EP1252676A1 - Flüssigbrennstoffzellensystem - Google Patents
FlüssigbrennstoffzellensystemInfo
- Publication number
- EP1252676A1 EP1252676A1 EP00985075A EP00985075A EP1252676A1 EP 1252676 A1 EP1252676 A1 EP 1252676A1 EP 00985075 A EP00985075 A EP 00985075A EP 00985075 A EP00985075 A EP 00985075A EP 1252676 A1 EP1252676 A1 EP 1252676A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- temperature
- concentration
- circuit line
- anode
- 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- Withdrawn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
- H01M8/04—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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
-
- 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 system and a method for operating such a fuel cell system with the features according to the preamble of patent claims 1 and 6, respectively.
- a generic fuel cell system is known from DE 198 07 876 AI. There, a liquid methanol / water mixture is circulated on the anode side. To ensure a constant concentration of methano, the anode circuit is metered in from a methanol reservoir. The dosing amount is determined with the help of a concentration sensor in the anode circuit. Liquids or ionic or nonionic additives to the water with good frost protection properties are proposed as cooling agents. In particular for a DMFC, such suitable coolants are currently and probably not available in the foreseeable future.
- the physical background is as follows:
- the DMFC is usually operated at temperatures around 100 ° C.
- the methanol concentration is typically between 0.5 and 2 mol / 1 or 1.6 and 6.4 percent by weight.
- the cause is the methanol permeability of available membranes. If methanol is used in higher concentrations, the excess methanol diffuses through the membrane to the cathode. The result is a drastically reduced efficiency.
- the cryoscopic constant of the water is 1.86 K kg / mol, which means that the freezing point drops by only 1.86 ° C per oil / kg of additive. Since this is a colligative property, this value is independent of the type of additive.
- the freezing point of the commonly used water / methanol mixtures is around -1
- an additive with a concentration of over 16 mol / kg is required.
- Such an additive is currently not available. In principle, it will not be detectable in the long term either, because even a relatively small molecule with an assumed molar mass of 50 g / mol was required in a concentration of 800 g / kg. However, a mixture of this composition is no longer sufficient to stoichiometrically supply the water with water. However, water and methanol in a stochiometric ratio of 1: 1 are required for the anode reaction.
- frost protection By increasing the fuel concentration in the anode circuit line as the temperature drops, the freezing point of the fuel / coolant mixture is increased and thus frost protection is ensured, while at the same time the efficiency in normal operation of the system does not deteriorate. With this measure, frost protection down to -35 ° C is possible.
- the cold start behavior is improved by faster heating of the fuel cell, because the fuel increasingly diffuses through the membrane to the cathode due to the increased concentration and is oxidized there catalytically immediately after the start of the air supply with heat emission. This speeds up the cold start process considerably.
- the frost resistance can be warrants ⁇ that the fuel concentration m the AnodenJ-creis ein either durcn continuous adjustment of the concentration setpoint is increased to the decreasing temperature or raised abruptly by comparing the detected temperature with a predetermined temperature threshold in a simple manner.
- the additional amount of fuel required can be reduced despite adequate frost protection, thus improving overall efficiency.
- the system is not always switched to maximum frost protection when the temperature falls below a threshold value, but the frost protection is adapted to the actual temperature.
- the fuel cell designated overall by 1, consists of an anode compartment 2 and a cathode compartment 3, which are separated from one another by a proton-conducting membrane 4.
- a liquid fuel / coolant mixture is led through the anode compartment 2 via an anode circuit line 5, which connects an anode compartment outlet 6 with an anode compartment inlet 7 of the fuel cell 1.
- No suitable substance that is liquid and electrochemically oxidizable at room temperature can be used as the fuel.
- the system described in the exemplary embodiment is operated with liquid methanol as the fuel and water as the coolant. Although only the use of a methanol / water mixture is described in the following, the scope of protection of this application should not be restricted to this exemplary embodiment.
- Such a system operated with liquid methanol / water mixture is commonly referred to as direct methanol fuel cell (DMFC).
- An oxygen-containing gas is fed into the cathode compartment 3 via a cathode feed line 8.
- ambient air is used for this.
- the fuel cell 1 the fuel is oxidized at the anode and the atmospheric oxygen at the cathode is reduced.
- the proton-conducting membrane 4 is coated on the corresponding surfaces with suitable catalysts, such as, for example, high-surface-area precious metal tubes or supported catalysts.
- suitable catalysts such as, for example, high-surface-area precious metal tubes or supported catalysts.
- Protons can now migrate through the proton-conducting membrane 4 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 2 via the anode circuit line 5.
- the cathode exhaust air containing residual oxygen and water vapor is discharged via a cathode exhaust gas device 9.
- the ambient air in the cathode compartment 3 can preferably be provided with overpressure.
- the methanol / water mixture is circulated through the anode circuit line 5 at a predetermined pressure with the aid of a pump 10.
- the ratio of water to methanol m of the anode circuit line 5 is adjusted with the aid of a sensor 11 which measures the methanol concentration m of the anode circuit line 5.
