CN115411316A - Fuel cell and method for operating the fuel cell - Google Patents

Fuel cell and method for operating the fuel cell Download PDF

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Publication number
CN115411316A
CN115411316A CN202210504209.6A CN202210504209A CN115411316A CN 115411316 A CN115411316 A CN 115411316A CN 202210504209 A CN202210504209 A CN 202210504209A CN 115411316 A CN115411316 A CN 115411316A
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China
Prior art keywords
fuel cell
gas
unit
anode
expansion unit
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CN202210504209.6A
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Chinese (zh)
Inventor
F·S·克鲁格
A-S·朗根汉
D·R·维特迈尔
L·鲍姆加特纳
D·梅耶
F·毛斯
F·鲍曼
P·霍尔斯特曼
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Robert Bosch GmbH
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Robert Bosch GmbH
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Publication of CN115411316A publication Critical patent/CN115411316A/en
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    • 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
    • H01M8/04156—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal
    • H01M8/04164—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying with product water removal by condensers, gas-liquid separators or filters
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C25B15/021—Process control or regulation of heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • 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
    • H01M8/04—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
    • H01M8/04067—Heat exchange or temperature measuring elements, thermal insulation, e.g. heat pipes, heat pumps, fins
    • 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
    • H01M8/04097—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with recycling of the 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
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • 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
    • H01M8/04291—Arrangements for managing water in solid electrolyte fuel cell systems
    • 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
    • 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
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to a fuel cell and a method for operating the fuel cell. The invention relates to a method (56) for operating a fuel cell (10), in particular a solid oxide fuel cell, comprising at least one fuel cell and/or electrolyser unit (12) having at least one anode, wherein a recycle designed as anode exhaust gas is recycled in at least one recycling module (18) from an anode gas outlet (14) of the fuel cell and/or electrolyser unit (12) to an anode gas inlet (16) of the fuel cell and/or electrolyser unit (12). It is proposed that in at least one operating state a fluid, in particular water, is expanded, preferably evaporated, by means of at least one expansion unit (32) in a circulation module (18).

Description

Fuel cell and method for operating the fuel cell
Technical Field
A method for operating a fuel cell has already been proposed, which comprises at least one fuel cell and/or electrolyser unit having at least one anode, wherein a recycle designed as anode exhaust gas is recycled in at least one recycling module from an anode gas outlet of the fuel cell and/or electrolyser unit to an anode gas inlet of the fuel cell and/or electrolyser unit.
Disclosure of Invention
The invention relates to a method for operating a fuel cell, in particular a solid oxide fuel cell, comprising at least one fuel cell and/or electrolyser unit having at least one anode, wherein a recycle designed as anode exhaust gas is recycled in at least one recycling module from an anode gas outlet of the fuel cell and/or electrolyser unit to an anode gas inlet of the fuel cell and/or electrolyser unit.
It is proposed to superheat a fluid, in particular water, in at least one operating state in a circulation module by means of at least one expansion unit. By means of the configuration of the method according to the invention, the anode exhaust gas can be circulated in a particularly advantageous manner. By means of the arrangement according to the invention, the fuel cell for circulating the anode exhaust gas can advantageously be operated without or with only a small supply of mechanical energy, in particular depending on the requirements for the dynamic system behavior. In particular, with the arrangement according to the invention, the volumetric flow of the anode exhaust gas to be conveyed can advantageously be operated without or with only little mechanical energy supply. Thereby a fuel cell with an advantageously high efficiency, in particular an electrical efficiency, can be provided. Preferably, the fuel cell is designed as a stationary fuel cell, for example as a heating module. Alternatively, the fuel cell may be designed as a mobile fuel cell, for example in a vehicle. In principle, the method can also be used for alternative applications in which a heat medium is conveyed. Preferably, the solid oxide fuel cell is a "solid oxide fuel cell". Thermoelectric utilization is particularly preferably integrated into the available heat flow of the fuel cell, in particular of the solid oxide fuel cell. By "fuel cell and/or electrolyser unit" is preferably understood a fuel cell, in particular a flat solid oxide fuel cell, and/or an electrolyser, in particular a high-temperature electrolyser, at least a part, in particular a base module, which is used, in particular, for stationary or mobile applications. In particular, the in particular metal-supported fuel cell and/or electrolyser unit can also comprise the entire fuel cell, in particular the entire solid oxide fuel cell, the entire electrolyser, in particular the entire high-temperature electrolyser, a fuel cell and/or electrolyser stack, and/or a composite of a plurality of fuel cells and/or electrolyser