longer occur or only insignificantly.
- the evaporative cooling according to the invention in the fuel cell also has the advantage that the mass flow of dry air is increased to 1.5 to 2 times, which is associated with an increase in expander performance by the same factor. This is also associated with energy savings for the air supply in full load operation.
- An air cooler is advantageously provided behind the expander, which is in thermal coupling with the vehicle cooler and which serves to condense water out to achieve a positive water balance in the system.
- the single figure shows a schematic representation of the basic structure of a fuel cell system according to the invention.
- the fuel cell system of the illustrated embodiment is operated with liquid methanol as the fuel and water as the coolant.
- liquid methanol as the fuel
- water as the coolant.
- Liquids or ionic or nonionic additives to the water with good antifreeze properties are also particularly suitable as coolants.
- the possible fuels are, for example, branched variants of the above general formula, such as di- or trimethoxymethane.
- An oxygen-containing gas is fed into the cathode compartment 14 via a cathode feed line 20.
- ambient air is used for this.
- the fuel cell 10 the fuel is oxidized at the anode and the atmospheric oxygen at the cathode is reduced.
- the proton-conducting membrane 16 is coated on the corresponding surfaces with suitable catalysts. Protons can now migrate through the proton-conducting membrane 16 from the anode side and combine with the oxygen ions to form water on the cathode side.
- This electrochemical reaction creates a voltage between the two electrodes.
- the product produced at the anode outlet is a carbon dioxide gas enriched with water and methanol.
- This liquid / gas mixture is discharged from the anode compartment 12 via an anode discharge line 22.
- the residual oxygen and water vapor contain
- the cathode exhaust air is discharged via a cathode exhaust line 24.
- the ambient air in the cathode compartment 14 is provided with overpressure.
- a compressor 28, which is driven by an electric motor 26 and has a downstream air charging cooler 29, is arranged in the cathode feed line 20, which draws in the desired air mass flow and compresses it to the required pressure level.
- an air filter 30 is also preferably provided in the inlet area of the cathode feed line 20 upstream of the compressor 28. Part of the energy required for the compression of the ambient air can be recovered with the help of an expander 32 arranged in the cathode exhaust gas line 24.
- the compressor 28, the expander 32 and the electric motor 26 are preferably arranged on a common shaft. The control of the fuel line output is carried out by controlling or regulating the compressor speed and thus the available air mass flow.
- the water / methanol mixture is circulated at a predetermined pressure with the aid of a pump 34 in order to constantly ensure an excess supply of fuel at the anode.
- the ratio of water to methanol in the anode feed line 18 is adjusted with the aid of a sensor 36, which measures the methanol concentration in the anode feed line 18.
- a concentration control for the water / methanol mixture then takes place as a function of this sensor signal, the liquid methanol being fed from a methanol tank 38 via a methanol feed line 40 and injected into the anode feed line 18 with the aid of an injection nozzle 44 (not shown).
- the injection pressure is generated by an injection pump 42 arranged in the methanol feed line 40.
- a water / methanol mixture with constant methanol concentration is thus continuously supplied to the anode compartment 12.
- the carbon dioxide enriched with methanol and water vapor must now be separated from the liquid / gas mixture discharged through the anode lead 22.
- the liquid keits- / gas mixture via the anode lead 22 fed to a gas separator 52, in which the carbon dioxide is separated.
- the water / methanol mixture remaining in the gas separator 52 is returned to the anode feed line 18 via a line 54.
- the moist carbon dioxide gas separated off in the gas separator 52 is cooled to a temperature as low as possible in a cooler 56 and further methanol and water are condensed out in a downstream water separator 58.
- the remaining dry carbon dioxide with a low residual methanol content is fed via a line 60 to the cathode exhaust line 24, where it is mixed with the oxygen-rich cathode exhaust air.
- a first water separator 59 is provided behind the outlet of the cathode chamber 14 and a further water separator 61 downstream of the expander 32. As much as possible of the water vapor formed on the cathode side is fed to the expander 32.
- the expander 32 serves as a compact condensation turbine, at the outlet of which some of the water vapor condenses.
- the water collected in the water separators 59, 61 is then returned via a return line 64 with an integrated return pump 62 to a collecting and cleaning tank 50 of a branch branch 48, 66 of the anode circuit.
- the collection and cleaning container 50 is, in particular, an ion exchanger.