- a concentration control for the methanol / water mixture the liquid methanol from one
- Methanol reservoir 12 is fed via a feed line 13 and the anode circuit line 5 is injected with the aid of an injection nozzle 14 m (not shown in more detail).
- the injection pressure is generated by an injection pump 15 arranged in the supply line 13.
- the methanoidosing is carried out by a suitable control of the injection nozzle 14.
- a control device 17 is provided, which is connected to the pump 10, the sensor 11, the injection pump 15, the injection nozzle 14 and possibly other components via dotted measurement or control lines.
- a methanol / water mixture with a preferably constant methanol concentration is thus continuously supplied to the anode compartment 2.
- a gas separator 16 is used to separate the carbon dioxide enriched with methanol and water vapor from the liquid / gas mixture m in the anode circuit line 5. Too much methanol discharge through the carbon dioxide gas is to be prevented, since otherwise the overall efficiency of the system is reduced and at the same time unburned methanol was released into the environment. Contrary to the gas separator shown in simplified form in the drawing, more complex devices are usually used for this purpose.
- a device for determining a temperature T 1 ⁇ ⁇ is provided.
- Conventional temperature sensors can be used for this. It is advantageous if the sensor 11 is designed as a combined concentration and temperature sensor. Additional components can thus be saved. However, it is of course, it is also possible to provide a separate temperature sensor.
- the sensor 11 m of the anode circuit line 5 is arranged between the gas separator 16 and the pump 10. However, it is also possible to arrange the sensor 11 at a different location m in the anode circuit line 5 or also directly in the fuel cell 1. It is also possible to use a temperature sensor that measures the ambient temperature. However, the heat that was still present in the system after switching off could not be taken into account.
- frost protection for the system is ensured by adapting the concentration K Me0H of the methanol / water mixture to the temperature T lst - m of the anode circuit line 5 or to the prevailing ambient temperature. If the temperature T drops , the concentration K Me oH is increased and thus the freezing point of the methanol / water mixture is lowered. This ensures frost protection.
- the increased methanoconcentration K Me oH also leads to faster heating of the fuel cell 1, because the methanol diffuses more and more through the membrane 4 to the cathode 3 and is oxidized there catalytically immediately after the start of the air supply with heat emission. This speeds up the cold start process considerably.
- the temperature monitoring and the associated concentration adjustment are preferably carried out only when the system is at a standstill because the temperatures are sufficiently high during operation of the fuel cell 1. However, for other applications, the temperature can also be monitored during operation.
- the sensor 11 continuously monitors the temperature T actual and possibly the concentration K Me oH of the methanol / water mixture.
- the measured temperature T actual with a predetermined temperature threshold value is then in the control device 17 S compared.
- the temperature T falls below the temperature threshold T BLK ei ⁇ , for example below 0 ° C, the methanol concentration MeOH K is increased in the anode circuit line 5, by additional methanol is fed into the anode circuit line. 5
- the injection pump 15 and the injection nozzle 14 are controlled accordingly by the control unit 17.
- the concentration can be increased either by adding a predetermined amount of methanol once or by means of a control system by means of concentration monitoring.
- the concentration sensor 11 is then preferably arranged upstream of the injection nozzle 14 in the anode circuit line 5, so that the setpoint K sol ⁇ for the methanol concentration is only reached when the concentration has spread over the entire anode circuit line 5 to the sensor 11.
- a concentration target value K should predefined as a function of the current temperature T is and then the actual methanol concentration K Me0 H using a conventional control or regulating method by driving the injection pump 15 and the injector 14 set to the predetermined concentration setpoint K so u.
- a control may be performed based on a stored in the control unit 17 characteristic map, for example, the map is predetermined injection amount for the methanol function of the measured temperature T and the current methanol concentration K Me oH contains in the anode circuit line. 5
- T Schwe ⁇ _i several temperature thresholds T Schwe ⁇ _i can be specified, if, when decreasing Temperature T is below the next lower temperature threshold T SC hwei ⁇ _ ⁇ + ⁇ , a further predetermined amount of methanol is added or a higher methanol concentration K Me0 H is set.
- the system is therefore not always immediately switched to maximum frost protection, but the frost protection is adapted to the actual temperature. As a result, the additional amount of methanol required can be reduced despite adequate frost protection and the overall efficiency can be improved.