stacks. Preferably, the at least one preferably supported, in particular metal supported, fuel cell and/or electrolyser unit is provided for combusting a fuel in a combustion process under the supply of an oxidant to obtain electrical energy. Alternatively or additionally, the at least one fuel cell and/or electrolyser unit is provided for separating a fluid into at least two components under supply of electrical energy in a separation process. Preferably, the at least one fuel cell and/or electrolyser unit comprises at least one electrode unit. Preferably, the at least one electrode unit comprises at least one anode. Preferably, the at least one anode comprises or forms a functional layer designed as an electrode layer. Preferably, the at least one electrode unit comprises at least one cathode. Preferably, the at least one cathode comprises or forms a functional layer designed as an electrode layer. The at least one anode and the at least one cathode preferably participate directly in the combustion process and/or the separation process performed by means of the at least one fuel cell and/or electrolyser unit. Particularly preferably, the at least one cathode and the at least one anode are arranged to function as a cathode-anode pair. Preferably, the at least one electrode unit comprises at least one separating element, in particular a functional layer designed as an electrolyte layer. Preferably, the separating element is arranged between the at least one anode and the at least one cathode. Preferably, the at least one anode and/or the at least one cathode are designed as oxidant electrodes, in particular for contacting the oxidant and/or the cleavage products. Preferably, the at least one anode and/or the at least one cathode are designed as fuel electrodes, which are used in particular for contacting with a fuel, in particular a fuel gas, and/or another cleavage product. By "anode off-gas" is preferably understood a gas mixture which is discharged at the at least one anode from the at least one fuel cell and/or electrolyser unit, in particular at the anode gas outlet, after the end of the combustion process/separation process. By "recycle" is understood in particular a gas mixture which is re-supplied to the combustion process and/or the separation process in the at least one fuel cell and/or electrolyser unit after the combustion process/separation process. Preferably, the recycle comprises a fuel gas, in particular methane, which is not combusted in the at least one fuel cell and/or electrolyser unit. Preferably, the recycle comprises water. Preferably, the recycle comprises carbon dioxide. Preferably, the water and carbon dioxide are reaction products of a combustion process. An "anode gas inlet" is to be understood in particular as an inlet opening into the reaction chamber of the at least one anode. By "anode gas outlet" is understood in particular an outlet opening from the reaction chamber of the at least one anode. By a "recycling module" is preferably understood a module which is provided for resupplying recycled matter output from the at least one fuel cell and/or electrolyser unit to the at least one fuel cell and/or electrolyser unit. Preferably, the circulation module is designed as a fluid-technical line system, which comprises a plurality of fluid-technical components and/or assemblies. An "operating state" is preferably understood to mean a state in which the at least one fuel cell and/or electrolyser unit is operated for a combustion process and/or separation process and the at least one recycling module conducts recycle from the anode gas outlet of the at least one fuel cell and/or electrolyser unit back to the anode gas inlet of the at least one fuel cell and/or electrolyser unit. Preferably, the fluid is designed as water, in particular as water vapor. Alternatively, the fluid can also be designed as a fuel, in particular methanol. Preferably, the at least one expansion unit expands the fluid. Preferably, the at least one expansion unit is designed as an evaporator. Particularly preferably, the at least one expansion unit evaporates the fluid. Preferably, the at least one expansion unit superheats a fluid, in particular water. "superheating" is preferably understood to mean that the temperature of the water is raised above the boiling point of water at the respective pressure. Preferably, the water is converted from the liquid state to the gaseous state in an expansion unit designed as an evaporator. Preferably, the water superheated by means of the expansion unit designed as an evaporator is designed as superheated steam in at least one operating state. By "superheated steam" is preferably understood the state of water, in particular water vapor, wherein water, in particular water vapor, has a temperature above the boiling point of water. Alternatively, however, it is conceivable that the water is expanded in the at least one expansion unit without being superheated, so that moist steam is present.
In addition, it is proposed to separate a liquid fluid, in particular liquid water, from the discharged cycle product in a cycle module, in particular by means of a condenser. By means of this configuration, the output circuit can advantageously be cooled simply and the liquid fluid can be separated from the circuit. It is thus advantageously possible to provide a working medium for cogeneration which is already part of the material composition of the recyclate. The term "recirculated material discharged" is preferably understood to mean recirculated material discharged from the anode gas outlet. Preferably, the liquid fluid is fed to the at least one expansion unit in at least one state of operation. Preferably, the liquid water is fed in at least one state of operation into an expansion unit designed as an evaporator. Preferably, the liquid fluid is transported from the condenser to the at least one expansion unit by a geodetic pressure difference without a supply of mechanical energy.
