WO2014111686A1 - Système de pile à combustible - Google Patents

Système de pile à combustible Download PDF

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Publication number
WO2014111686A1
WO2014111686A1 PCT/GB2014/050013 GB2014050013W WO2014111686A1 WO 2014111686 A1 WO2014111686 A1 WO 2014111686A1 GB 2014050013 W GB2014050013 W GB 2014050013W WO 2014111686 A1 WO2014111686 A1 WO 2014111686A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel cell
electrolyte
cell stack
heat
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2014/050013
Other languages
English (en)
Inventor
Naveed AKHTAR
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AFC Energy PLC
Original Assignee
AFC Energy PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AFC Energy PLC filed Critical AFC Energy PLC
Priority to GB1511912.6A priority Critical patent/GB2530142A/en
Publication of WO2014111686A1 publication Critical patent/WO2014111686A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M8/04007—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
    • H01M8/04029—Heat exchange using liquids
    • 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
    • H01M8/08—Fuel cells with aqueous 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
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/249—Grouping of fuel cells, e.g. stacking of fuel cells comprising two or more groupings of fuel cells, e.g. modular assemblies
    • 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
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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 present invention relates to liquid electrolyte fuel cell systems, preferably but not exclusively incorporating alkaline liquid-electrolyte fuel cells, and to methods of operating such fuel systems.
  • Fuel cells have been identified as a relatively clean and efficient source of electrical power.
  • Alkaline fuel cells with a liquid electrolyte are of particular interest because they operate at relatively low temperatures, are efficient and mechanically and electrochemically durable. Acid fuel cells and fuel cells employing other liquid electrolytes are also of interest.
  • Such fuel cells typically comprise an electrolyte chamber separated from a fuel gas chamber (containing a fuel gas, typically hydrogen) and a further gas chamber (containing an oxidant gas, usually air).
  • the electrolyte chamber is separated from the gas chambers using electrodes.
  • Typical electrodes for alkaline fuel cells comprise a conductive metal, typically nickel, that provides mechanical strength to the electrode, and the electrode also incorporates a catalyst coating which may comprise activated carbon and a catalyst metal, typically platinum.
  • the fuel cell system of the present invention addresses or mitigates one or more problems of the prior art.
  • a liquid electrolyte fuel cell system comprising at least two fuel cell stacks, each fuel cell stack comprising a plurality of fuel cells, each fuel cell comprising a liquid electrolyte chamber between opposed electrodes, the electrodes being an anode and a cathode; the fuel cell stacks comprising at least one first fuel cell stack arranged to operate at an elevated temperature, and at least one second fuel cell stack arranged to operate at a temperature below the elevated temperature; and the system comprising a heat exchanger to transfer heat from at least one first fuel cell stack to at least one second fuel cell stack.
  • a first electrolyte may be recirculated through at least one first fuel cell stack, and a second electrolyte may be circulated through at least one second fuel cell stack, and the heat exchanger may be arranged to exchange heat between the first electrolyte and the second electrolyte.
  • the heat exchanger may be arranged to exchange heat between the first electrolyte after it has passed through the first fuel cell stack, and the second electrolyte as it is passed towards the second fuel cell stack.
  • the invention provides a method of operating a liquid electrolyte fuel cell system comprising at least two fuel cell stacks, the method comprising operating at least one first fuel cell stack at an elevated temperature, and operating at least one second fuel cell stack at a temperature below the elevated temperature, and transferring heat from at least one first fuel cell stack to at least one second fuel cell stack.
  • the elevated temperature at which each first fuel cell stack operates may be between 50 °C and 90 °C, more preferably between 60°C and 70°C; the lower temperature, at which each second fuel cell stack operates, may be between 25 °C and 50 °C, for example between 30 °C and 50 °C, or about 40 °C.
  • the electrolyte or the stack is generally cooled by circulating a coolant fluid such as air or water, and the heat is dissipated into the environment, or may be utilised for domestic heating or other purposes.
  • a coolant fluid such as air or water
  • the present invention enables at least some of the excess heat to be utilised to improve the total efficiency of the system, in generating additional electrical power.
  • Figure 1 shows a schematic diagram of the fluid flows supplied to a fuel cell stack to which the invention would be applicable;
  • Figure 2 shows a schematic diagram of the fluid flows of a fuel cell system incorporating fuel cell stacks as described in relation to figure 1 ;