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 |
---|---|---|---|
DE10000514A DE10000514C2 (de) | 2000-01-08 | 2000-01-08 | Brennstoffzellensystem und Verfahren zum Betreiben eines solchen |
DE10000514 | 2000-01-08 | ||
PCT/EP2000/011587 WO2001052339A1 (de) | 2000-01-08 | 2000-11-21 | Flüssig brennstoffzellensystem |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1252676A1 true EP1252676A1 (de) | 2002-10-30 |
Family
ID=7626978
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00985075A Withdrawn EP1252676A1 (de) | 2000-01-08 | 2000-11-21 | Flüssigbrennstoffzellensystem |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1252676A1 (de) |
JP (1) | JP2003520399A (de) |
DE (1) | DE10000514C2 (de) |
WO (1) | WO2001052339A1 (de) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10035756A1 (de) | 2000-07-22 | 2002-01-31 | Daimler Chrysler Ag | Brennstoffzellensystem und Verfahren zum Betreiben eines solchen |
US20030003336A1 (en) * | 2001-06-28 | 2003-01-02 | Colbow Kevin Michael | Method and apparatus for adjusting the temperature of a fuel cell by facilitating methanol crossover and combustion |
DE10140176A1 (de) * | 2001-08-22 | 2003-03-13 | Audi Ag | Brennstoffzellensystem mit einer Wasserzufuhreinrichtung |
US6727013B2 (en) * | 2001-09-07 | 2004-04-27 | General Motors Corporation | Fuel cell energy management system for cold environments |
DE10160474A1 (de) * | 2001-12-08 | 2003-06-18 | Ballard Power Systems | Abschaltprozedur für ein Methanol-Brennstoffzellensystem |
US6884529B2 (en) * | 2002-02-06 | 2005-04-26 | E. I. Du Pont Canada Company | Method of heating up a solid polymer electrolyte fuel cell system |
JP3671917B2 (ja) | 2002-02-08 | 2005-07-13 | 日産自動車株式会社 | 燃料電池システム |
DE10314605A1 (de) * | 2002-07-26 | 2004-02-05 | Daimlerchrysler Ag | Anordnung und Verfahren zur optischen Messung von Wasser in einer Membran-Elektroden-Anordnung |
JP3878092B2 (ja) * | 2002-08-30 | 2007-02-07 | ヤマハ発動機株式会社 | 直接改質型燃料電池システム |
WO2004027913A1 (ja) * | 2002-09-18 | 2004-04-01 | Nec Corporation | 燃料電池システムおよびその使用方法 |
JP2005032609A (ja) * | 2003-07-07 | 2005-02-03 | Sony Corp | 燃料電池の凍結防止方法、燃料電池の発電方法、及び燃料電池システム |
JP2005183354A (ja) * | 2003-11-27 | 2005-07-07 | Nissan Motor Co Ltd | 燃料電池システム |
US20080233437A1 (en) * | 2004-04-01 | 2008-09-25 | Yamaha Hatsudoki Kabushiki Kaisha | Fuel Cell System and Control Method Therefor |
JP2005340174A (ja) * | 2004-04-07 | 2005-12-08 | Yamaha Motor Co Ltd | 燃料電池システムおよびその制御方法 |
JP2005317436A (ja) * | 2004-04-30 | 2005-11-10 | Seiko Epson Corp | 燃料電池システムおよび機器 |
WO2005112171A1 (ja) * | 2004-05-14 | 2005-11-24 | Kurita Water Industries Ltd. | 燃料電池のための燃料貯蔵・供給装置 |
JP2006004868A (ja) | 2004-06-21 | 2006-01-05 | Sony Corp | 燃料電池システム及び燃料電池起動方法 |
JP5074032B2 (ja) | 2004-08-31 | 2012-11-14 | ヤマハ発動機株式会社 | 燃料電池システムおよびその制御方法 |
JP4924786B2 (ja) | 2004-09-06 | 2012-04-25 | ソニー株式会社 | 燃料電池発電装置の運転方法及び燃料電池発電装置 |
WO2007010834A1 (ja) * | 2005-07-21 | 2007-01-25 | Nec Corporation | 燃料電池及び燃料電池運転方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1907737A1 (de) * | 1969-02-15 | 1970-08-20 | Bosch Gmbh Robert | Verfahren zur Regelung eines Brennstoffzellenaggregates |
JPS6158170A (ja) * | 1984-08-29 | 1986-03-25 | Shin Kobe Electric Mach Co Ltd | 液体燃料電池の操作装置 |
JPS63184267A (ja) * | 1987-01-24 | 1988-07-29 | Hitachi Ltd | 電源装置 |
DE19701560C2 (de) * | 1997-01-17 | 1998-12-24 | Dbb Fuel Cell Engines Gmbh | Brennstoffzellensystem |
JPH10223249A (ja) * | 1997-02-03 | 1998-08-21 | Toyota Motor Corp | 燃料電池装置および燃料電池装置の流路凍結防止方法 |
DE19807876C2 (de) * | 1998-02-25 | 2002-10-24 | Xcellsis Gmbh | Brennstoffzellensystem |
JP3553377B2 (ja) * | 1998-07-02 | 2004-08-11 | 本田技研工業株式会社 | 燃料電池システムおよびその排水方法 |
-
2000
- 2000-01-08 DE DE10000514A patent/DE10000514C2/de not_active Expired - Fee Related
- 2000-11-21 JP JP2001552460A patent/JP2003520399A/ja active Pending
- 2000-11-21 EP EP00985075A patent/EP1252676A1/de not_active Withdrawn
- 2000-11-21 WO PCT/EP2000/011587 patent/WO2001052339A1/de not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO0152339A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE10000514C2 (de) | 2002-01-10 |
WO2001052339A1 (de) | 2001-07-19 |
JP2003520399A (ja) | 2003-07-02 |
DE10000514A1 (de) | 2001-08-09 |
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Legal Events
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Inventor name: MUELLER, JENS, THOMAS |
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Effective date: 20030801 |
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Designated state(s): DE FR GB IT |
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