It is also proposed that the expansion unit is operated by the residual heat of at least one functional unit, in particular of the at least one fuel cell and/or electrolyser unit. By this arrangement, a favorable effective use of the waste heat can be achieved. This advantageously makes it possible to dispense with an additional mechanical and/or electrical energy input for operating the circulation module. Preferably, the expansion unit transfers heat from the residual heat of the fuel cell and/or electrolyser unit to a fluid, in particular liquid, located in the expansion unit. Thereby, thermal energy can be supplied to the liquid fluid and thereby it can be heated, preferably evaporated. A "functional unit" is understood to mean a unit which, in at least one operating state, performs a specific function and releases heat in the process. The at least one functional unit is preferably designed as a heat source. "residual heat" is preferably understood to mean heat which is excess in the course of the at least one functional unit and/or is provided for release into the environment. The at least one functional unit is preferably necessary for the operation of the fuel cell. The at least one functional unit is preferably part of a fuel cell. Basically, the at least one functional unit can be designed as the at least one fuel cell and/or electrolyser unit, an adjacent fuel cell and/or electrolyser unit, a heat exchanger, a reformer or other module with heat release as appears suitable to the person skilled in the art. It is conceivable here for the waste heat to be exchanged crosswise between a plurality of fuel cells and/or electrolyser units or fuel cells. Alternatively, the at least one functional unit can also be designed as an external unit which can be operated independently of the fuel cell. The waste heat is particularly preferably designed as exhaust gas heat from the at least one fuel cell and/or electrolyser unit. Preferably, the expansion unit is operated by exhaust gas heat from the at least one fuel cell and/or electrolyser unit. Exhaust gas heat from the at least one fuel cell and/or electrolyser unit can thereby be advantageously reduced. Furthermore, an advantageous efficient energy utilization can be achieved.
It is also proposed that the expanded, in particular evaporated, fluid from the expansion unit be used as a propellant gas for an injection pump which delivers dry cycle material and/or fuel gas in at least one operating state. By this configuration, cogeneration can be particularly advantageously used for circulating the recyclate. Furthermore, with this arrangement it is advantageously possible to use the water contained in the recirculated material that is discharged as a working medium for the propulsion gas. This advantageously makes it possible to dispense with an additional supply of substance. Furthermore, an advantageous robust and maintenance-free delivery of the drying circuit and/or the fuel gas can be achieved by this configuration, since the jet pump is at least substantially free of moving elements. By "jet pump" is preferably understood a pump in which a pumping effect is produced by a fluid jet formed in particular by a propellant gas, wherein the fluid jet sucks in, accelerates and compresses a further medium by pulse exchange, which is designed in particular as a dry circuit and/or as a fuel gas. By "dry recycle" is preferably understood a recycle which is freed from the water fraction and is discharged. Preferably, the dry circuit delivered by the jet pump at least partially forms the suction gas. Preferably, the suction gas is sucked by the ejector pump. The fuel gas is preferably supplied to the jet pump at least from time to time. Preferably, the fuel gas is part of the suction gas.
In addition, it is proposed that, in at least one operating state, the cycle to be circulated is heated in a heat exchanger by means of heat from the output cycle. By this arrangement, an advantageous heat exchange between the output circulation substance and the circulation substance to be circulated can be achieved. Thus, the heat from the output recycles can be used effectively in an advantageous energy source. The output recyclate preferably has a higher temperature than the recyclate to be recycled. By "recyclate to be recycled" is preferably understood a recyclate which is supplied to the anode gas inlet by means of the recycling module. The recyclate to be recycled preferably comprises fuel gas mixed with dry recyclate.
The invention further relates to a fuel cell for carrying out the method according to the invention, in particular the above-described fuel cell, comprising the at least one fuel cell and/or electrolyser unit having at least one anode and the at least one circulation module for circulating a recyclate designed as anode off-gas. It is proposed that the circulation module comprises at least one expansion unit, which is designed in particular as an evaporator, which is provided for expanding, preferably evaporating, a fluid, in particular water. By the configuration of the fuel cell according to the present invention, the anode off-gas can be advantageously circulated energy-efficiently. Thereby a fuel cell with an advantageously high efficiency, in particular an electrical efficiency, can be provided. The at least one expansion unit is preferably designed as a heat exchanger. Preferably, the at least one expansion unit is coupled for heat transfer with a waste gas line of the at least one fuel cell and/or electrolyser unit. Preferably, the at least one expansion unit is provided for evaporating a fluid, in particular water.
It is further proposed that the circulation module comprises at least one heat exchanger which is provided for transferring heat from the output circulation to the circulation to be circulated and/or the fuel gas. By this arrangement, an advantageous heat exchange between the output circulation substance and the circulation substance to be circulated can be achieved. Thus, the heat from the output circulation material can be effectively utilized. Furthermore, the cycle material and/or the fuel gas to be circulated can thereby be advantageously heated energy-efficiently.
It is also proposed that the circulation module has at least one condenser, which is provided to separate liquid water from the discharged circulation. With this arrangement, it is advantageously possible simply to cool the output circuit and to separate liquid water from the circuit. It is thus advantageously possible to provide a working medium for cogeneration which is already part of the material composition of the recyclate.