  • a fuel cell system 10 includes a fuel cell stack 20 (represented schematically), which uses an aqueous solution of potassium hydroxide as electrolyte 12, for example at a concentration of 6 moles/litre.
  • the fuel cell stack 20 is supplied with hydrogen gas as fuel, air as oxidant, and electrolyte 12.
  • Hydrogen gas is supplied to the fuel cell stack 20 from a hydrogen storage cylinder 22 through a regulator 24 and a control valve 26, and an exhaust gas stream emerges through a first gas outlet duct 28.
  • Air is supplied by a blower 30, and any C0 2 is removed by passing the air through a scrubber 32 and a filter 34 before the air flows through a duct 36 to the fuel cell stack 20, and spent air emerges through a second gas outlet duct 38.
  • the fuel cell stack 20 is represented schematically, as its detailed structure is not the subject of the present invention, but in this example it consists of a stack of fuel cells, each fuel cell comprising a liquid electrolyte chamber between opposed electrodes, the electrodes being an anode and a cathode. In each cell, air flows through a gas chamber adjacent to the cathode, to emerge as the spent air. Similarly, in each cell, hydrogen flows through a gas chamber adjacent to the anode, and emerges as the exhaust gas stream.
  • a fuel cell may use a different source of oxygen, instead of air; and may use a different source of fuel, other than hydrogen.
  • Operation of the fuel cell stack 20 generates electricity, and heat, and also generates water by virtue of the chemical reactions described above.
  • water evaporates in both the anode and cathode gas chambers so both the exhaust gas stream and the spent air contain water vapour.
  • the rate of evaporation depends on the electrode surface area exposed to reactant gases, the flow rate of the reactant gases, and the operating temperature. It also depends on the partial pressure of water vapour in the anode and cathode gas chambers.
  • the overall result would be a steady loss of water from the electrolyte 12; the loss of water can be prevented by condensing water vapour from the spent air in the outlet duct 38 (or from the exhaust gas), for example by providing a condenser 39.
  • the chemical reaction occurring at the cathode generates hydroxyl ions and consumes water, so concentrating the electrolyte in the vicinity of the cathode.
  • the electrolyte 12 is stored in an electrolyte storage tank 40 provided with a vent 41 .
  • a pump 42 circulates electrolyte from the storage tank 40 into a header tank 44 provided with a vent 45, the header tank 44 having an overflow pipe 46 so that electrolyte returns to the storage tank 40. This ensures that the level of electrolyte in the header tank 44 is constant.
  • the electrolyte is supplied at constant pressure through a duct 47 to the fuel cell stack 20; and spent electrolyte returns to the storage tank 40 through a return duct 48.
  • the storage tank 40 includes a heat exchanger 49 to remove excess heat.
  • the air stream passes through a heat exchanger 50, and then a humidification chamber 52.
  • An aqueous liquid such as distilled water is supplied through a duct 53 to the humidification chamber 52; the excess water emerging from the
  • humidification chamber 52 is discharged through a duct 55 to waste.
  • the water supplied through the duct 53 is preferably at an elevated temperature, for example it may be heated by heat exchange with the electrolyte in the return duct 48. This will ensure that it is at a temperature only a few degrees lower than the operating temperature of the fuel cell stack 20.
  • the water may be passed through a heat exchanger (not shown) to exchange heat with the spent electrolyte in the return duct, before being supplied through the duct 53.
  • the humidification chamber 52 may be sufficiently warm that no separate heat exchanger 50 is required: the humidification chamber 52 both heats and humidifies the air stream at the same time, by direct contact with water.
  • a fuel cell system 10 might include a plurality of fuel cell stacks 20 supplied with the electrolyte in parallel, and with a common recirculation system for the electrolyte.
  • the electrolyte 12 would be maintained at an elevated temperature between 60 °C and 70 °C during operation.
  • the internal electrical resistance of the fuel cells decreases with temperature, so operation at such an elevated temperature reduces the internal resistance, and so increases the power output of the fuel cell stack 20.
  • it may therefore be necessary to provide an external source of heat for example by supplying a hot liquid to the heat exchanger 49, so as to raise the temperature of the electrolyte 12 to the desired operating value.
  • a fuel cell system 60 of the present invention incorporates at least two fuel cell systems 10: a first fuel cell system 10a operates as described above, at an operating temperature of between 60° and 70°C; and a second fuel cell system 10b operates at a lower operating temperature, which may be between 30° and 50°C.
  • FIG. 1 Components within the first and second fuel cell systems 10a and 10b which are the same as components described in relation to figure 1 , are referred to by the same reference numerals, but distinguished by the suffixes a and b respectively; figure 2 is a schematic representation, and does not shown all the features that were shown in figure 1 .