- a branch line 48 which leads to the collecting and cleaning container 50, is provided in the anode circuit 22 downstream of the anode outlet.
- the outlet of the collecting and cleaning container 50 is connected again to the anode lead 22 via a line 66 with an integrated valve 68 upstream of the gas separator 52.
- the collection and cleaning container 50 is used to collect and clean the water / methanol mixture coming from the anode space 12 and in the Water separator 58 of separated water and of the product water accumulated on the cathode side via the return line 64 into the anode circuit.
- the valve 68 serves on the one hand to prevent a backflow from the anode lead 22 into the line 66, and on the other hand to create the proportion of the mixture from the anode lead 22 which is to be passed through the collecting and cleaning container.
- the fuel cell 10 is operated with water breakthrough from the andode space 12 into the cathode space 14.
- the liquid water entering the cathode compartment 14 in this way is partially taken up by the dry and hot air entering the cathode compartment 14 via the cathode feed line 20 as steam up to the saturation limit.
- the water breakthrough is the result of an electroosmotic transport phenomenon through the membrane 16.
- water molecules are deposited around each proton. This migrates due to the electroosmotic pressure through the ion channels of the membrane 16, such as Nafion ®, on the cathode side.
- the number of attached water molecules is slightly temperature-dependent and is also dependent on the ion channel diameter of the membrane 16. The higher the electroosmotic transport coefficient of the membrane 16, the more water reaches the cathode side, can evaporate there and thus be used for evaporative cooling of the fuel cell 10.
- the transport over the membrane 16 brings about ten times more water into the cathode chamber 14 than there is caused by the actual water-forming reaction, the oxidation of hydrogen.
- the oxidation of hydrogen For example, in a Nafion membrane, about 5 water molecules are attached to a proton which passes through the membrane 16 8th
- the water passing through the membrane 16 evaporates on the cathode side and cools the fuel cell 10 by evaporative cooling.
- the temperature of the cathode 14 is preferably close to the boiling point of water in order to evaporate as much of the water which has passed through.
- the overpressure prevailing on the cathode 14 can be adjusted in a simple manner to regulate the boiling point of water. At 1 bar overpressure, the boiling point is around 120 ° C instead of 100 ° C at normal pressure.
- the temperature of the fuel cell is set in accordance with the overpressure offered on the cathode side.
- the water vapor is fed to the expander 32. It is particularly advantageous to prevent water vapor from condensing out on the way to the expander 32; the lines are advantageously thermally insulated in order to prevent the water vapor from condensing out. It is also expedient to take into account the increased volume requirement of the water vapor in the connecting lines between the cathode 16 and the expander 32 by means of adequate line diameters.
- the fuel cell 10 Due to the operation with water breakthrough and the omission of the cooler otherwise provided in the anode circuit, the fuel cell 10 accordingly becomes stationary at a temperature which, in addition to the overpressure in the cathode compartment 14, depends on the one hand on the properties of the proton-conducting membrane 16 and on the other hand also by the speed of the pump 34, which prepares the volume flow on the anode side. poses, can be set.
- the stationary operating temperature is advantageously between 90 and 110 ° C., in particular 105 ° C. As a result, the fuel cell or a stack formed from a plurality of fuel cells can be operated almost isothermally.
- Evaporative cooling has the additional advantage of increasing the mass flow of dry air by 1.5 to 2 times.
- the performance of the expander 32 is thus increased by the same factor, which is associated with energy savings for the air supply. This saving is approx. 8 kW in full load operation.
- An air cooler 46 arranged downstream of the expander 32 is in thermal coupling with the vehicle cooler (not shown in more detail) and has the task of condensing out the water missing from the exhaust air stream in order to achieve a positive water balance in the system described.