Furthermore, it is proposed that the condenser is arranged geodetically higher than the at least one expansion unit. By this arrangement, the liquid fluid, in particular liquid water, separated in the condenser can be fed to the expansion unit without the supply of mechanical energy. Thereby, an advantageously high efficiency of the fuel cell can be achieved. The term "geodetically higher" should preferably be understood as meaning that the expansion unit is spaced apart from the condenser in the direction of gravity, wherein the expansion unit is preferably aligned closer to the direction of gravity than the condenser. Preferably, the liquid fluid flows automatically into the expansion unit in at least one operating state due to gravity.
It is furthermore proposed that the circulation module comprises at least one non-return valve which is arranged fluidically between the condenser and the expansion unit. By means of this configuration, the fluid can be superheated in the at least one expansion unit in an advantageously defined manner. Thereby, an advantageous automatic cogeneration can be achieved, which in particular does not require external influences. "in terms of fluid technology" is preferably understood to mean a connection property in which at least two components or assemblies are coupled to one another in such a way that fluids, in particular circulators and/or fuel gases, can be exchanged between them, in particular without fluid losses.
It is further proposed that the circulation module comprises at least one jet pump which is fluidically connected to the expansion unit, is located downstream of the expansion unit and is provided for conveying the cycle material and/or the fuel gas to be circulated. By this configuration, cogeneration can be particularly advantageously used for circulating the recyclate. Furthermore, by means of this configuration, an advantageous robust and maintenance-free delivery of the drying circuit and/or the fuel gas can be achieved, since the jet pump is at least substantially free of moving elements. Preferably, the injection pump is designed as an injector. Preferably, the ejector pump is arranged for generating a negative pressure for sucking in suction gas. Preferably, the ejector pump is arranged for delivering the suction gas together with the propulsion gas.
Furthermore, it is proposed that the ejector pump be fluidically connected to the condenser. With this configuration, dry recyclate and/or in particular fresh fuel gas can advantageously be sucked in simply and effectively by the injection pump. Preferably, the intake region of the ejector pump is fluidically connected to a condenser.
The method according to the invention and the fuel cell according to the invention should not be limited to the above-described applications and embodiments here. In particular, the method according to the invention and the fuel cell according to the invention can have a number of individual elements, components and units and method steps different from the number mentioned here to realize the operating principle described here. Furthermore, within the numerical ranges shown in the present disclosure, numerical values within the mentioned limits should also be considered as disclosed and can be used at will.
Drawings
Further advantages result from the following description of the figures. Embodiments of the invention are shown in the drawings. The figures, description and claims contain various features in combination. Those skilled in the art will also suitably consider these features individually and combine them into other meaningful combinations.
In which is shown:
FIG. 1 is a schematic representation of a fuel cell according to the invention, and
fig. 2 shows a method according to the invention for operating the fuel cell in the form of a schematic diagram.
Description of the embodiments
Fig. 1 shows a fuel cell 10 according to the present invention. In the present case, the fuel cell 10 is designed as a stationary fuel cell, for example as a heating module. Alternatively, the fuel cell 10 can also be designed as a mobile fuel cell, for example in a vehicle. In the present case, the fuel cell 10 is designed as a solid oxide fuel cell. The solid oxide fuel cell is also referred to as "solid oxide fuel cell". Thermoelectric utilization is integrated into the available heat flow of the fuel cell 10. The thermoelectric utilization integrated into the fuel cell 10 can be operated by the residual heat of the fuel cell 10.
The fuel cell 10 includes a fuel cell and/or electrolyzer unit 12. The fuel cell and/or electrolyser unit 12 is arranged for combusting fuel in a combustion process under a supply of oxidant to obtain electrical energy. The fuel is designed as fuel gas. In the present case, the fuel cell and/or electrolyser cell 12 has an anode which is not shown in detail. In the present case, the fuel cell and/or electrolyser unit 12 comprises an electrode unit not shown in detail. In the present case, the electrode unit includes an anode. The anode has or forms a functional layer which is designed as an electrode layer. In this case, the electrode unit includes a cathode. The cathode has or forms a functional layer which is designed as an electrode layer. The anode and cathode directly participate in the combustion process by means of the fuel cell and/or electrolyser unit 12. The cathode and anode are arranged to function as a cathode-anode pair. The electrode unit comprises in the present case a separating element which is designed in particular as a functional layer of the electrolyte layer. The separating element is arranged between the anode and the cathode. The cathode is designed as an oxidant electrode, which is used in particular for contacting the oxidant and/or the cleavage products. The anode is designed as a fuel electrode, which is intended in particular for contact with a fuel, in particular fuel gas and/or another cleavage product. The fuel cell and/or electrolyser cell unit 12 has an anode gas outlet 14. The fuel cell and/or electrolyser cell 12 has an anode gas inlet 16.