  • each fuel cell system 10a or 10b includes a fuel cell stack 20a or 20b, to which hydrogen is supplied from a storage cylinder 22a or 22b, air is supplied by a blower 30a or 30b, and electrolyte 12a or 12b is supplied from a header tank 44a or 44b which is fed from a storage tank 40a or 40b by a pump 42a or 42b; and spent electrolyte returns to the storage tank 40a or 40b through a return duct 48a or 48b.
  • the fuel cell system 60 includes a heat exchanger 62 to enable heat transfer between spent electrolyte 12a in the return duct 48a, and electrolyte 12b as it is flowing to the header tank 44b.
  • the first fuel cell system 10a is operated as described above. Initially, starting at ambient temperature the electrolyte is heated up using the heat exchanger 49a, such that the electrolyte 12a is at an operating temperature between 60 °C and 70 °C. During operation it is not necessary to remove heat from the electrolyte 12a using the heat exchanger 49a, as the excess heat is removed by the heat exchanger 62.
  • the second fuel cell system 10b uses the heat from the heat exchanger 62 to raise the temperature of the electrolyte 12b from ambient temperature to an operating temperature which may be 35°C or 40 °C.
  • the fuel cell system 60 enables a larger number of fuel cell systems 10 to be operated, without requiring an external source of heat to heat the electrolyte for each fuel cell system 10.
  • the external source of heat is used only to heat up the electrolyte 12a in each fuel cell system 10a that is arranged to operate at the elevated temperature.
  • the waste heat from the fuel cell systems 10a that operate at an elevated temperature is then used to heat the electrolyte for additional fuel cell systems 10b operating at a lower temperature that is nevertheless above ambient temperature.
  • each fuel cell system 10b that is operating at such a lower temperature will be less than it would have output at the elevated temperature, nevertheless the system 60 produces a greater electrical output, because it combines the output from the elevated temperature fuel cell systems 10a with that from the lower temperature fuel cell systems 10b.
  • the waste heat from the fuel cell system 10b that operates at a lower temperature may be removed using the heat exchanger 49b, and may be used as a source of low-temperature heat, for example for domestic heating.
  • fuel cell failures are more likely to occur in a fuel cell stack 20a operating at an elevated temperature than in a fuel cell stack 20b operating at a lower temperature.
  • fuel cells operating at 70 °C were found to operate on average for only 6 weeks before a pronounced degradation was observed, whereas identical fuel cells operating at 32 °C have been found to operate for over 24 weeks without any major degradation.
  • a significant reason for this difference is that evaporation of water from the electrolyte occurs much more rapidly at the elevated temperature of 70°C than at the lower temperature of 32 q C.
  • the system 60 is described as exchanging heat between spent electrolyte 12a in the return duct 48a, and the electrolyte being supplied between the pump 42b and the header tank 44b, by means of the heat exchanger 62, it will be appreciated that the exchange of heat may be brought about differently.
  • the storage tank 40b may be provided with an additional heat exchanger 64, and the heat exchanger 62 omitted, with the electrolyte return duct 48a communicating via the heat exchanger 64 with the storage tank 40a, and the pump 42b communicating directly with the header tank 44b.
  • These alternative connections 66 and 67 are indicated by broken lines in figure 2. In this case the electrolyte 12b is therefore heated in the storage tank 40b.
  • a fuel cell system 70 represents an alternative modification of the fuel cell system 60. As with the fuel cell system 60, it incorporates at least two fuel cell systems 10: a first fuel cell system 10a operates as described above, at an operating temperature of between 60° and 70 q C; and a second fuel cell system 10b operates at a lower operating temperature, which may be between 30° and 50°C.
  • FIG. 1 Components within the first and second fuel cell systems 10a and 10b which are the same as components described in relation to figure 1 , are referred to by the same reference numerals, but distinguished by the suffixes a and b respectively; figure 3 is a schematic representation, and does not shown all the features that were shown in figure 1 .
  • the return electrolyte duct 48a returns the used electrolyte directly to the electrolyte storage tank 40a.
  • the electrolyte pump 42b is arranged to pass the electrolyte 12b through the heat exchanger 49a of the electrolyte storage tank 40a, via three-way valves 71 , before it flows into the header tank 44b.
  • the three-way valves 71 are arranged to supply hot fluid to the heat exchanger 49a, and so to heat up the electrolyte 12a.
  • the electrolyte pump 42b is started up and the three-way valves 71 are switched so the electrolyte 12b flows through the heat exchanger 49a and so takes heat out of the storage tank 40a.
  • the heat generated in the first fuel cell system 10a is used to maintain the temperature of the second fuel cell system 10b.
  • the excess heat generated in the second fuel cell system 10b may be removed using the heat exchanger 49b, and may be used as a source of low-temperature heat, for example for domestic heating.