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
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19807876A DE19807876C2 (en) | 1998-02-25 | 1998-02-25 | The fuel cell system |
DE19807876 | 1998-02-25 | ||
PCT/EP1999/001144 WO1999044250A1 (en) | 1998-02-25 | 1999-02-23 | Liquid fuel cell system |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1060532A1 true EP1060532A1 (en) | 2000-12-20 |
Family
ID=7858843
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99913181A Withdrawn EP1060532A1 (en) | 1998-02-25 | 1999-02-23 | Liquid fuel cell system |
Country Status (7)
Country | Link |
---|---|
US (2) | US6759153B1 (en) |
EP (1) | EP1060532A1 (en) |
JP (1) | JP2002505508A (en) |
AU (1) | AU3141399A (en) |
CA (1) | CA2321548A1 (en) |
DE (1) | DE19807876C2 (en) |
WO (1) | WO1999044250A1 (en) |
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DE19958830B4 (en) * | 1999-11-30 | 2005-09-22 | P21 - Power For The 21St Century Gmbh | Fuel cell system and its use |
US6331694B1 (en) * | 1999-12-08 | 2001-12-18 | Lincoln Global, Inc. | Fuel cell operated welder |
DE10000514C2 (en) * | 2000-01-08 | 2002-01-10 | Daimler Chrysler Ag | Fuel cell system and method for operating such a system |
DE10001717C1 (en) * | 2000-01-18 | 2001-04-26 | Xcellsis Gmbh | Fuel cell system with Coanda flow amplifier used for increasing ventilation flow for fuel cell box, cathode gas or cold-starting gas flow or cathode or anode exhaust feedback flow |
DE10024531A1 (en) * | 2000-02-22 | 2001-09-13 | Gen Motors Corp | Fuel cell system has pressure increasing pump and cooler in line leading from liquid fuel container to fuel cells, nozzle in line from fuel cell back to container |
US6599652B2 (en) | 2000-02-22 | 2003-07-29 | General Motors Corporation | Fuel cell with a degassing device |
DE10015332A1 (en) * | 2000-03-28 | 2001-10-04 | Volkswagen Ag | Loading fuel mixture for fuel cell with fuel constituents involves storing and/or delivering water as mixture with another fuel constituent that lowers freezing point relative to that of water |
DE10034401A1 (en) * | 2000-07-14 | 2002-01-24 | Daimler Chrysler Ag | Fuel cell system comprises cooling fluid and fuel mixture and vent line for controlling system pressure |
DE10035756A1 (en) | 2000-07-22 | 2002-01-31 | Daimler Chrysler Ag | Fuel cell system has device for dosing and feeding combustion medium to cathode chamber depending on determined temperature |
DE10037402A1 (en) * | 2000-08-01 | 2002-02-28 | Daimler Chrysler Ag | Device for processing a hydrocarbon-water mixture |
DE10040084A1 (en) * | 2000-08-16 | 2002-03-07 | Siemens Ag | Process for mixing fuel in water, associated device and use of this device |
DE10040086C1 (en) * | 2000-08-16 | 2002-01-10 | Siemens Ag | Process for removing carbon dioxide from a water-fuel mixture present in a fuel cell comprises using a separating device operating according to the principle of a fuel cell |
DE10039960C1 (en) * | 2000-08-16 | 2001-11-08 | Siemens Ag | Removal of carbon dioxide from a mixture of water and fuel in a fuel cell, using an electro-osmosis separating device |
DE10130095B4 (en) * | 2000-08-25 | 2020-12-17 | General Motors Corporotion | Fuel cell system with a drive device, fuel cell system with a device operated with electrical energy and method for operating a fuel cell system |
JP2003288908A (en) * | 2002-03-28 | 2003-10-10 | Honda Motor Co Ltd | Fuel cell automobile |
DE10225557B4 (en) * | 2002-06-10 | 2007-03-29 | Forschungszentrum Jülich GmbH | Low-temperature fuel cell system and method for operating such |
KR100533298B1 (en) * | 2002-09-30 | 2005-12-05 | 가부시끼가이샤 도시바 | Fuel cell system |
US20040247960A1 (en) * | 2003-03-31 | 2004-12-09 | Kabushiki Kaisha Toshiba | Fuel cell system |
WO2005001969A1 (en) * | 2003-06-25 | 2005-01-06 | Toray Industries, Inc. | Polymer electrolyte, polymer electrolyte membrane therefrom, membrane electrode assembly and polymer electrolyte fuel cell |
US8318368B2 (en) | 2003-06-27 | 2012-11-27 | UltraCell, L.L.C. | Portable systems for engine block |