The fuel cell 10 includes a circulation module 18 for circulating a circulation substance designed as an anode off-gas. The recycling module 18 is provided for redirecting the exported recyclate from the fuel cell and/or electrolyser cell 12 back to the fuel cell and/or electrolyser cell 12 without additional supply of mechanical energy to the fuel cell 10. The recycling module is provided for automatically re-transporting recycled material from the fuel cell and/or electrolyser unit 12 to the fuel cell and/or electrolyser unit 12 by means of cogeneration, in particular without supplying energy to the fuel cell 10. The electrical efficiency of the fuel cell 10 is decisively determined by the fuel gas utilization. The circulation of the anode off-gas provides a possibility of increasing the fuel gas utilization rate in the fuel cell. In order to create favorable reaction conditions, the gas on the anode side, i.e. the anode exhaust gas, must be circulated with heat of about 600 ℃. The circulation module 18 is designed as a line system in terms of fluid technology. The recycle module 18 is provided for resupplying the anode off-gas output from the fuel cell and/or electrolyzer unit 12 to the fuel cell and/or electrolyzer unit 12 as recycle. The recycle module 18 is configured to transport recycle from the anode gas outlet 14 to the anode gas inlet 16. Anode exhaust gas is discharged from the fuel cell and/or electrolyzer unit 12 at the anode after the combustion process is complete, particularly at the anode gas outlet 14. The anode off-gas is designed as a recycle. The recycle is resupplied to the combustion process in the fuel cell and/or electrolyser unit 12 after the combustion process. The recycle contains fuel gas that is not combusted in the combustion process in the at least one fuel cell and/or electrolyser unit 12. In this case, the fuel gas is methane. The recyclate comprises water. The recycle comprises carbon dioxide. Water and carbon dioxide are reaction products of the combustion process.
The circulation module 18 includes a heat exchanger 20. The heat exchanger 20 is fluidically connected to the anode gas outlet 14 via a first line element 22 of the circulation module 18. The heat exchanger 20 is provided for cooling the output circuit.
The recirculation module 18 includes a condenser 24. The condenser 24 is fluidically connected to the heat exchanger 20 via a second line element 26 of the feedback module 18. The first line element 22 and the second line element 26 are connected to one another in terms of flow by the heat exchanger 20. The condenser 24 is provided for separating liquid fluid, in particular liquid water, from the recirculated material that is discharged.
The circulation module 18 includes a check valve 28. The check valve 28 is fluidically connected to the condenser 24 via a third line element 30 of the circulation module 18.
The circulation module 18 includes an expansion unit 32. The expansion unit 32 is designed in the present case as an evaporator. The expansion unit 32 is fluidically connected to the non-return valve 28 via a fourth line element 34 of the circulation module 18. The check valve 28 is arranged in terms of flow between the condenser 24 and the expansion unit 32. The check valve 28 is provided to prevent fluid flow from the expansion unit 32 to the condenser 24. The check valve 28 is arranged for allowing fluid to flow from the condenser 24 to the expansion unit 32 above a certain pressure threshold in the third line element 30. The condenser 24 is geodetically arranged higher than the expansion unit 32. The expansion unit 32 is provided for expanding a fluid, in particular water. The expansion unit 32 is arranged to evaporate water. The expansion unit 32 is provided for superheating water. The expansion unit 32 is designed as a heat exchanger. For heat transfer, the expansion unit 32 is coupled to a waste gas line 36 of the fuel cell and/or electrolyser unit 12. An exhaust line 36 is provided for introducing residual heat from the exhaust gas from the fuel cell and/or electrolyser unit 12 into the expansion unit 32.
The circulation module 18 includes a jet pump 38. The ejector pump 38 is fluidically connected to the expansion unit 32. The jet pump 38 is downstream of the expansion unit 32. The ejector pump 38 is fluidically connected to the expansion unit 32 via a fifth line element 40 of the circulation module 18. The ejector pump 38 is downstream of the expansion unit 32 with respect to flow. The expansion unit 32 is arranged to provide propulsion gas for the jet pump 38. The injection pump 38 is provided for supplying the recirculated cycle material and/or the fuel gas. The jet pump 38 is designed as an injector. The ejector pump 38 is provided for generating a negative pressure for sucking in suction gas. An ejector pump 38 is provided for delivering the suction gas together with the propulsion gas.
The ejector pump 38 is fluidically connected to the condenser 24. The ejector pump 38 is fluidically connected to the condenser 24 via a sixth line element 42 of the circulation module 18. The intake region 44 of the ejector pump 38 is fluidically connected to the condenser 24.
The circulation module 18 includes a fuel gas connection element 46. A fuel gas connection element 46 is provided for supplying fresh fuel gas to the sixth line element 42. The fuel gas connection element 46 is connected to a fuel gas reservoir or in particular an external gas line 48, which is not shown in detail. The recirculation module 18 comprises a regulating valve 50, which is provided for regulating the supply of fresh fuel gas. A control valve 50 is arranged fluidically between the fuel gas connection element 46 and the jet pump 38.