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

Abstract

L'invention concerne un système (60) de pile à combustible à électrolyte liquide, qui comprend au moins deux empilements (20a, 20b) de piles à combustible, chacun comprenant une pluralité de piles à combustible, chaque pile à combustible comprenant une chambre d'électrolyte liquide entre des électrodes opposées, les électrodes étant constituées d'une anode et d'une cathode. Au moins un empilement (20a) de piles à combustible est agencé pour fonctionner à une température élevée, telle que 65 °C et au moins un empilement (20b) de piles à combustible est agencé pour fonctionner à une température inférieure à la température élevée, telle que 35 °C. Le système (60) comprend un échangeur thermique (62 ; 64) afin de transférer la chaleur depuis au moins un empilement (20a) de piles à combustible à température élevée vers au moins un empilement (20b) de piles à combustible à température inférieure. Cela peut être réalisé par l'échange thermique entre les électrolytes respectifs.
PCT/GB2014/050013 2013-01-18 2014-01-03 Système de pile à combustible Ceased WO2014111686A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB1511912.6A GB2530142A (en) 2013-01-18 2014-01-03 Fuel cell system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1300906.3 2013-01-18
GBGB1300906.3A GB201300906D0 (en) 2013-01-18 2013-01-18 Fuel cell system

Publications (1)

Publication Number Publication Date
WO2014111686A1 true WO2014111686A1 (fr) 2014-07-24

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PCT/GB2014/050013 Ceased WO2014111686A1 (fr) 2013-01-18 2014-01-03 Système de pile à combustible

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GB (2) GB201300906D0 (fr)
WO (1) WO2014111686A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3075480A1 (fr) * 2017-12-20 2019-06-21 Commissariat A L'energie Atomique Et Aux Energies Alternatives Systeme de generation d'electricite incluant deux piles a combustible a temperatures de fonctionnement differentes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843410A (en) * 1972-03-27 1974-10-22 Varta Ag Fuel cell power station
US6294278B1 (en) * 1998-12-12 2001-09-25 General Motors Corporation Combination of low and high temperature fuel cell device
JP2006294402A (ja) * 2005-04-11 2006-10-26 Toyota Motor Corp 燃料電池システム
US20100003545A1 (en) * 2008-07-07 2010-01-07 Enervault Corporation Redox Flow Battery System for Distributed Energy Storage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843410A (en) * 1972-03-27 1974-10-22 Varta Ag Fuel cell power station
US6294278B1 (en) * 1998-12-12 2001-09-25 General Motors Corporation Combination of low and high temperature fuel cell device
JP2006294402A (ja) * 2005-04-11 2006-10-26 Toyota Motor Corp 燃料電池システム
US20100003545A1 (en) * 2008-07-07 2010-01-07 Enervault Corporation Redox Flow Battery System for Distributed Energy Storage

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BIDAULT F ET AL: "Review of gas diffusion cathodes for alkaline fuel cells", JOURNAL OF POWER SOURCES, ELSEVIER SA, CH, vol. 187, no. 1, 1 February 2009 (2009-02-01), pages 39 - 48, XP025866068, ISSN: 0378-7753, [retrieved on 20081105], DOI: 10.1016/J.JPOWSOUR.2008.10.106 *
K. TOMANTSCHGER ET AL: "Development of low cost alkaline fuel cells", JOURNAL OF POWER SOURCES, vol. 18, no. 4, 1 November 1986 (1986-11-01), pages 317 - 335, XP055110978, ISSN: 0378-7753, DOI: 10.1016/0378-7753(86)80089-1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3075480A1 (fr) * 2017-12-20 2019-06-21 Commissariat A L'energie Atomique Et Aux Energies Alternatives Systeme de generation d'electricite incluant deux piles a combustible a temperatures de fonctionnement differentes
EP3503276A1 (fr) * 2017-12-20 2019-06-26 Commissariat à l'Énergie Atomique et aux Énergies Alternatives Système de génération d'électricité incluant deux piles à combustible à temperatures de fonctionnement differentes

Also Published As

Publication number Publication date
GB201300906D0 (en) 2013-03-06
GB2530142A (en) 2016-03-16
GB201511912D0 (en) 2015-08-19

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