WO2005004257A2 (en) * | 2003-06-27 | 2005-01-13 | Ultracell Corporation | Efficient micro fuel cell systems and methods |
US7381489B2 (en) * | 2003-08-04 | 2008-06-03 | Utc Power Corporation | PEM fuel cell with high porosity hydrophilic water transport plates and temperature increase before shutdown in environment which may reach subfreezing temperatures |
US20050233182A1 (en) * | 2004-04-20 | 2005-10-20 | Fuss Robert L | Method for real-time monitoring and control of cathode stoichiometry in fuel cell system |
CA2576887C (en) * | 2004-09-03 | 2013-04-23 | Toray Industries, Inc. | Polymer electrolyte material, polymer electrolyte part, membrane electrode assembly, and polymer electrolyte type fuel cell |
US20060141329A1 (en) * | 2004-12-28 | 2006-06-29 | Utc Fuel Cells, Llc | Fuel cell demineralizers integrated with coolant accumulator |
WO2006071580A2 (en) * | 2004-12-29 | 2006-07-06 | Utc Power Corporation | Fuel cells evaporatively reactant gas cooling and operational freeze prevention |
JP2006278159A (en) * | 2005-03-29 | 2006-10-12 | Toshiba Corp | Fuel cell |
US8293418B2 (en) * | 2005-06-16 | 2012-10-23 | Industrial Technology Research Institute | Fuel supply control method and system for fuel cells |
TWI282639B (en) * | 2005-06-16 | 2007-06-11 | Ind Tech Res Inst | Fuel supply control systems of fuel cell systems |
DE102006024694A1 (en) * | 2006-05-19 | 2007-11-22 | Samsung Sdi Germany Gmbh | Combination device for the separation of liquids and gas from liquid mixtures and for mixing of liquids, comprises housing at which inlets and outlets for the liquid mixture are arranged, and gas permeable and liquid tight membrane |
US20080168009A1 (en) | 2007-01-08 | 2008-07-10 | Robert Paul Johnson | Business methods of renewable hydrocarbon-based fuel |
US8071248B2 (en) * | 2007-01-23 | 2011-12-06 | Bloom Energy Corporation | Structure and method for optimizing system efficiency when operating an SOFC system with alcohol fuels |
US8367256B2 (en) * | 2008-01-09 | 2013-02-05 | Fuelcell Energy, Inc. | Water recovery assembly for use in high temperature fuel cell systems |
US8652694B2 (en) * | 2008-03-04 | 2014-02-18 | Fuelcell Energy, Inc. | Water recovery assembly for transferring water from fuel cell cathode exhaust |
US7923162B2 (en) * | 2008-03-19 | 2011-04-12 | Dana Canada Corporation | Fuel cell assemblies with integrated reactant-conditioning heat exchangers |
EP2483959B1 (en) * | 2009-09-25 | 2015-02-11 | Danmarks Tekniske Universitet - DTU | Method of operating a direct dme fuel cell system |
US9093676B2 (en) | 2012-10-29 | 2015-07-28 | Nissan North America, Inc. | Apparatus and method of in-situ measurement of membrane fluid crossover |
US8951690B2 (en) * | 2012-10-29 | 2015-02-10 | Nissan North America, Inc. | Apparatus and method of in-situ measurement of membrane fluid crossover |
JP6986047B2 (en) * | 2019-05-31 | 2021-12-22 | 本田技研工業株式会社 | Fuel cell system |
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-
1998
- 1998-02-25 DE DE19807876A patent/DE19807876C2/en not_active Expired - Fee Related
-
1999
- 1999-02-23 EP EP99913181A patent/EP1060532A1/en not_active Withdrawn
- 1999-02-23 JP JP2000533915A patent/JP2002505508A/en active Pending
- 1999-02-23 CA CA002321548A patent/CA2321548A1/en not_active Abandoned
- 1999-02-23 US US09/623,011 patent/US6759153B1/en not_active Expired - Fee Related
- 1999-02-23 WO PCT/EP1999/001144 patent/WO1999044250A1/en not_active Application Discontinuation
- 1999-02-23 AU AU31413/99A patent/AU3141399A/en not_active Abandoned
- 1999-02-24 US US09/256,386 patent/US6777116B1/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9944250A1 * |
Also Published As
Publication number | Publication date |
---|---|
US6777116B1 (en) | 2004-08-17 |
DE19807876C2 (en) | 2002-10-24 |
AU3141399A (en) | 1999-09-15 |
CA2321548A1 (en) | 1999-09-02 |
JP2002505508A (en) | 2002-02-19 |
WO1999044250A1 (en) | 1999-09-02 |
DE19807876A1 (en) | 1999-08-26 |
US6759153B1 (en) | 2004-07-06 |
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