The ejector pump 38 is fluidically connected to the heat exchanger 20 via a seventh line element 52 of the circulation module 18. The heat exchanger 20 is arranged to heat the circulation to be circulated. The heat exchanger 20 is provided for transferring heat from the output cycle to the cycle to be circulated and/or the fuel gas. The heat exchanger 20 is fluidically connected to the anode gas inlet 16 via an eighth line element 54 of the circulation module 18. The seventh line element 52 and the eighth line element 54 are connected to one another in terms of flow by the heat exchanger 20. The first line element 22 and the eighth line element 54 are not fluidically connected to one another by the heat exchanger 20.
A method 56 for operating the fuel cell 10 is shown in fig. 2. Fuel cell 10 is used to perform method 56. The recycle module 18 directs recycle from the anode gas outlet 14 of the fuel cell and/or electrolyzer unit 12 back to the anode gas inlet 16 of the fuel cell and/or electrolyzer unit 12. The recycle, which is designed as anode off-gas, is circulated in the circulation module 18 from the anode gas outlet 14 of the fuel cell and/or electrolyser unit 12 to the anode gas inlet 16 of the fuel cell and/or electrolyser unit 12.
In a cooling method step 58 of the method 56, the output recyclate is cooled. In the present case, the temperature of the output recycle at the anode gas outlet 14 is about 600 ℃. In the present case, the pressure of the output recycle at the anode gas outlet 14 is about 1 bar. In the present case, the temperature of the output circuit in the first line element 22 is about 600 ℃. In the present case, the pressure of the output recycle in the first line element 22 is about 1 bar. The output circuit 20 is cooled by means of a heat exchanger 20. In this case, heat exchanger 20 transfers 2300W of heat. The temperature of the output circuit in the second line element 26 is above the dew point. In the present case, the temperature of the output recyclate in the second line element 26 is about 140 ℃. In the present case, the pressure of the output recycle in the second line element 26 is about 1 bar. The pressure of the output recycle is lower than the recycle to be recycled.
In a condensation method step 60 of the method 56, a liquid fluid, in this case liquid water, is separated off from the output recycle. In the condenser 24, the output recycle is further cooled until a temperature is reached that results in a significant proportion of the water condensing. The output recycle was cooled to significantly below 100 ℃. In the recirculation module 18, liquid water is separated from the recirculated material that is discharged by means of a condenser 24. The liquid water is designed as condensate. In this case, the condenser 24 transfers approximately 2000W of heat. The liquid water flows in particular automatically into the third line element 30. The temperature of the liquid water is below the boiling point of water. In the present case, the temperature of the liquid water in the third line element 30 is about 69 ℃. In the present case, the pressure of the liquid water in the third line element 30 is about 1 bar. The output recycle is separated in a condensation method step 60 into a liquid fluid, in particular liquid water and dry recycle. The dried recycle is led to the sixth line element 42. In the present case, the temperature of the dried recyclate in the sixth line element 42 is about 69 ℃. In the present case, the pressure of the dried recycle in the sixth line element 42 is about 1 bar.
In a method step 62 of method 56, a liquid fluid, in particular liquid water, is fed to expansion unit 32. Liquid water is fed to the expansion unit 32 in at least one operating state. Liquid water is transported from the condenser 24 to the expansion unit 32 by a geodetic pressure difference without the supply of mechanical energy. The execution of the feed method step 62 depends on the amount of water in the third line element 30. Liquid water flows in batches through the check valve 28 into the expansion unit 32.
In an evaporation method step 64 of the method 56, a liquid fluid, in particular liquid water, is heated in the expansion unit 32. The expansion unit 32 is operated by the waste heat of at least one functional unit. In the present case, the functional unit is designed as a fuel cell and/or electrolyser unit 12. In the present case, the expansion unit 33 is operated by the residual heat of the fuel cell and/or the electrolysis cell unit 12, in particular the exhaust gas heat. The expansion unit 32 transfers heat from the residual heat from the fuel cell and/or the electrolyzer unit 12 to the water located in the expansion unit 32. In this case, the expansion unit 32 transfers 1800W of heat. In this case, liquid fluids, in particular liquid water, can be heated. The exhaust line 36 has a section 66 upstream of the expansion unit 32 and a section 68 downstream of the expansion unit 32. In the present case, the temperature of the exhaust gas in the upstream section 66 of the exhaust line 36 is about 236 ℃. In the present case, the pressure of the exhaust gas in the upstream region 66 of the exhaust line 36 is about 1 bar. In the present case, the temperature of the exhaust gas in the downstream section 68 of the exhaust line 36 is about 172 ℃. In the present case, the pressure of the exhaust gas in the downstream section 68 of the exhaust line 36 is about 1 bar. The exhaust gas is designed to be gaseous in both the upstream section 66 and the downstream section 68. In at least one operating state, the fluid is expanded in the circulation module 18 by means of the expansion unit 32. In this case, the fluid is water. Alternatively, however, other fluids, such as methanol, may be used as would appear suitable to those skilled in the art. In this case, in at least one operating state, water is evaporated in the circulation module 18 by means of the expansion unit 32. In this case, the water is superheated in the circulation module 18 by means of the expansion unit 32 in at least one operating state. The water superheated by means of the expansion unit 32 is designed as superheated steam in at least one operating state. In the present case, the temperature of the superheated steam in the fifth line element 40 is about 230 ℃. In the present case, the pressure of the superheated steam in the fifth line element 40 is about 4 bar. In the expansion unit 32, the liquid water is evaporated. The resulting pressure increase closes the check valve 28 and allows superheated water under pressure to enter the jet pump 38 as a propellant gas. The evaporation energy of the expansion unit 32 can be taken from the exhaust gas. In principle, it is conceivable that the evaporation energy does not lead to sufficient superheating of the vapor and that droplet formation takes place in the ejector pump 38. Such an operating action may be avoided, for example, by pulling the heat exchanger 20 above the jet pump 38 so that the vapor is sufficiently superheated before exiting from the nozzle of the jet pump 38. In principle, liquid fluids, in particular liquid water, can also be heated and expanded in the expansion unit 32 without overheating. Here, the wet vapor will enter the jet pump 38 as a propulsion gas.
No mechanical energy is consumed in the transfer of condensate, in particular from the third line element 30 to the injection pump 38. Due to the principle, the condensate is pulsed.
In a delivery method step 70 of method 56, jet pump 38 is operated. The expanded, in particular evaporated, fluid, in particular water vapor of the expansion unit 32 is used as a propellant gas for the injection pump 38 for conveying the drying cycle and/or the fuel gas in at least one operating state. The superheated steam from the expansion unit 32 is used as propulsion gas for the ejector pump 38 in at least one operating state. The propulsion gas is supplied to the ejector pump 38 by a pressure difference via a fifth line element 40. The jet pump 38 delivers dry cycle and/or fresh fuel gas. The ejector pump 38 sucks in suction gas, which is designed in particular as dry cycle and/or fuel gas. The drying cycle delivered by the ejector pump 38 at least partially forms the suction gas. In the present case, the temperature of the circuit to be circulated in the seventh line element 52 is about 110 ℃. In the present case, the pressure of the circulation to be circulated in the seventh line element 52 is approximately 1.075 bar.
In fuel gas supply method step 72, fresh fuel gas is supplied to the circulation module 18. The fresh fuel gas is supplied fluidically to the drying circuit upstream of the injection pump 38. The fuel gas is supplied to the drying circuit in the sixth line element 42. The fuel gas is supplied fluidically between the condenser 24 and the jet pump 38 to the drying circuit. The pressure is advantageously particularly low here. The fuel gas is supplied to the jet pump 38 at least temporarily. Fuel gas supply method step 72 is independent of the other method steps of the method 56. The fuel gas is a part of the suction gas. In the present case, the temperature of the fresh fuel gas in the fuel gas connection element 46 is about 45 ℃. In the present case, the pressure of the fresh fuel gas in the fuel gas connection element 46 is about 1 bar.
In a heating method step 74 of method 56, the recyclate to be recycled is heated. In at least one state, the cycle to be circulated is heated in the heat exchanger 20 by means of heat from the output cycle. In the eighth line element 54, a counter flow is guided relative to the first line element 22. The temperature of the output cycle is higher than that of the cycle to be circulated. The recyclate to be recycled contains fresh fuel gas, which is mixed with the dry recyclate. In the present case, the temperature of the circulation to be circulated in the eighth line element 54 is about 500 ℃. In the present case, the pressure of the circuit to be circulated in the eighth line element 54 is approximately 1.075 bar.
The sequence of the method steps 58, 60, 62, 64, 70, 72, 74 of the method 56 shown in fig. 2 is to be understood as meaning the sequence of the conveyed recyclates in the circulation module 18, wherein the method steps 58, 60, 62, 64, 70, 72, 74 can in principle also be carried out simultaneously and/or continuously.
In principle, it is conceivable in an alternative configuration of the fuel cell 10 according to the invention for the circulation module 18 to comprise a small pump, in particular a feed pump, which continuously feeds liquid fluid, in particular water, into the expansion unit 32, instead of the check valve 28. Thereby, pulses can advantageously be avoided. Here, a small amount of mechanical or electrical energy is required to operate the pump, which, however, has a relatively small effect on the overall efficiency of the fuel cell 10 due to the small volume of liquid water.
Furthermore, it is basically conceivable in an alternative configuration of the fuel cell 10 according to the invention for the circulation module 18 to comprise a further expansion unit (which is designed in particular as a further evaporator) and a further check valve. Here, the check valve 28 and the expansion unit 32 form a first condensate path, and the further check valve and the further expansion unit form a second condensate path. The first condensate path is designed here separately from the second condensate path. In the first condensate path and the second condensate path, the condensates are each expanded, in particular superheated, independently of one another. Here, the two expansion units or the two condensate paths can be alternated by installing suitable valves. Pulses can thereby advantageously be avoided.
In principle, other conceptual configurations of the loop module are also conceivable, which are listed in the following paragraphs. However, other configurations of these recycling modules cannot operate without a supply of mechanical energy, and therefore will reduce the overall efficiency of the fuel cell 10.
In principle, it is conceivable that an alternative circulation module comprises a cryogenic blower with an upstream heat exchanger and a downstream heat exchanger for the temporary cooling. However, a complex construction with a plurality of heat exchangers, lines and, in addition, mechanical blowers which require regular maintenance is disadvantageous here. Furthermore, it is conceivable in principle for an alternative circulation module to comprise an injection pump, in particular an "injection pump", into which fresh fuel gas is fed as propulsion gas. The necessary kinetic energy comes from the overpressure of the fuel gas fed in. The efficiency of the flow pump is disadvantageous here, in particular, because in stationary fuel cells methane from the natural gas network is generally used as an energy carrier, which, in contrast to the fuel gas from the pressure accumulator for operating the ejector pump, must be compressed, whereby additional compression energy must be provided. Furthermore, there is the option of operating with hydrogen or a mixture of hydrogen and methane in the case of stationary fuel cells. In this case, however, the operation of the ejector pump is difficult because the hydrogen density is low and only predictable pulses for accelerating the intake gas can be provided. Furthermore, it is conceivable in principle that an alternative circulation module comprises a high-temperature blower. However, the manufacture of high-temperature blowers is accompanied by considerable expenditure due to the load on the material caused by the temperature. Furthermore, the transport of hot gases is counterproductive in terms of energy, since the power required is proportional, to a first approximation, to the volume transported and therefore to the absolute temperature of the medium.

Claims (12)

1. Method (56) for operating a fuel cell (10), in particular a solid oxide fuel cell, comprising at least one fuel cell and/or electrolyser unit (12) having at least one anode, wherein a recycle designed as anode exhaust gas is recycled in at least one recycling module (18) from an anode gas outlet (14) of the fuel cell and/or electrolyser unit (12) to an anode gas inlet (16) of the fuel cell and/or electrolyser unit (12), characterized in that in at least one operating state a fluid, in particular water, is expanded, preferably evaporated, by means of at least one expansion unit (32) in the recycling module (18).
2. Method (56) according to claim 1, characterized in that a liquid fluid, in particular liquid water, is separated from the output circuit in the circuit module (18), in particular by means of a condenser (24).
3. Method (56) according to claim 1 or 2, characterized in that the expansion unit (32) is operated by the residual heat of at least one functional unit, in particular of the at least one fuel cell and/or electrolyser unit (12).
4. Method (56) according to any of the preceding claims, characterized in that the expanded, in particular evaporated, fluid from the expansion unit (32) is used in at least one operating state as a propulsion gas for an injection pump (38) which delivers dry cycle and/or fuel gas.
5. Method (56) according to one of the preceding claims, characterized in that in at least one operating state the circulation to be circulated is heated in the heat exchanger (20) by means of heat from the output circulation.
6. Fuel cell (10), in particular solid oxide fuel cell, for carrying out the method (56) according to one of the preceding claims, comprising at least one fuel cell and/or electrolyser cell (12) having at least one anode and at least one circulation module (18) for circulating a recyclate designed as anode off-gas, characterized in that the circulation module (18) comprises at least one expansion unit (32), in particular designed as an evaporator, which is provided for expanding, preferably evaporating, a fluid, in particular water.
7. Fuel cell (10) according to claim 6, characterized in that the circulation module (18) comprises at least one heat exchanger (20) arranged for transferring heat of the output recyclate to the recyclate to be circulated and/or the fuel gas.
8. Fuel cell (10) according to claim 6 or 7, characterized in that the circulation module (18) comprises at least one condenser (24) which is provided for separating a liquid fluid, in particular liquid water, from the output circulation.
9. The fuel cell (10) according to claim 8, characterized in that the condenser (24) is geodetically arranged higher than the at least one expansion unit (32).
10. The fuel cell (10) according to claim 8, characterized in that the circulation module (18) comprises at least one check valve (28) which is arranged fluid-technically between the condenser (24) and the expansion unit (32).
11. Fuel cell (10) according to one of claims 6 to 10, characterized in that the circulation module (18) comprises at least one jet pump (38) which is fluidically connected to the expansion unit (32), is located downstream of the expansion unit (32) and is provided for conveying the recirculated cycle material and/or the fuel gas.
12. Fuel cell (10) according to claim 11, characterised in that the ejector pump (38) is fluidically connected to the condenser (24).
CN202210504209.6A 2021-05-11 2022-05-10 Fuel cell and method for operating the fuel cell Pending CN115411316A (en)

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